Fungicidal halomethyl ketones and hydrates and their mixtures
Patent Information
- Application Number
- MDE20230081T
- Authority / Receiving Office
- MD · MD
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2020-03-18
- Filing Date
- 2021-03-11
- Publication Date
- 2023-02-28
AI Technical Summary
Current fungicides for controlling plant diseases caused by fungal pathogens are often ineffective, costly, toxic, and may develop resistance, necessitating the need for new compounds and combinations that are environmentally safer and have different modes of action to broaden spectrum control and retard resistance development.
A fungicidal composition comprising halomethyl ketone and hydrate derivatives, including specific compounds of Formula 1 and their stereoisomers, oxides, salts, and mixtures with additional fungicidal compounds, applied to plants or seeds to control fungal diseases effectively.
The composition provides effective control of plant diseases by offering a safer, more environmentally friendly option with potential synergistic effects, reducing the risk of resistance development and improving crop yield and vigor.
Abstract
Description
[0001] TITLE
[0002] FUNGICIDAL HALOMETHYL KETONES AND HYDRATES AND THEIR MIXTURES
[0003] FIELD OF THE INVENTION
[0004] This invention relates to certain halomethyl ketone and hydrate derivatives, their A-oxidcs and salts, and to mixtures and compositions comprising such halomethyl ketone and hydrate derivatives and methods for using such derivatives and their mixtures and compositions as fungicides.
[0005] BACKGROUND OF THE INVENTION
[0006] The control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. In addition to often being highly destructive, plant diseases can be difficult to control and may develop resistance to commercial fungicides. Many products are commercially available for these purposes, but the need continues for new fungicidal compounds which are more effective, less costly, less toxic, environmentally safer or have different sites of action. Besides introduction of new fungicides, combinations of fungicides are often used to facilitate disease control, to broaden spectrum of control and to retard resistance development. Furthermore, certain rare combinations of fungicides demonstrate a greater-than-additive (i.e. synergistic) effect to provide commercially important levels of plant disease control. The advantages of particular fungicide combinations are recognized in the art to vary, depending on such factors as the particular plant species and plant disease to be treated, and whether the plants are treated before or after infection with the fungal plant pathogen. Accordingly new advantageous combinations are needed to provide a variety of options to best satisfy particular plant disease control needs. Such combinations have now been discovered.
[0007] SUMMARY OF THE INVENTION
[0008] This invention relates to a fungicidal composition (i.e. combination, mixture) comprising
[0009] (a) at least one compound selected from the compounds of Formula 1 (including all stereoisomers), tautomers, A-oxidcs, and salts thereof,
[0010] 1 wherein T is selected from the group consisting of: wherein the bond extending to the left is attached to A;
[0011] R1is CF3, CHF2, CC13, CHC12, CF2C1, CFC12or CHFC1;
[0012] W is O, S or NR3;
[0013] R3is H, cyano, nitro, C(=0)0H, benzyl, C4-C4alkyl, C2-C4alkylcarbonyl, C2-C4haloalkylcarbonyl, OR3aor NR3bR3c;
[0014] R3ais H, benzyl, C4-C4alkyl, C2-C4alkylcarbonyl or C2-C4haloalkylcarbonyl;
[0015] R3bis H, C4-C4alkyl, C2-C4alkylcarbonyl or C2-C4haloalkylcarbonyl;
[0016] R3Cis H or C4-C4alkyl; or
[0017] R3band R3care taken together to form a 4- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups;
[0018] X is O, S or NR5a;
[0019] Y is O, S or NR5b;
[0020] R5aand R5bare each independently H, hydroxy or C4-C4alkyl;
[0021] R2aand R2bare each independently H, C4-C4alkyl, C2-C4alkenyl, C3-C|5 trialkylsilyl, C3-C15halotrialkylsilyl, (CR4aR4b)p-OH, (CR4aR4b)p-SH, (CR4aR4b)p-Cl or (CR4aR4b)p-Br; or
[0022] R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5- to 7-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 2 carbon atom ring members are independently selected from C(=0) and C(=S), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, C|-C2alkyl, C|-C2haloalkyl, C|-C2alkoxy and C|-C2haloalkoxy on carbon atom ring members;
[0023] R2Cis C4-C4alkyl, C4-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl or trifluoromethylsulfonyl, each optionally substituted with up 2 substituents independently selected from cyano, hydroxy, SCºN and C|-C2alkoxy; R2dis H, cyano, halogen or C1-C4 alkyl; each R4aand R4bis independently H or C4-C4 alkyl; p is 2 or 3; when T is T-l or T-2, then A is A1-A2-CR6aR6b, wherein A1is connected to J, and CR6aR6bis connected to T; when T is T-3, then A is A!-A2, wherein A1is connected to J, and A2is connected to T; A1is CR6cR6d, N(R7a), O or S;
[0024] A2is a direct bond, CR6eR6f, N(R7b), O or S;
[0025] R6a, R6b, R6c, R6d, R6eand R6fare each independently H, cyano, hydroxy, halogen, C(=0)0CH3or CrC4alkyl;
[0026] R7aand R7bare each independently H, C(=0)H, cyano, C|-C4alkyl or C2-C4 alkylcarbonyl;
[0027] J is selected from the group consisting of:
[0028] J-13 J- 14 wherein the bond extending to the left is attached to L, and the bond extending to the right is attached to A; each R8is independently F, Cl, I, Br, cyano, methyl, trifluoromethyl or methoxy; q is 0, 1, 2, 3 or 4;
[0029] L is (CR9aR9b)n; each R9aand R9bis independently H, halogen, cyano, hydroxy, nitro, C1-C3 alkyl, C3-C3 haloalkyl, C3-C3 alkoxy or C3-C3 haloalkoxy; haloalkyl; or
[0030] E1is amino, cyano, hydroxy, nitro, CH(=0), C(=0)OH, C(=0)NH2, C(=S)NH2, OC(=0)NH2, OC(=S)NH2, NHC(=0)NH2, NHC(=S)NH2, SCºN, -CH=NNHC(=0)OCrC6alkyl or -N(0CH3)C(=0)CrC6alkyl; or E1is C^-C^ alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C|-C^ alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C|-C^ alkylsulfinyl, C2-C6 alkenylsulfinyl, C2-C6 alkynylsulfinyl, C^-C^ alkylsulfonyl, C2-C6 alkenylsulfonyl, C2-C6 alkynylsulfonyl, C^-C^ alkylsulfonylamino, C2-C6 alkenylsulfonylamino, C2-C6 alkynylsulfonylamino, C|-C^ alkylaminosulfonyl, C2-C6 dialkylaminosulfonyl, C2-C6 alkenylaminosulfonyl, C2-C6 alkynylaminosulfonyl, C^-C^ alkylaminosulfonylamino, C2-C6 alkenylaminosulfonylamino, C2-C6 alkynylaminosulfonylamino, C2-C6 alkylcarbonyl, CyC^ alkenylcarbonyl, CyC^ alkynylcarbonyl, C2-C6 alkylaminocarbonyl, CyC^ alkenylaminocarbonyl, CyC^ alkynylaminocarbonyl, C2-C6 alkylcarbonylamino, CyC^ alkenylcarbonylamino, CyC^ alkynylcarbonylamino, C2-C6 alkylaminocarbonylamino, CyC^ alkenylaminocarbonylamino, CyC^ alkynylaminocarbonylamino, C2-C6 alkylcarbonyloxy, CyC^ alkenylcarbonyloxy, CyC^ alkynylcarbonyloxy, C2-C6 alkoxycarbonyl, CyC^ alkenyloxycarbonyl, CyC^ alkynyloxycarbonyl, C2-C6 alkylaminocarbonyloxy, CyC^ alkenylaminocarbonyloxy, CyC^ alkynylaminocarbonyloxy, C2-C6 alkoxycarbonylamino, CyC^ alkenyloxycarbonylamino, CyC^ alkynyloxycarbonylamino, C2-C6 alkylamino(thiocarbonyl)oxy, CyC^ alkenylamino(thiocarbonyl)oxy, CyC^ alkynylamino(thiocarbonyl)oxy, C2-C6 alkoxy(thiocarbonyl)amino, CyC^ alkenyloxy(thiocarbonyl)amino, CyC^ alkynyloxy(thiocarbonyl)amino, C2-C6 alkyl(thiocarbonyl), C2-C6 (alkylthio)carbonyl, CyC^ alkenyl(thiocarbonyl), CyC^ (alkenylthio)carbonyl, CyC^ alkynyl(thiocarbonyl), CyC^ (alkynylthio)carbonyl, C2-C6 alkylamino(thiocarbonyl), CyC^ alkenylamino(thiocarbonyl), CyC^ alkynylamino(thiocarbonyl), C2-C6 alkyl(thiocarbonyl)amino, C2-C6 (alkylthio)carbonylamino, C^-C^ alkenyl(thiocarbonyl)amino, C^-C^ (alkenylthio)carbonylamino, CyC^ alkynyl(thiocarbonyl)amino, CyC^ (alkynylthio)carbonylamino, alkylamino(thiocarbonyl)amino, CyC^ alkenylamino(thiocarbonyl)amino or CyC^ alkynylamino(thiocarbonyl)amino, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b;
[0031] RlOa jsphenyl optionally substituted with up to 3 substituents independently selected from Rlla; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon atom ring members are independently selected from C(=0) and C(=S), and sulfur atom ring members are independently S(=0)u(=NR12)v, each ring optionally substituted with up to 3 substituents independently selected from Rllaon carbon atom ring members and Rl lbon nitrogen atom ring members; each R10bis independently amino, cyano, halogen, hydroxy, nitro, SCºN, -SH, C4-C4alkyl, C4-C4haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C4alkoxy,
[0032] C4-C4haloalkoxy, C4-C4alkylthio, C4-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, C1-C4alkylamino, C2-C4dialkylamino, C2-C4alkylcarbonyl, C2-C4haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C2-C5 haloalkoxycarbonyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl; each Rl lais independently halogen, hydroxy, cyano, amino, nitro, C4-C4alkyl, C4-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C4hydroxyalkyl, CyC^ cycloalkyl, C4-C7cycloalkylalkyl, C1-C4alkoxy, C4-C4haloalkoxy, C2-C4alkenyloxy, C2-C4alkynyloxy, C2-C4alkoxyalkyl, C2-C6 alkylcarbonyloxy, C4-C4alkylthio, C1-C4haloalkylthio, C2-C6 alkylcarbonylthio, C1-C4alkylsulfinyl, C1-C4haloalkylsulfinyl, C4-C4alkylsulfonyl, C4-C4haloalkylsulfonyl, alkylsulfonyloxy, alkylamino, C2-Cg dialkylamino, CyC^ cycloalkylamino, C2-C4alkylcarbonyl, C3-C5 alkenylcarbonyl, C3-C5 alkynylcarbonyl, C4-C7cycloalkylcarbonyl, C5-Cg cycloalkylalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C7alkenyloxycarbonyl, C3-C7alkynyloxycarbonyl, C4-C7cycloalkoxylcarbonyl, C5-Cg cycloalkylalkoxylcarbonyl, C2-C6 alkylaminocarbonyl, CyC^ alkenylaminocarbonyl, CyC^ alkynylaminocarbonyl, C4-C7cycloalkylaminocarbonyl, C5-Cg cycloalkylalkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or CyC^ trialkylsilyl; each Rl lbis independently C(=0)H, C|-C3 alkyl, C|-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl; each R12is independently H, cyano, C1-C3 alkyl or C|-C3 haloalkyl; each u and v are independently 0, 1 or 2, provided that the sum of u and v are 0, 1 or 2;
[0033] E2is G-Z, wherein Z is attached to L;
[0034] G is phenyl optionally substituted with up to 3 substituents independently selected from R13; or
[0035] G is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R13; or
[0036] G is a 3- to 7-membered nonaromatic ring or an 8- to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=0), C(=S), S(=0) and S(=0)2, each ring or ring system optionally substituted with up to 3 substituents independently selected from R13; each R13is independently cyano, halogen, hydroxy, nitro, -SH, SF5, CH(=0), C(=0)OH, C(=S)NR14aR14b, alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C7cycloalkyl, C3-C7cycloalkenyl, C|-Cf, alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7cycloalkoxy, C^-Cg alkylthio, C|-Cf, alkylsulfinyl, C^-Cg alkylsulfonyl, C^-Cg alkylaminosulfinyl, C2-C6 dialkylaminosulfinyl, C^-Cg alkylsulfonyloxy, C^-Cg alkylsulfonylamino, C2-C6 alkylcarbonyl, C4-C7cycloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7cycloalkoxycarbonyl, yCf alkoxycarbonylcarbonyl, C2-C6 alkylcarbonyloxy, C4-C7cycloalkylcarbonyloxy, C2-C6 alkoxycarbonyloxy, C4-C7cycloalkoxycarbonyloxy, C2-C6 alkylaminocarbonyloxy, C4-C7cycloalkylaminocarbonyloxy, C2-C6 alkylcarbonylamino, C4-C7cycloalkylcarbonylamino, C2-C6 alkoxycarbonylamino, C4-C7cycloalkoxycarbonylamino, C2-C6 alkylaminocarbonylamino, C4-C7cycloalkylaminocarbonylamino or C2-C6 dialkoxyphosphinyl, each optionally substituted with up to 3 substituents independently selected from R19; each R14ais independently H, cyano, hydroxy, C|-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C|-C5 alkoxy, C2-C4 alkoxy alkyl, C4-C4alkylsulfonyl, C4-C4haloalkylsulfonyl, C2-C4alkylthioalkyl, C2-C4alkylsulfinylalkyl, C2-C4alkylsulfonylalkyl, C2-C4alkylcarbonyl, C2-C4haloalkylcarbonyl, C4-C7cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl; each R14bis independently H, C^-C^ alkyl, C^-C^ haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, alkynyl, haloalkynyl, C|-C^ hydroxy alkyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C4-C IQalkylcycloalkyl, C4-C IQcycloalkylalkyl, C4-C10 halocycloalkylalkyl, CQ-C14cycloalky lcycloalkyl, C5-C IQalkylcycloalkylalkyl, C2-C6 alkoxyalkyl, C2-CQhaloalkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-CQalkylthioalkyl, C2-CQalkylsulfinylalkyl, C2-CQalkylsulfonylalkyl, C2-CQalkylaminoalkyl, C2-CQhaloalkylaminoalkyl, C3-C8 dialkylaminoalkyl or C4-C1Qcycloalkylaminoalkyl, each optionally substituted with up to 1 substituent selected from cyano, hydroxy, nitro, C2-C4alkylcarbonyl, C2-C4alkoxycarbonyl, C3-C45 trialkylsilyl, C3-C15 halotrialkylsilyl and pyrimidinyl; or R14aand R14bare taken together to form a 4- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 3 substituents independently selected from halogen and C4-C3 alkyl; each R15is independently H, cyano, halogen, methyl, methoxy, methylthio or methoxycarbonyl; each R16is independently hydroxy or NR20aR20b; or C4-C4alkoxy, C2-C4alkenyloxy, C2-C4alkynyloxy, C2-C4alkylcarbonyloxy, C2-C5 alkoxycarbonyloxy, C2-C5 alkylaminocarbonyloxy or C3-C5 dialkylaminocarbonyloxy, each optionally substituted with up to 1 substituent selected from cyano, halogen, hydroxy and C(=0)OH; each R17is independently H, methyl, methoxy or methylthio; each R18aand R18bis independently H or C4-C4alkyl; or
[0037] R18aand R18bare taken together to form a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups; each R19is independently amino, cyano, halogen, hydroxy, nitro, -SH, C4-C4alkyl, C4-C4haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C4alkoxy, C4-C4haloalkoxy, C2-C4alkoxyalkoxy, C1-C4alkylthio, C4-C4alkylsulfinyl, C1-C4alkylsulfonyl, C4-C4haloalkylsulfonyl, C2-C4alkylcarbonyl, C2-C4haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C|-C^ alkylamino, C2-C6 dialkylamino, C2-C5 alkylaminocarbonyl, C3-C5 dialkylaminocarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C15 trialkylsily, C3-C15halotrialkylsilyl, C(R21)=NOR22or C(R23)=NR24; each U is independently a direct bond, C(=0)0, C(=0)N(R25) or C(=S)N(R26), wherein the atom to the left is connected to G, and the atom to the right is connected to V ; each V is independently a direct bond; or C|-C^ alkylene, C2-C6 alkenylene, CyC^ alkynylene, CyC^ cycloalkylene or CyC^ cycloalkenylene, wherein up to 1 carbon atom is C(=0), each optionally substituted with up to 3 substituents independently selected from halogen, cyano, nitro, hydroxy, C4-C2alkyl, C4-C2haloalkyl, C4-C2alkoxy and C4-C2haloalkoxy; each Q is independently phenyl or phenoxy, each optionally substituted with up to 2 substituents independently selected from R27; or each Q is independently a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R27; or each Q is independently a 3- to 7-membered nonaromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=0), C(=S), S(=0) and S(=0)2, each ring optionally substituted with up to 2 substituents independently selected from R27; each R20ajsindependently H, C4-C4alkyl or C2-C4alkylcarbonyl; each R20bjsindependently H, cyano, C|-C5 alkyl, C2-C5 alkylcarbonyl, C2-C5 haloalkylcarbonyl, C4-C7cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl; or R20aand R20barc taken together to form a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups; each R21and R23is independently H, cyano, halogen, C|-C3 alkyl, C|-C3 haloalkyl,
[0038] CyC^ cycloalkyl or C|-C3 alkoxy; or phenyl optionally substituted with up to 2 substituents independently selected from halogen and C1-C3 alkyl; each R22is independently H, C3-C5 alkyl, C3-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C5 alkylcarbonyl or C2-C5 alkoxycarbonyl; or each R22is phenyl optionally substituted with up to 2 substituents independently selected halogen and C3-C3 alkyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 substituents independently selected from halogen and C3-C3 alkyl; each R24is independently H, cyano, C3-C3 alkyl, C3-C3 haloalkyl, C3-C4alkoxy, C2-C4alkylcarbonyl or C2-C4alkoxycarbonyl; each R25and R26is independently H, cyano, hydroxy, C4-C4alkyl, C4-C4haloalkyl, C2-C4alkylcarbonyl, C2-C4haloalkylcarbonyl, C2-C4alkoxycarbonyl or C2-C4haloalkoxycarbonyl; each R27is independently halogen, cyano, hydroxy, nitro, C4-C4alkyl, C4-C4haloalkyl, C2-C4alkenyl, C4-C4alkoxy, C2-C4alkylcarbonyl or C2-C4alkoxycarbonyl;
[0039] Z is a direct bond, O, S(=0)m, N(R28), C(=0), C(=0)0, C(=0)N(R28), NR28C(=0), N(R28)C(=0)N(R28), N(R28)C(=S)N(R28), 0C(=0)N(R28), N(R28)C(=0)0, S(0)2N(R28), N(R28)S(=0)2or N(R28)S(0)2N(R28), wherein the atom to the right is connected to L; each R28is independently H, C4-C3 alkyl, C3-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl; and m is 0, 1 or 2; and
[0040] (b) at least one additional fungicidal compound; provided that:
[0041] (a) when A1is N(R7a), O or S, then A2is a direct bond or CR6eR6f; and
[0042] (b) when A2is N(R7b), O or S; then A1is CR6cR6d.
[0043] This invention also relates to a composition comprising: (a) at least one compound selected from the compounds of Formula 1 described above, / V-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.
[0044] This invention also relates to a composition comprising one of the aforesaid compositions comprising component (a) and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
[0045] This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of one of the aforesaid compositions.
[0046] The aforedescribed method can also be described as a method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of one of the aforesaid compositions to the plant (or portion thereof) or plant seed (directly or through the environment (e.g., growing medium) of the plant or plant seed).
[0047] This invention also relates to a compound of Formula 1 described above, a tautomer, an A-oxidc or salt thereof.
[0048] DETAILS OF THE INVENTION
[0049] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.
[0050] The transitional phrase “consisting of’ excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
[0051] The transitional phrase “consisting essentially of’ is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of’.
[0052] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of’ or “consisting of.”
[0053] Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[0054] Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
[0055] The term “agronomic” refers to the production of field crops such as for food and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).
[0056] The term “nonagronomic” refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
[0057] The term “crop vigor” refers to rate of growth or biomass accumulation of a crop plant. An “increase in vigor” refers to an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant. The term “crop yield” refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant. An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.
[0058] The term “biologically effective amount” refers to the amount of a biologically active compound (e.g., a compound of Formula 1 or a mixture with at least one other fungicidal compound) sufficient to produce the desired biological effect when applied to (i.e. contacted with) a fungus to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the fungal disease or for other desired effect (e.g., increasing plant vigor). As referred to in the present disclosure and claims, “plant” includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds). Portions of plants include geotropic members typically growing beneath the surface of the growing medium (e.g., soil), such as roots, tubers, bulbs and corms, and also members growing above the growing medium, such as foliage (including stems and leaves), flowers, fruits and seeds.
[0059] As referred to herein, the term “seedling”, used either alone or in a combination of words means a young plant developing from the embryo of a seed.
[0060] As referred to herein, the term “broadleaf ’ used either alone or in words such as “broadleaf crop” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.
[0061] As referred to in this disclosure, the terms “fungal pathogen” and “fungal plant pathogen” include pathogens in the Ascomycota, Basidiomycota and Zygomycota phyla, and the fungal-like Oomycota class that are the causal agents of a broad spectrum of plant diseases of economic importance, affecting ornamental, turf, vegetable, field, cereal and fruit crops. In the context of this disclosure, “protecting a plant from disease” or “control of a plant disease” includes preventative action (interruption of the fungal cycle of infection, colonization, symptom development and spore production) and / or curative action (inhibition of colonization of plant host tissues).
[0062] As used herein, the term “mode of action” (MO A) is as define by the Fungicide Resistance Action Committee (FRAC), and is used to distinguish fungicides according to their biochemical mode of action in the biosynthetic pathways of plant pathogens, and their resistance risk. FRAC-defined modes of actions include (A) nucleic acids metabolism, (B) cytoskeleton and motor protein, (C) respiration, (D) amino acids and protein synthesis, (E) signal transduction, (F) lipid synthesis or transport and membrane integrity or function, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell wall, (P) host plant defense induction, (U) unknown mode of action, (M) chemicals with multi-site activity and (BM) biologicals with multiple modes of action. Each mode of action (i.e. letters A through BM) contain one or more subgroups (e.g., A includes subgroups Al, A2, A3 and A4) based either on individual validated target sites of action, or in cases where the precise target site is unknown, based on cross resistance profiles within a group or in relation to other groups. Each of these subgroups (e.g., Al, A2, A3 and A4) is assigned a FRAC code which is a number and / or letter. For example, the FRAC code for subgroup Al is 4. Additional information on target sites and FRAC codes can be obtained from publicly available databases maintained, for example, by FRAC.
[0063] As used herein, the term “cross resistance” refers to the phenomenon that occurs when a pathogen develops resistance to one fungicide and simultaneously becomes resistant to one or more other fungicides. These other fungicides are typically, but not always, in the same chemical class or have the same target site of action, or can be detoxified by the same mechanism.
[0064] In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain and branched alkyl, such as, methyl, ethyl, n -propyl, / -propyl, and the different butyl, pentyl and hexyl isomers. “Alkenyl” includes straight- chain and branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain and branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkylene” denotes a straight-chain or branched alkanediyl. Examples of “alkylene” include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3), and the different butylene isomers. “Alkenylene” denotes a straight-chain or branched alkenediyl containing one olefinic bond. Examples of “alkenylene” include CH=CH, CH2CH=CH, CH=C(CH3) and the different butenylene isomers. “Alkynylene” denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of “alkynylene” include CH2CºC, CºCCH2, and the different butynylene, pentynylene or hexynylene isomers. The term “cycloalkylene” denotes a cycloalkanediyl ring. Examples of “cycloalkylene” include cyclobutanediyl, cyclopentanediyl and cyclohexanediyl. The term “cycloalkenylene” denotes a cycloalkenediyl ring containing one olefinic bond. Examples of “cycloalkenylene” include cyclopropenediyl and cyclopentenediyl.
[0065] “Alkoxy” includes, for example, methoxy, ethoxy, 77-propyloxy, / -propyloxy, and the different butoxy, pentoxy and hexyloxy isomers. “Alkenyloxy” includes straight-chain and branched alkenyl attached to and linked through an oxygen atom. Examples of “alkenyloxy” include H2C=CHCH20 and CE^CE^CHCEE O. “Alkynyloxy” includes straight-chain and branched alkynyl attached to and linked through an oxygen atom. Examples of “alkynyloxy” include HCºCCH20 and CH3CºCCH20.
[0066] The term “alkylthio” includes straight-chain and branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers. “Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH3S(=0), CH3CH2S(=0), CH3CH2CH2S(=0), (CH3)2CHS(=0), and the different butylsulfinyl isomers. Examples of “alkylsulfonyl” include CH3S(=0)2, CH3CH2S(=0)2, CH3CH2CH2S(=0)2, (CH3)2CHS(=0)2, and the different butylsulfonyl isomers. “Alkenylthio” includes straight-chain and branched alkenyl attached to and linked through a sulfur atom. Examples of “alkenylthio” include H2C=CHCH2S and CH3CH=CHCH2S. “Alkenylsulfinyl” includes both enantiomers of an alkenylsulfinyl group. Examples of “alkenylsulfinyl” include H2C=CHCH2S(=0), CH3CH=CHCH2S(=0), (CH3)2C=CHCH2S(=0). Examples of “alkenylsulfonyl” include CH3CH=CHS(=0)2, (CH3)2C=CHCH2S(=0)2. “Alkynylthio” includes straight-chain and branched alkynyl attached to and linked through a sulfur atom. Examples of “alkynylthio” include HCºCCH2S and CH3CºCCH2S. “Alkynylsulfinyl” includes both enantiomers of an alkynylsulfinyl group. Examples of “alkynylsulfinyl” include HCºCCH2S(=0), CH3CºCCH2S(=0). Examples of “alkynylsulfonyl” include CH3CºCS(=0)2, CH3CºCCH2S(=0)2.
[0067] “Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2SCH2and CH3CH2SCH2CH2; “alkylsulfinylalkyl” and “alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones, respectively.
[0068] “(Alkylthio)carbonyl” denotes a straight-chain or branched alkylthio group bonded to a C(=0) moiety. Examples of “(alkylthio)carbonyl” include CH3SC(=0), CH3CH2CH2SC(=0) and (CH3)2CHSC(=0). The terms “(alkenylthio)carbonyl” and “(alkynylthio)carbonyl” are likewise defined. Examples of “(alkenylthio)carbonyl” include H2C=CHCH2SC(=0) and CH3CH2CH=CHSC(=0). Examples of “(alkynylthio)carbonyl” include HCºCCH2SC(=0) and CH3CºCCH2SC(=0).
[0069] “Alkyl(thiocarbonyl)” denotes a straight-chain or branched alkyl group bonded to a C(=S) moiety. Examples of “alkyl(thiocarbonyl)” include CH3CH2C(=S), CH3CH2CH2C(=S) and (CH3)2CHCH2C(=S). The terms “alkenyl(thiocarbonyl)” and “alkynyl(thiocarbonyl)” are likewise defined. Examples of “alkenyl(thiocarbonyl)” include H2C=CHCH2CH2C(=S) and CH3CH2CH=CHC(=S). Examples of “alkynyl(thiocarbonyl)” include HCºCCH2CH2C(=S) and CH3CºCCH2C(=S).
[0070] “Alkylamino(thiocarbonyl)” denotes a straight-chain or branched alkylamino group bonded to a C(=S) moiety. Examples of “alkylamino(thiocarbonyl)” include CH3NHC(=S), CH3CH2CH2NHC(=S) and (CH3)2CHNHC(=S). The terms “alkenylamino(thiocarbonyl)” and “alkynylamino(thiocarbonyl)” are likewise defined. Examples of “alkenylamino(thiocarbonyl)” include H2C=CHCH2CH2NHC(=S) and CH3CH2CH=CHNHC(=S). Examples of “alkynylamino(thiocarbonyl)” include HCºCCH2CH2NHC(=S) and CH3CºCCH2NHC(=S). “(Alkylthio)carbonylamino” denotes a straight-chain or branched alkylthio group bonded to a C(=0)NH moiety. Examples of “(alkylthio)carbonylamino” include CH3CH2SC(=0)NH, CH3CH2CH2SC(=0)NH and (CH3)2CHSC(=0)NH. The terms “(alkenylthio)carbonylamino” and “(alkynylthio)carbonylamino” are likewise defined. Examples of
[0071] “(alkenylthio)carbonylamino include H2C=CHCH2SC(=0)NH and CH3CH=CHSC(=0)NH. Examples of “(alkynylthio)carbonylamino” include HCºCCH2CH2SC(=0)NH and CH3CºCCH2CH2SC(=0)NH.
[0072] “Alkylamino” includes an NH radical substituted with a straight-chain or branched alkyl group. Examples of “alkylamino” include CH3CH2NH, CH3CH2CH2NH, and
[0073] (CH3)2CHCH2NH. Examples of “dialkylamino” include (CH3)2N, (CH3CH2CH2)2N and CH3CH2(CH3)N. “Alkylaminoalkyl” denotes alkylamino substitution on alkyl. Examples of ‘ ‘alky laminoalky G ’ include CH3NHCH2, CH3NHCH2CH2, CH3CH2NHCH2,
[0074] CH3CH2CH2CH2NHCH2and CH3CH2NHCH2CH2.
[0075] “Alkylcarbonyl” denotes a straight-chain or branched alkyl group bonded to a C(=0) moiety. Examples of “alkylcarbonyl” include CH3C(=0), CH3CH2CH2C(=0) and
[0076] (CH3)2CHC(=0). The terms “alkenylcarbonyl” and “alkynylcarbonyl” are likewise defined. Examples of “alkenylcarbonyl” include H2C=CHCH2C(=0) and CH3CH2CH=CHC(=0). Examples of “alkynylcarbonyl” include HCºCCH2C(=0) and CH3CºCCH2C(=0).
[0077] “Alkoxycarbonyl” includes a C(=0) moiety substituted with a straight-chain or branched alkoxy group. Examples of “alkoxycarbonyl” include CH3OC(=0), CH3CH20C(=0),
[0078] CH3CH2CH20C(=0), (CH3)2CH0C(=0). The terms “alkenyloxycarbonyl” and
[0079] “alkynyloxycarbonyl” are likewise defined. Examples of “alkenyloxycarbonyl” include H2C=CHCH20C(=0) and CH3CH2CH=CH0C(=0). Examples of “alkynyloxycarbonyl” include HCºCCH2OC(=0) and CH3CºCCH20C(=0).
[0080] “Alkylaminocarbonyl” denotes a straight-chain or branched alkyl group bonded to a NHC(=0) moiety. Examples of “alkylaminocarbonyl” include CH3NHC(=0), CH3CH2NHC(=0), CH3CH2CH2NHC(=0), (CH3)2CHNHC(=0). The terms
[0081] “alkenylaminocarbonyl” and “alkynylaminocarbonyl” are likewise defined. Examples of ‘ ‘alkeny laminocarbony G ’ include H2C=CHCH2NHC(=0) and (CH3)2C=CHCH2NHC(=0). Examples of “alkynylaminocarbonyl” include CH3CºCNHC(=0) and CH3CºCCH2NHC(=0). Examples of “dialkylaminocarbonyl” include (CH3)2N(=0), (CH3CH2)2NC(=0),
[0082] CH3CH2(CH3)NC(=0), (CH3)2CH(CH3)NC(=0) and CH3CH2CH2(CH3)NC(=0).
[0083] The term “alkylcarbonylamino” denotes a straight-chain or branched alkyl group bonded to a C(=0)NH moiety. Examples of “alkylcarbonylamino” include CH3CH2C(=0)NH and CH3CH2CH2C(=0)NH. The terms “alkenylcarbonylamino” and “alkynylcarbonylamino” are likewise defined. Examples of “alkenylcarbonylamino” include H2C=CHCH2C(=0)NH and (CH3)2C=CHCH2C(=0)NH. Examples of “alkynylcarbonylamino” include
[0084] CH3CºCCH(CH3)C(=0)NH and HCºCCH2CH2C(=0)NH. The term “alkoxycarbonylamino” denotes alkoxy bonded to a C(=0)NH moiety. Examples of “alkoxycarbonylamino” include CH3OC(=0)NH and CH3CH20C(=0)NH.
[0085] The term “alkylaminocarbonylamino” denotes a straight-chain or branched alkyl group bonded to a NHC(=0)NH moiety. Examples of “alkylaminocarbonylamino” include CH3CH2NHC(=0)NH and (CH3CH2)2CH2NHC(=0)NH. The terms
[0086] “alkenylaminocarbonylamino” and “alkynylaminocarbonylamino” are likewise defined. Examples of “alkenylaminocarbonylamino” include H2C=CHCH2NHC(=0)NH and
[0087] (CH3)2C=CHCH2NHC(=0)NH. Examples of “alkynylaminocarbonylamino” include
[0088] CH3CºCCH(CH3)NHC(=0)NH and HCºCCH2CH2NHC(=0)NH.
[0089] “Alkylsulfonylamino” denotes an NH radical substituted with alkylsulfonyl. Examples of “alkylsulfonylamino” include CH3CH2S(=0)2NH and (CH3)2CHS(=0)2NH. The terms “alkenylsulfonylamino” and “alkynylsulfonylamino” are likewise defined. Examples of ‘ ‘alkeny lsulfony lamino’ ’ include H2C=CHCH2CH2S(=0)2NH and (CH3)2C=CHCH2S(=0)2NH. Examples of “alkynylsulfonylamino” include CH3CºCCH(CH3)S(=0)2NH and HCºCCH2CH2S(=0)2NH. The term “alkylsulfonyloxy” denotes an alkylsulfonyl group bonded to an oxygen atom. Examples of “alkylsulfonyloxy” include CH3S(=0)20, CH3CH2S(=0)20, CH3CH2CH2S(=0)20, (CH3)2CHS(=0)20, and the different butylsulfonyloxy, pentylsulfonyloxy and hexylsulfonyloxy isomers.
[0090] “Alkylaminosulfonyl” denotes a straight-chain or branched alkyl group bonded to a NHS(=0)2 moiety. Examples of “alkylaminosulfonyl” include CH3CH2NHS(=0)2 and (CH3)2CHNHS(=0)2- The terms “alkenylaminosulfonyl” and “alkynylaminosulfonyl” are likewise defined. Examples of “alkenylaminosulfonyl” include H2C=CHCH2CH2NHS(=0)2 and (CH3)2C=CHCH2NHS(=0)2- Examples of “alkynylaminosulfonyl” include
[0091] CH3CºCCH(CH3)NHS(=0)2and HCºCCH2CH2NHS(=0)2.
[0092] “ Alky lamino sulfony lamino” denotes a straight-chain or branched alkyl group bonded to a NHS(=0)2NH moiety. Examples of “alkylaminosulfonylamino” include CH3CH2NHS(=0)2NH and (CH3)2CHNHS(=0)2NH. The terms “alkenylaminosulfonylamino” and
[0093] “alky ny lamino sulfony lamino” are likewise defined. Examples of “alkenylaminosulfonylamino” include H2C=CHCH2CH2NHS(=0)2NH and (CH3)2C=CHCH2NHS(=0)2NH. Examples of “alky ny lamino sulfony lamino” include CH3CºCCH(CH3)NHS(=0)2NH and HCºCCH2CH2NHS(=0)2NH.
[0094] “Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH30CH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2and CH3CH2OCH2CH2. “Alkoxyalkoxy” denotes alkoxy substitution on another alkoxy moiety. “Alkoxyalkoxyalkyl” denotes alkoxyalkoxy substitution on alkyl. Examples of “alkoxyalkoxyalkyl” include CH3OCH2OCH2, CH3OCH2OCH2CH2and CH3CH2OCH2OCH2.
[0095] The term “alkylcarbonyloxy” denotes a straight-chain or branched alkyl bonded to a C(=0)0 moiety. Examples of “alkylcarbonyloxy” include CH3CH2C(=0)0 and (CH3)2CHC(=0)0. The terms “alkenylcarbonyloxy” and “alkynylcarbonyloxy” are likewise defined. Examples of “alkenylcarbonyloxy” include H2C=CHCH2CH2C(=0)0 and (CH3)2C=CHCH2C(=0)0. Examples of “alkynylcarbonyloxy” include
[0096] CH3CºCCH(CH3)C(=0)0 and HCºCCH2CH2C(=0)0. The term “alkoxycarbonyloxy” denotes a straight-chain or branched alkoxy bonded to a C(=0)0 moiety. Examples of “alkoxycarbonyloxy” include CH3CH2CH20C(=0)0 and (CH3)2CH0C(=0)0. The term “alkoxycarbonylalkyl” denotes alkoxycarbonyl substitution on alkyl. Examples of ‘ ‘alkoxy carbonylalkyl’ ’ include CH3CH20C(=0)CH2, (CH3)2CH0C(=0)CH2and
[0097] CH30C(=0)CH2CH2. The term “alkylaminocarbonyloxy” denotes a straight-chain or branched alkylaminocarbonyl attached to and linked through an oxygen atom. Examples of “alkylaminocarbonyloxy” include (CH3)2CHCH2NHC(=0)0 and CH3CH2NHC(=0)0. The terms “alkenylaminocarbonyloxy” and “alkynylaminocarbonyloxy” are likewise defined.
[0098] The term “alkylcarbonylthio” denotes a straight-chain or branched alkyl group bonded to a C(=0)S moiety. Examples of “alkylcarbonylthio” include CH3CH2C(=0)S and CH3CH2CH2C(=0)S.
[0099] “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to a straight-chain or branched alkyl group. The term “alkylcycloalkyl” denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, z-propylcyclobutyl, methylcyclopentyl and methylcyclohexyl. “Alkylcycloalkylalkyl” denotes alkylcycloalkyl substitution on alkyl. Examples of “alkylcycloalkylalkyl” include methylcyclohexylmethyl and ethylcycloproylmethyl. “Cycloalkenyl” includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- or 1,4-cyclohexadienyl. The term “cycloalky lcycloalkyl” denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members. Examples of cycloalky lcycloalkyl include cyclopropylcyclopropyl (such as 1,1'- bicyclopropyl-l-yl, l,l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4- cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as I,G-bicyclohexyl-l-yl), and the different cis- and / ra nv - c y c 1 o a 1 k y 1 c y c 1 o a 1 k y 1 isomers, (such as ( 1 R.2S)- 1 , 1 '-bicyclopropyl-2-yl and ( IR,2R)- 1 , 1 '-bicyclopropyl-2-yl) .
[0100] The term “cycloalkoxy” denotes cycloalkyl attached to and linked through an oxygen atom including, for example, cyclopentyloxy and cyclohexyloxy. The term “cycloalkoxyalkyl” denotes cycloalkoxy substitution on an alkyl moiety. Examples of “cycloalkoxyalkyl” include cyclopropyloxymethyl, cyclopentyloxyethyl, and other cycloalkoxy groups bonded to a straight-chain or branched alkyl moiety.
[0101] The term “cycloalkylaminoalkyl” denotes cycloalkylamino substitution on an alkyl group. Examples of “cycloalkylaminoalkyl” include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to a straight-chain or branched alkyl group.
[0102] “Cycloalkylcarbonyl” denotes cycloalkyl bonded to a C(=0) group including, for example, cyclopropylcarbonyl and cyclopentylcarbonyl. “Cycloalkylcarbonyloxy” denotes cycloalkylcarbonyl attached to and linked through an oxygen atom. Examples of “cycloalkylcarbonyloxy” include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy. The term “cycloalkoxycarbonyl” means cycloalkoxy bonded to a C(=0) group, for example, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. “Cycloalkylaminocarbonylamino” denotes cycloalkylamino bonded to a C(=0)NH group, for example, cyclopentylaminocarbonylamino and cyclohexylaminocarbonylamino.
[0103] The term “halogen”, either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include CF3, CICH2, CF3CH2 and CF3CCI2. The terms “haloalkenyl”, “haloalkynyl” “haloalkoxy”, “haloalkylsulfonyl”, “halocycloalkyl”, and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkenyl” include Cl2C=CHCH2 and CF3CH2CH=CHCH2. Examples of “haloalkynyl” include HOCCHC1, CF3CºC, CC13CºC and FCH2CºCCH2. Examples of “haloalkoxy” include CF30, CC13CH20, F2CHCH2CH20 and CF3CH2O. Examples of “haloalkylsulfonyl” include CF3S(=0)2, CC13S(=0)2, CF3CH2S(=0)2 and CF3CF2S(=0)2. Examples of “halocycloalkyl” include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chorocyclohexyl. “Cyanoalkyl” denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH2, NCCH2CH2and CH3CH(CN)CH2. “Hydroxyalkyl” denotes an alkyl group substituted with one hydroxy group. Examples of “hydroxyalkyl” include HOCH2CH2, CH3CH2(OH)CH and HOCH2CH2CH2CH2.
[0104] “Trialkylsilyl” includes 3 branched and / or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and / <? / 7-butyldi methyl si lyl. The term “halotrialkylsilyl” is likewise defined. Examples of “halotrialkylsilyl” include trifluormethylsilyl and trichloromethylsilyl.
[0105] The total number of carbon atoms in a substituent group is indicated by the “Cj-Cj” prefix where i and j are numbers from 1 to 15. For example, C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C2alkoxyalkyl designates CH3OCH2; C3alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2and CH3CH2OCH2CH2.
[0106] Generally when a molecular fragment (i.e. radical) is denoted by a series of atom symbols (e.g., C, H, N, O and S) the implicit point or points of attachment will be easily recognized by those skilled in the art. In some instances herein, particularly when alternative points of attachment are possible, the point or points of attachment may be explicitly indicated by a hyphen
[0107] C-”).
[0108] The term “unsubstituted” in connection with a group such as a ring or ring system means the group does not have any substituents other than its one or more attachments to the remainder of Formula 1. The term “optionally substituted” means that the number of substituents can be zero. Unless otherwise indicated, optionally substituted groups may be substituted with as many optional substituents as can be accommodated by replacing a hydrogen atom with a non-hydrogen substituent on any available carbon or nitrogen atom. Commonly, the number of optional substituents (when present) ranges from 1 to 3. As used herein, the term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.”
[0109] The number of optional substituents may be restricted by an expressed limitation. For example, the phrase “optionally substituted with up to 3 substituents independently selected from R13” means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows). When a range specified for the number of substituents (e.g., x being an integer from 0 to 3 in Exhibit A) exceeds the number of positions available for substituents on a ring (e.g., 1 position available for (R13)xon G-7 in Exhibit A), the actual higher end of the range is recognized to be the number of available positions.
[0110] When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can vary (e.g., (R13)xin Exhibit A wherein x is 1 to 3), then said substituents are independently selected from the group of defined substituents, unless otherwise indicated. When a variable group is shown to be optionally attached to a position, for example (R13)xin Exhibit A wherein x may be 0, then hydrogen may be at the position even if not recited in the definition of the variable group.
[0111] The dotted line in rings depicted in the present description (e.g., the rings G-44, G-45, G-48 and G-49 shown in Exhibit A) represents that the bond indicated can be a single bond or double bond.
[0112] Naming of substituents in the present disclosure uses recognized terminology providing conciseness in precisely conveying to those skilled in the art the chemical structure. For sake of conciseness, locant descriptors may be omitted.
[0113] Unless otherwise indicated, a “ring” or “ring system” as a component of Formula 1 (e.g., G) is carbocyclic or heterocyclic. The term “ring system” denotes two or more connected rings. The term “spirocyclic ring system” denotes a ring system consisting of two rings connected at a single atom (so the rings have a single atom in common). The term “bicyclic ring system” denotes a ring system consisting of two rings sharing two or more common atoms. In a “fused bicyclic ring system” the common atoms are adjacent, and therefore the rings share two adjacent atoms and a bond connecting them.
[0114] The term “ring member” refers to an atom (e.g., C, O, N or S) or other moiety (e.g., C(=0), C(=S), S(=0) and S(=0)2) forming the backbone of a ring or ring system. The term “aromatic” indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and that (4n + 2) p electrons, where n is a positive integer, are associated with the ring to comply with HiickeTs rule
[0115] The term “carbocyclic ring” denotes a ring wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies HiickeTs rule, then said ring is also called an “aromatic ring”. “Saturated carbocyclic” refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
[0116] As used herein, the term “partially unsaturated ring" or "partially unsaturated heterocycle” refers to a ring which contains unsaturated ring atoms and one or more double bonds but is not aromatic. The terms “heterocyclic ring” or “heterocycle” denotes a ring wherein at least one of the atoms forming the ring backbone is other than carbon. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies HiickeTs rule, then said ring is also called a “heteroaromatic ring” or aromatic heterocyclic ring. “Saturated heterocyclic ring” refers to a heterocyclic ring containing only single bonds between ring members.
[0117] Unless otherwise indicated, heterocyclic rings and ring systems are attached to the remainder of Formula 1 through any available carbon or nitrogen atom by replacement of a hydrogen on said carbon or nitrogen atom.
[0118] Compounds of this invention can exist as one or more stereoisomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis- and / ran.s-isomcrs (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and / or to selectively prepare said stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds , John Wiley & Sons, 1994.
[0119] Compounds of this invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. For example, when T is T-3, then Formula 1 compounds contain at least one double bond and the configuration of substituents about that double bond can be (Z) or (E) ( cis or trans), or a mixture thereof. In the context of the present disclosure and claims, a wavy bond (e.g., as shown in the T-3 moiety in the Summary of the Invention) indicates a single bond which is linked to an adjacent double bond wherein the geometry about the adjacent double bond is either (Z)-configuration (svn-isomcr or cA-isomer) or (C)-con figuration (anti- isomer or trans- isomer), or a mixture thereof. That is, a wavy bond represents an unspecified (Z)- or ( E )- (cis- or trans-) isomer, or mixture thereof. In addition, the compounds of the present invention can contain one or more chiral centers and therefore exist in enantiomeric and diastereomeric forms. Unless the structural formula or the language of this application specifically designate a particular cis- or trans- isomer, or a configuration of a chiral center, the scope of the present invention is intended to cover all such isomers per se, as well as mixtures of cis- and / ran.s-isomcrs, mixtures of diastereomers and racemic mixtures of enantiomers (optical isomers) as well.
[0120] This invention also includes compounds of Formula 1 wherein one stereoisomer is enriched relative to the other stereoisomer(s). Of note are compounds of Formula 1 wherein T is T-3 and the substituents attached to the double bond in the T-3 moiety are in a predominately (Z)- configuration, or predominately an (Tj-configuration. The ratio of the (Z)- to (^-isomers in any compounds of Formula 1, whether produced stereoselectivity or non-stereoselectivity, may take on a broad range of values. For example, compounds of Formula 1 may comprise from about 10 to 90 percent by weight of the (Z)- isomer to about 90 to 10 percent by weight of the (C)-isomcr. In other embodiments, Formula 1 compounds may contain from about 15 to 85 percent by weight of the (Z)- isomer and about 85 to 15 percent by weight of the (^-isomer; in another embodiment, the mixture contains about 25 to 75 percent by weight of the (Z)- isomer and about 75 to 25 percent by weight of the (C)-isomcr; in another embodiment, the mixture contains about 35 to 65 percent by weight of the (Z)- isomer and about 65 to 35 percent by weight of the (C)-isomcr; in another embodiment, the mixture contains about 45 to 55 percent by weight of the (Z)- isomer and about 55 to 45 percent by weight of the (C)-isomcr. These percentages by weight are based on the total weight of the composition, and it will be understood that the sum of the weight percent of the (Z)- isomer and the (^-isomer is 100 weight percent. In other words, compounds of Formula 1 might contain 65 percent by weight of the (Z)- isomer and 35 percent by weight of the (T)-isomcr, or vice versa.
[0121] In addition, this invention includes compounds that are enriched compared to the racemic mixture in an enantiomer of Formula 1. Also included are the essentially pure enantiomers of compounds of Formula 1. When enantiomerically enriched, one enantiomer is present in greater amounts than the other, and the extent of enrichment can be defined by an expression of enantiomeric excess (“ee”), which is defined as (2x-l)· 100%, where x is the mole fraction of the dominant enantiomer in the mixture (e.g., an ee of 20% corresponds to a 60:40 ratio of enantiomers).
[0122] Preferably the compositions of this invention have at least a 50% enantiomeric excess; more preferably at least a 75% enantiomeric excess; still more preferably at least a 90% enantiomeric excess; and the most preferably at least a 94% enantiomeric excess of the more active isomer. Of particular note are enantiomerically pure embodiments of the more active isomer.
[0123] Compounds of this invention can exist as one or more conformational isomers due to restricted rotation about an amide bond (e.g., C(=0)-N) in Formula 1. This invention comprises mixtures of conformational isomers. In addition, this invention includes compounds that are enriched in one conformer relative to others. This invention comprises all stereoisomers, conformational isomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
[0124] One skilled in the art will appreciate that not all nitrogen containing heterocycles can form A-oxidcs since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form / V-oxides. One skilled in the art will also recognize that tertiary amines can form / V-oxides. Synthetic methods for the preparation of N- oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as / -butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N- oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis , vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and
[0125] A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and
[0126] B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
[0127] One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of the compounds of Formula 1 are useful for control of plant diseases caused by fungal plant pathogens (i.e. are agriculturally suitable). The salts of the compounds of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, V-oxides, and agriculturally suitable salts, and solvates thereof.
[0128] Compounds selected from Formula 1, stereoisomers, tautomers, / V-oxides, and salts thereof, typically exist in more than one form, and Formula 1 thus includes all crystalline and non crystalline forms of the compounds that Formula 1 represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and / or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1. Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry , Wiley-VCH, Weinheim, 2006.
[0129] One skilled in the art recognizes that compounds of Formula 1 can exist as mixtures of ketonic and solvated forms (e.g., hemiketals, ketals and hydrates) and each are independently interconvertible and agriculturally active. For example, ketones of Formula l1(i.e. compounds of Formula 1 wherein T is T-l) may exist in equilibrium with their corresponding hydrates of Formula l2(i.e. compounds of Formula 1 wherein T is T-2, and R2aX and R2bY are both OH). In cases where the ketone group is in close proximity to an electron-withdrawing group, such as when R1is a trifluoromethyl group, the equilibrium typically favors the hydrate form. l1l2
[0130] This invention comprises all ketonic and solvated forms of Formula 1 compounds, and mixtures thereof in all proportions. Unless otherwise indicated, reference to a compound by one tautomer description is to be considered to include all tautomers.
[0131] Additionally, some of the unsaturated rings and ring systems depicted in Exhibit A can have an arrangement of single and double bonds between ring members different from that depicted. Such differing arrangements of bonds for a particular arrangement of ring atoms correspond to different tautomers. For these unsaturated rings and ring systems, the particular tautomer depicted is to be considered representative of all the tautomers possible for the arrangement of ring atoms shown.
[0132] As described in the Summary of the Invention, an aspect of the present invention is directed at a composition comprising (a) at least one compound selected from Formula 1, / V-oxides, and salts thereof, with (b) at least one additional fungicidal compound. More particularly, Component (b) is selected from the group consisting of
[0133] (bl) methyl benzimidazole carbamate (MBC) fungicides;
[0134] (b2) dicarboximide fungicides;
[0135] (b3) demethylation inhibitor (DMI) fungicides;
[0136] (b4) phenylamide (PA) fungicides;
[0137] (b5) amine / morpholine fungicides;
[0138] (b6) phospholipid biosynthesis inhibitor fungicides;
[0139] (b7) succinate dehydrogenase inhibitor (SDHI) fungicides;
[0140] (b8) hydroxy(2-amino-)pyrimidine fungicides;
[0141] (b9) anilinopyrimidine (AP) fungicides;
[0142] (blO) V-phcnyl carbamate fungicides;
[0143] (b 11) quinone outside inhibitor (Qol) fungicides;
[0144] (bl2) phenylpyrrole (PP) fungicides;
[0145] (bl3) azanaphthalene fungicides;
[0146] (bl4) cell peroxidation inhibitor fungicides;
[0147] (bl5) melanin biosynthesis inhibitor-reductase (MBI-R) fungicides;
[0148] (bl6a) melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides;
[0149] (bl6b) melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicides;
[0150] (bl7) keto reductase inhibitor (KRI) fungicides;
[0151] (bl8) squalene-epoxidase inhibitor fungicides;
[0152] (bl9) polyoxin fungicides;
[0153] (b20) phenylurea fungicides;
[0154] (b21) quinone inside inhibitor (Qil) fungicides;
[0155] (b22) benzamide and thiazole carboxamide fungicides; (b23) enopyranuronic acid antibiotic fungicides;
[0156] (b24) hexopyranosyl antibiotic fungicides;
[0157] (b25) glucopyranosyl antibiotic: protein synthesis fungicides;
[0158] (b26) glucopyranosyl antibiotic fungicides;
[0159] (b27) cyanoacetamideoxime fungicides;
[0160] (b28) carbamate fungicides;
[0161] (b29) oxidative phosphorylation uncoupling fungicides;
[0162] (b30) organo tin fungicides;
[0163] (b31) carboxylic acid fungicides;
[0164] (b32) heteroaromatic fungicides;
[0165] (b33) phosphonate fungicides;
[0166] (b34) phthalamic acid fungicides;
[0167] (b35) benzotriazine fungicides;
[0168] (b36) benzene-sulfonamide fungicides;
[0169] (b37) pyridazinone fungicides;
[0170] (b38) thiophene-carboxamide fungicides;
[0171] (b39) complex I NADH oxido-reductase inhibitor fungicides;
[0172] (b40) carboxylic acid amide (CAA) fungicides;
[0173] (b41) tetracycline antibiotic fungicides;
[0174] (b42) thiocarbamate fungicides;
[0175] (b43) benzamide fungicides;
[0176] (b44) microbial fungicides;
[0177] (b45) quinone outside inhibitor, stigmatellin binding (QoSI) fungicides;
[0178] (b46) plant extract fungicides;
[0179] (b47) cyanoacrylate fungicides;
[0180] (b48) polyene fungicides;
[0181] (b49) oxy sterol binding protein inhibitor (OSBPI) fungicides;
[0182] (b50) aryl-phenyl-ketone fungicides;
[0183] (b51) host plant defense induction fungicides;
[0184] (b52) multi-site activity fungicides;
[0185] (b53) biologicals with multiple modes of action;
[0186] (b54) fungicides other than fungicides of component (a) and components (bl) through (b53); and salts of compounds of (bl) through (b54). Of note are embodiments wherein component (b) comprises at least one fungicidal compound from each of two different groups selected from (bl) through (b54).
[0187] “Methyl benzimidazole carbamate (MBC) fungicides (bl)” (FRAC code 1) inhibit mitosis by binding to b-tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Methyl benzimidazole carbamate fungicides include benzimidazole and thiophanate fungicides. The benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole. The thiophanates include thiophanate and thiophanate-methyl.
[0188] “Dicarboximide fungicides (b2)” (FRAC code 2) inhibit a mitogen-activated protein (MAP) / histidine kinase in osmotic signal transduction. Examples include chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.
[0189] “Demethylation inhibitor (DMI) fungicides (b3)” (FRAC code 3) (Sterol Biosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylase, which plays a role in sterol production. Sterols, such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. DMI fungicides are divided between several chemical classes: piperazines, pyridines, pyrimidines, imidazoles, triazoles and triazolinthiones. The piperazines include triforine. The pyridines include buthiobate, pyrifenox, pyrisoxazole and (aS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3- pyridinemethanol. The pyrimidines include fenarimol, nuarimol and triarimol. The imidazoles include econazole, imazalil, oxpoconazole, pefurazoate, prochloraz and triflumizole. The triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, a-(l-chlorocyclopropyl)-a-[2-(2,2- dichlorocyclopropyl)ethyl]-l - 1,2, 4-triazole- 1 -ethanol, rel- 1 -[[(2 / C3S)-3-(2-chlorophcnyl)-2-
[0190] (2, 4-difluorophenyl)-2-oxiranyl]methyl]-l - 1,2, 4-triazole, re / -2-[[(2R,3S)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-l,2-dihydro-3 -l,2,4-triazole-3-thione and rel- 1- [[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-l-ylthio)- IH- 1,2,· 4-triazole. The triazolinthiones include prothioconazole. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.
[0191] “Phenylamide (PA) fungicides (b4)” (FRAC code 4) are specific inhibitors of RNA polymerase in Oomycete fungi. Sensitive fungi exposed to these fungicides show a reduced capacity to incorporate uridine into rRNA. Growth and development in sensitive fungi is prevented by exposure to this class of fungicide. Phenylamide fungicides include acylalanine, oxazolidinone and butyrolactone fungicides. The acylalanines include benalaxyl, benalaxyl-M (also known as kiralaxyl), furalaxyl, metalaxyl and metalaxyl-M (also known as mefenoxam). The oxazolidinones include oxadixyl. The butyrolactones include ofurace.
[0192] “Amine / morpholine fungicides (b5)” (FRAC code 5) (SBI: Class II) inhibit two target sites within the sterol biosynthetic pathway, A8A7isomerase and A14reductase. Sterols, such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. Amine / morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine, piperidine and spiroketal-amine fungicides. The morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide. The piperidines include fenpropidin and piperalin. The spiroketal-amines include spiroxamine.
[0193] “Phospholipid biosynthesis inhibitor fungicides (b6)” (FRAC code 6) inhibit growth of fungi by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include phophorothiolate and dithiolane fungicides. The phosphorothiolates include edifenphos, iprobenfos and pyrazophos. The dithiolanes include isoprothiolane.
[0194] “Succinate dehydrogenase inhibitor (SDHI) fungicides (b7)” (FRAC code 7) inhibit complex II fungal respiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibiting respiration prevents the fungus from making ATP, and thus inhibits growth and reproduction. SDHI fungicides include phenylbenzamide, phenyloxoethylthiophene amide, pyridinylethylbenzamide, furan carboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazole-4-carboxamide, / V-cyclopropyl-ZV-benzyl-pyrazole carboxamide, / V-methoxy-(phenyl-ethyl)-pyrazole carboxamide, pyridine carboxamide and pyrazine carboxamide fungicides. The phenylbenzamides include benodanil, flutolanil and mepronil. The phenyloxoethylthiophene amides include isofetamid. The pyridinylethylbenzamide s include fluopyram. The furan carboxamides include fenfuram. The oxathiin carboxamides include carboxin and oxycarboxin. The thiazole carboxamides include thifluzamide. The pyrazole-4-carboxamides include benzovindiflupyr, bixafen, flubeneteram (provisional common name, Registry Number 1676101-39-5), fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne (provisional common name, Registry Number 1803108-03-3), sedaxane and / V-[2-(2,4-dichlorophenyl)-2- mcthoxy- 1 -mcthylcthylJ-3-(difluoiOmcthyl)- 1 -methyl- 1 / / -pyrazolc-4-carboxamidc. The N- cyc lopropy 1 - A- benzy 1 -py azo lc carboxamides include isoflucypram. The A- mcthoxy-iphcnyl- ethyl)-pyrazole carboxamides include pydiflumetofen. The pyridine carboxamides include boscalid. The pyrazine carboxamides include pyraziflumid.
[0195] “Hydroxy-(2-amino-)pyrimidine fungicides (b8)” (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.
[0196] “Anilinopyrimidine (AP) fungicides (b9)” (FRAC code 9) are proposed to inhibit biosynthesis of the amino acid methionine and to disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim and pyrimethanil.
[0197] “A- Phenyl carbamate fungicides (blO)” (FRAC code 10) inhibit mitosis by binding to b- tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include diethofencarb.
[0198] “Quinone outside inhibitor (Qol) fungicides (b 11 )” (FRAC code 11) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol is blocked at the “quinone outside” (Qo) site of the cytochrome be\complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone outside inhibitor fungicides include methoxyacrylate, methoxyacetamide, methoxycarbamate, oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides (collectively also known as strobilurin fungicides), and oxazolidinedione, imidazolinone and benzy lcarbamate fungicides. The methoxy acrylates include azoxystrobin, coumoxystrobin, enoxastrobin (also known as enestroburin), flufenoxystrobin, picoxystrobin and pyraoxystrobin. The methoxyacetamides include mandestrobin. The methoxy- carbamates include pyraclostrobin, pyrametostrobin and triclopyricarb. The oximinoacetates include kresoxim-methyl and trifloxystrobin. The oximinoacetamides include dimoxystrobin, fenaminstrobin, metominostrobin and orysastrobin. The dihydrodioxazines include fluoxastrobin. The oxazolidinediones include famoxadone. The imidazolinones include fenamidone. The benzylcarbamates include pyribencarb.
[0199] “Phenylpyrrole (PP) fungicides (bl2)” (FRAC code 12) inhibit a MAP / histidine kinase associated with osmotic signal transduction in fungi. Fenpiclonil and fludioxonil are examples of this fungicide class.
[0200] “Azanaphthalene fungicides (bl3)” (FRAC code 13) are proposed to inhibit signal transduction by a mechanism which is as yet unknown. They have been shown to interfere with germination and / or appressorium formation in fungi that cause powdery mildew diseases. Azanaphthalene fungicides include ary loxy quinolines and quinazolinones. The aryloxyquinolines include quinoxyfen. The quinazolinones include proquinazid.
[0201] “Cell peroxidation inhibitor fungicides (bl4)” (FRAC code 14) are proposed to inhibit lipid peroxidation which affects membrane synthesis in fungi. Members of this class, such as etridiazole, may also affect other biological processes such as respiration and melanin biosynthesis. Cell peroxidation fungicides include aromatic hydrocarbon and 1,2,4-thiadiazole fungicides. The aromatic hydrocarboncarbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos-methyl. The 1,2,4-thiadiazoles include etridiazole.
[0202] “Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides (bl5)” (FRAC code 16.1) inhibit the naphthal reduction step in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranone, pyrroloquinolinone and triazolobenzothiazole fungicides. The isobenzofuranones include fthalide. The pyrroloquinolinones include pyroquilon. The triazolobenzothiazoles include tricyclazole.
[0203] “Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides (bl6a)” (FRAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides. The cyclopropanecarboxamides include carpropamid. The carboxamides include diclocymet. The propionamides include fenoxanil.
[0204] “Melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicides (bl6b)” (FRAC code 16.3) inhibit polyketide synthase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-polyketide synthase fungicides include trifluoroethylcarbamate fungicides. The trifluoroethylcarbamates include tolprocarb.
[0205] “Keto reductase inhibitor (KRI) fungicides (bl7)” (FRAC code 17) inhibit 3-keto reductase during C4-demethylation in sterol production. Keto reductase inhibitor fungicides (also known as Sterol Biosynthesis Inhibitors (SBI): Class III) include hydroxyanilides and amino- pyrazolinones. Hydroxyanilides include fenhexamid. Amino-pyrazolinones include fenpyrazamine. Quinofumelin (provisional common name, Registry Number 861647-84-9) and ipflufenoquin (provisional common name, Registry Number 1314008-27-9) are also believed to be keto reductase inhibitor fungicides.
[0206] “Squalene-epoxidase inhibitor fungicides (bl8)” (FRAC code 18) (SBI: Class IV) inhibit squalene-epoxidase in the sterol biosynthesis pathway. Sterols such as ergosterol are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides. The thiocarbamates include pyributicarb. The allylamines include naftifine and terbinafine.
[0207] “Polyoxin fungicides (bl9)” (FRAC code 19) inhibit chitin synthase. Examples include polyoxin.
[0208] “Phenylurea fungicides (b20)” (FRAC code 20) are proposed to affect cell division. Examples include pencycuron.
[0209] “Quinone inside inhibitor (Qil) fungicides (b21)” (FRAC code 21) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinone reductase. Reduction of ubiquinone is blocked at the “quinone inside” (Qi) site of the cytochrome be\complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone inside inhibitor fungicides include cyanoimidazole, sulfamoyltriazole and picolinamide fungicides. The cyanoimidazoles include cyazofamid. The sulfamoyltriazoles include amisulbrom. The picolinamides include fenpicoxamid (Registry Number 517875-34-2).
[0210] “Benzamide and thiazole carboxamide fungicides (b22)” (FRAC code 22) inhibit mitosis by binding to b-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. The benzamides include toluamides such as zoxamide. The thiazole carboxamides include ethylaminothiazole carboxamides such as ethaboxam.
[0211] “Enopyranuronic acid antibiotic fungicides (b23)” (FRAC code 23) inhibit growth of fungi by affecting protein biosynthesis. Examples include blasticidin-S.
[0212] “Hexopyranosyl antibiotic fungicides (b24)” (FRAC code 24) inhibit growth of fungi by affecting protein biosynthesis. Examples include kasugamycin.
[0213] “Glucopyranosyl antibiotic: protein synthesis fungicides (b25)” (FRAC code 25) inhibit growth of fungi by affecting protein biosynthesis. Examples include streptomycin.
[0214] “Glucopyranosyl antibiotic fungicides (b26)” (FRAC code U18, previously FRAC code 26 reclassified to U18) are proposed to inhibit trehalase and inositol biosynthesis. Examples include validamycin.
[0215] “Cyanoacetamideoxime fungicides (b27)” (FRAC code 27) include cymoxanil.
[0216] “Carbamate fungicides (b28)” (FRAC code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in cell membranes, which then disrupts cell membrane permeability. Iodocarb, propamacarb and prothiocarb are examples of this fungicide class.
[0217] “Oxidative phosphorylation uncoupling fungicides (b29)” (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development. This class includes dinitrophenyl crotonates such as binapacryl, meptyldinocap and dinocap, and 2,6-dinitroanilines such as fluazinam.
[0218] “Organo tin fungicides (b30)” (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in oxidative phosphorylation pathway. Examples include fentin acetate, fentin chloride and fentin hydroxide.
[0219] “Carboxylic acid fungicides (b31)” (FRAC code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
[0220] “Hetero aromatic fungicides (b32)” (FRAC code 32) are proposed to affect DNA / ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. The isoxazoles include hymexazole and the isothiazolones include octhilinone.
[0221] “Phosphonate fungicides (b33)” (FRAC code P07, previously FRAC code 33 reclassified to P07) include phosphorous acid and its various salts, including fosetyl-aluminum.
[0222] “Phthalamic acid fungicides (b34)” (FRAC code 34) include teclofthalam.
[0223] “Benzotriazine fungicides (b35)” (FRAC code 35) include triazoxide.
[0224] “Benzene-sulfonamide fungicides (b36)” (FRAC code 36) include flusulfamide.
[0225] “Pyridazinone fungicides (b37)” (FRAC code 37) include diclomezine.
[0226] “Thiophene-carboxamide fungicides (b38)” (FRAC code 38) are proposed to affect ATP production. Examples include silthiofam.
[0227] “Complex I NADH oxidoreductase inhibitor fungicides (b39)” (FRAC code 39) inhibit electron transport in mitochondria and include pyrimidinamines such as diflumetorim, pyrazole- 5-carboxamides such as tolfenpyrad, and quinazoline such as fenazaquin.
[0228] “Carboxylic acid amide (CAA) fungicides (b40)” (FRAC code 40) inhibit cellulose synthase which prevents growth and leads to death of the target fungus. Carboxylic acid amide fungicides include cinnamic acid amide, valinamide carbamate and mandelic acid amide fungicides. The cinnamic acid amides include dimethomorph, flumorph and pyrimorph. The valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb and valifenalate (also known as valiphenal). The mandelic acid amides include mandipropamid, N- [2- [4- [ [3 -(4-chloropheny l)-2-propyn- 1 -yl] oxy ] -3 -methoxyphenyl] ethyl] -3 -methyl-2- [(methylsulfonyl)amino]butanamide and A-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3- methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.
[0229] “Tetracycline antibiotic fungicides (b41)” (FRAC code 41) inhibit growth of fungi by affecting protein synthesis. Examples include oxy tetracycline.
[0230] “Thiocarbamate fungicides (b42)” (FRAC code M 12, previously FRAC code 42 reclassified to Ml 2) include methasulfocarb.
[0231] “Benzamide fungicides (b43)” (FRAC code 43) inhibit growth of fungi by delocalization of spectrin-like proteins. Examples include pyridinylmethyl benzamides such as fluopicolide and fluopimomide.
[0232] “Microbial fungicides (b44)” (FRAC code BM02, previously FRAC code 44 reclassified to BM02) disrupt fungal pathogen cell membranes. Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB 1600, D747, TJ100 (also called strain 1 BE; known from EP2962568), and the fungicidal lipopeptides which they produce.
[0233] “Quinone outside inhibitor, stigmatellin binding (QoSI) fungicides (b45)” (FRAC code 45) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinone reductase at the “quinone outside” (Qo) site, stigmatellin binding sub-site, of the cytochrome be\complex. Inhibiting mitochondrial respiration prevents normal fungal growth and development. QoSI fungicides include triazolopyrimidylamines such as ametoctradin.
[0234] “Plant extract fungicides (b46)” (FRAC code 46) cause cell membrane disruption. Plant extract fungicides include terpene hydrocarbons, terpene alcohols and terpen phenols such as the extract from Melaleuca alternifolia (tea tree) and plant oils (mixtures) such as eugenol, geraniol and thymol.
[0235] “Cyanoacrylate fungicides (b47)” (FRAC code 47) bind to the myosin motor domain and effect motor activity and actin assembly. Cyanoacrylates include fungicides such as phenamacril.
[0236] “Polyene fungicides (b48)” (FRAC code 48) cause disruption of the fungal cell membrane by binding to ergosterol, the main sterol in the membrane. Examples include natamycin (pimaricin).
[0237] “Oxysterol binding protein inhibitor (OSBPI) Fungicides (b49)” (FRAC code 49) bind to the oxysterol-binding protein in oomycetes causing inhibition of zoospore release, zoospore motility and sporangia germination. Oxysterol binding fungicides include piperdinylthiazoleisoxazolines such as oxathiapiprolin and fluoxapiprolin.
[0238] “Aryl-phenyl-ketone fungicides (b50)” (FRAC code 50, previously FRAC code U8 reclassified to 50) inhibit the growth of mycelium in fungi. Aryl-phenyl ketone fungicides include benzophenones such as metrafenone, and benzoylpyridines such as pyriofenone. “Host plant defense induction fungicides (b51)” induce host plant defense mechanisms. Host plant defense induction fungicides include benzothiadiazole (FRAC code P01), benzisothiazole (FRAC code P02), thiadiazole carboxamide (FRAC code P03), polysaccharide (FRAC code P04), plant extract (FRAC code P05), microbial (FRAC code P06) and phosphonate fungicides (FRAC code P07, see (b33) above). The benzothiadiazoles include acibenzolar-S- methyl. The benzisothiazoles include probenazole. The thiadiazole carboxamides include tiadinil and isotianil. The polysaccharides include laminarin. The plant extracts include extract from Reynoutria sachalinensis (giant knotweed). The microbials include Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS 117.
[0239] “Multi-site activity fungicides (b52)” inhibit fungal growth through multiple sites of action and have contact / preventive activity. Multi- site activity fungicides include copper fungicides (FRAC code M01), sulfur fungicides (FRAC code M02), dithiocarbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulfamide fungicides (FRAC code M06), multi-site contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code Mil) and thiocarbamate (FRAC code M12, see (b42) above) fungicides. Copper fungicides are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate and copper hydroxide (e.g., including compositions such as Bordeaux mixture (tribasic copper sulfate). Sulfur fungicides are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur. Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety; examples include ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb and ziram. Phthalimide fungicides contain a phthalimide molecular moiety; examples include folpet, captan and captafol. Chloronitrile fungicides contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil. Sulfamide fungicides include dichlofluanid and tolyfluanid. Multi-site contact guanidine fungicides include, guazatine, iminoctadine albesilate and iminoctadine triacetate. Triazine fungicides include anilazine. Quinone fungicides include dithianon. Quinoxaline fungicides include quinomethionate (also known as chinomethionate). Maleimide fungicides include fluoroimide.
[0240] “Biologicals with multiple modes of action (b53)” include agents from biological origins showing multiple mechanisms of action without evidence of a dominating mode of action. This class of fungicides includes polypeptide (lectin), phenol, sesquiterpene, tritepenoid and coumarin fungicides (FRAC code BM01) such as extract from the cotyledons of lupine plantlets. This class also includes momicrobial fungicides (FRAC code BM02, see (b44) above). “Fungicides other than fungicides of component (a) and components (bl) through (b53); (b54)”; include certain fungicides whose mode of action may be unknown. These include: (b54.1) “phenyl-acetamide fungicides” (FRAC code U06), (b54.2) “guanidine fungicides” (FRAC code U12), (b54.3) “thiazolidine fungicides” (FRAC code U13), (b54.4) “pyrimidinone-hydrazone fungicides” (FRAC code U14), (b54.5) “4-quinolylacetate fungicides” (FRAC code U16), (54.6) “tetrazolyloxime fungicides” (FRAC code U17) and “glucopyranosyl antibiotic fungicides” (FRAC code U18, see (b26) above). The phenyl-acetamides include cyflufenamid. The guanidines include dodine. The thiazolidines include flutianil. The pyrimidinonehydrazones include ferimzone. The 4-quinolylacetates include tebufloquin. The tetrazolyloximes include picarbutrazox.
[0241] The (b54) class also includes bethoxazin, dichlobentiazox (provisional common name, Registry Number 957144-77-3), dipymetitrone (provisional common name, Registry Number 16114-35-5), flometoquin, neo-asozin (ferric methanearsonate), pyrrolnitrin, tolnifanide (Registry Number 304911-98-6), A-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]- V- ct h y 1 - A- met h y 1 met h an i m i da m i dc, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenyl A-[l-[[[l-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate.
[0242] Additional “Fungicides other than fungicides of classes (1) through (54)” whose mode of action may be unknown, or may not yet be classified include a fungicidal compound selected from components (b54.7) through (b54.13), as described below.
[0243] Component (54.7) relates to (lS)-2,2-bis(4-fluorophenyl)-l-methylethyl A-[[3-(acetyloxy)- 4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name florylpicoxamid, Registry Number 1961312-55-9) which is believed to be a Quinone inside inhibitor (Qil) fungicide (FRAC code 21) inhibiting the Complex III mitochondrial respiration in fungi.
[0244] Component (54.8) relates to 1 -[ 2-[ [ [ 1 -(4-chlorophcnyl)-l / 7-pyrazol-3-yl]oxy]mcthyl]-3- mcthylphcnylj- 1 ,4-di hydro-4- mcthyl-5 / 7-tctrazol-5-onc (provisional common name metyltetraprole, Registry Number 1472649-01-6), which is believed to be a quinone outside inhibitor (Qol) fungicide (FRAC code 45) inhibiting the Complex III mitochondrial respiration in fungi, and is effective against Qol resistant strains.
[0245] Component (54.9) relates to 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (provisional common name pyridachlometyl, Registry Number 1358061-55-8), which is believed to be promoter tubulin polymerization, resulting antifungal activity against fungal species belonging to the phyla Ascomycota and Basidiomycota.
[0246] Component (54.10) relates to (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3- carboxylate (provisional common name aminopyrifen, Registry Number 1531626-08-0) which is believed to inhibit GWT-1 protein in glycosylphosphatidylinositol-anchor biosynthesis in Neurospora crassa.
[0247] Component (b54.11) relates a compound of Formula b54.11 wherein
[0248] Rbland Rb3are each independently halogen; and
[0249] Rb2is H, halogen, C^-Cg alkyl, C^-Cg haloalkyl or Cg-Cg cycloalkyl.
[0250] Examples of compounds of Formula b54.11 include (b54.11a) methyl / V-[[5-[l-(2,6-difluoro-4- formylphcnylj- 1 / / -pyrazol-3-yl]-2-mcthy lphcnyl] methyl] carbamate, (b54.11b) methyl / V-[[5-[l- (4-cyclopiOpyl-2,6-dichloiOphcnyl)-l / / -pyrazol-3-y lJ-2-mcthy lphcnyl J methyl Jcarbamatc,
[0251] (b54.1 lc) methyl / V-[[5-[l-(4-chloro-2,6-difluorophenyl)-l / / -pyrazol-3-yl]-2-methylphenyl]- methyl]carbamate, (b54.11d) methyl / V-[[5-[l-(4-cyclopropyl-2,6-difluorophenyl)-l / / -pyrazol-3- yl]-2-methylphenyl]methyl]carbamate, (b54.11e) methyl / V-[[5-[l-[2,6-difluoro-4-(l- mcthylcthyl)phcnyl]-l / 7-pyrazol-3-yl] -2- methy lphcnyl] mcthyljcarbamatc and (b54.1 If) methyl A / -[[5-[ 1 -[2,6-difluoiO-4-(tnfluoiOmethyl)phenyl]- 1 / 7-pyrazol-3-yl]-2-methy lphcnyl] methyl] carbamate. Compounds of Formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT Patent Publications WO 2008 / 124092, WO 2014 / 066120 and WO 2020 / 097012.
[0252] Component (b54.12) relates a compound of Formula b54.12 b54.12 wherein Rb4is Rb6is C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl;
[0253] L is CH2 or CH2O, wherein the atom to the right is connected to the phenyl ring in Formula b54.12; and
[0254] Rb5is Examples of compounds of Formula b54.12 include (b54.12a) / V-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide and (b54.12b) ethyl l-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenoxy]methyl]-l -pyrazole-4- carboxylate. Compounds of Formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT Patent Publication WO 2020 / 056090. Component (b54.13) relates a compound of Formula b54.13 wherein
[0255] Rb7, Rb8and Rb9are each independently H, halogen or cyano; and
[0256] Rbl° and Rbl 1are each independently H, halogen, C[-C3 alkyl or C[-C3 methoxy. Examples of compounds of Formula b54.13 include (b54.13a) 4-( 2-ch loro-4- fluorophenyl )- / V-( 2- fluoro-4-methyl-6-nitrophenyl)-l, 3-dimethyl- l / -pyrazol-5-amine, (b54.13b) 4-(2-chloro-4- fluorophenyl)- V-(2-fluoro-6-nitrophenyl)-l, 3-dimethyl- l / -pyrazol-5-amine, (b54.13c) 3,5- difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]- 1,3-dimethyl- l / -pyrazol-4-yl]-benzonitrile and (b54.13d) / V-(2-chloro-4-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)- 1,3-dimethyl- 1 / / -pyrazol-5-aminc. Compounds of Formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT Patent Publication WO 2020051402.
[0257] Embodiments of the present invention as described in the Summary of the Invention include those described below. In the following Embodiments, Formula 1 includes stereoisomers, / V-oxides, and salts thereof, and reference to “a compound of Formula 1” includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.
[0258] Embodiment 1. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-l.
[0259] Embodiment 2. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-2.
[0260] Embodiment 3. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-3.
[0261] Embodiment 3a. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-2 or T-3.
[0262] Embodiment 4. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, R1is CF3.
[0263] Embodiment 5. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 4 wherein in Formula 1, W is O or S.
[0264] Embodiment 6. The composition of Embodiment 5 wherein W is O.
[0265] Embodiment 7. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 4 wherein in Formula 1, W is NR3.
[0266] Embodiment 8. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 7 wherein in Formula 1, R3is H, cyano, C(=0)OH, C1-C2 alkyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, OR3aor NR3bR3c.
[0267] Embodiment 9. The composition of Embodiment 8 wherein R3is H, cyano, C1-C2 alkyl or OR3a.
[0268] Embodiment 10. The composition of Embodiment 9 wherein R3is H, cyano or OR3a.
[0269] Embodiment 11. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 10 wherein in Formula 1, R3ais H, C1-C2 alkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl.
[0270] Embodiment 12. The composition of Embodiment 11 wherein R3ais H.
[0271] Embodiment 13. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 12 wherein in Formula 1, when R3bis separate (i.e. not taken together with R3cto form a ring), then R3bis H, C1-C3 alkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl.
[0272] Embodiment 14. The composition of Embodiment 13 wherein R3bis H or methyl.
[0273] Embodiment 15. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 14 wherein in Formula 1, when R3cis separate (i.e. not taken together with R3bto form a ring), then R3Cis H or C1-C2 alkyl.
[0274] Embodiment 16. The composition of Embodiment 15 wherein R3cis H or methyl.
[0275] Embodiment 17. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 16 wherein in Formula 1, X is O or NR5a.
[0276] Embodiment 18. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 16 wherein in Formula 1, X is O, S, NH or NOH.
[0277] Embodiment 19. The composition of Embodiment 18 wherein X is O or NOH.
[0278] Embodiment 20. The composition of Embodiment 20 wherein X is O.
[0279] Embodiment 21. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 20 wherein in Formula 1, Y is O or NR5b.
[0280] Embodiment 22. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 20 wherein in Formula 1, Y is O, S, NH or NOH.
[0281] Embodiment 23. The composition of Embodiment 22 wherein Y is O or NOH.
[0282] Embodiment 24. The composition of Embodiment 23 wherein Y is O.
[0283] Embodiment 25. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 24 wherein in Formula 1, R5aand R5bare each independently H, hydroxy or C1-C2 alkyl.
[0284] Embodiment 26. The composition of Embodiment 25 wherein R5aand R5bare each independently H, hydroxy or methyl.
[0285] Embodiment 27. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 26 wherein in Formula 1, when R2aand R2bare separate (i.e. not taken together to form a ring), then R2aand R2bare each independently H, C1-C3 alkyl, C2-C3 alkenyl, (CR4aR4b)p-OH, (CR4aR4b)p-Cl or (CR4aR4b)p-Br. Embodiment 27a. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 26 wherein in Formula 1, when R2aand R2bare separate (i.e. not taken together to form a ring), then R2aand R2bare each independently H, C1-C3 alkyl, C3-C35 trialkylsilyl or C3-C35 halotrialkylsilyl.
[0286] Embodiment 27b. The composition of Embodiment 27a wherein R2aand R2bare each independently H, methyl, trimethylsilyl or halotrimethylsilyl.
[0287] Embodiment 27c. The composition of Embodiment 27b wherein R2aand R2bare each independently H, methyl, trimethylsilyl or trifluoromethylsilyl
[0288] Embodiment 27d. The composition of Embodiment 27c wherein R2aand R2bare each independently H, methy or trimethylsilyl.
[0289] Embodiment 27e. The composition of Embodiment 27d wherein R2ais H and R2bis trimethylsilyl.
[0290] Embodiment 27f. The composition of Embodiment 27d wherein R2ais methyl and R2bis trimethylsilyl.
[0291] Embodiment 28. The composition of Embodiment 27 wherein R2aand R2bare each independently H, CrC3alkyl, (CR4aR4b)p-Cl or (CR4aR4b)p-Br.
[0292] Embodiment 29. The composition of Embodiment 28 wherein R2aand R2bare each independently H, methyl, (CR4aR4b)p-Cl or (CR4aR4b)p-Br.
[0293] Embodiment 30. The composition of Embodiment 28 wherein R2aand R2bare each independently H or C3-C3 alkyl.
[0294] Embodiment 31. The composition of Embodiment 30 wherein R2aand R2bare each independently H or C3-C2 alkyl.
[0295] Embodiment 32. The composition of Embodiment 31 wherein R2aand R2bare each independently H or methyl.
[0296] Embodiment 33. The composition of Embodiment 32 wherein R2aand R2bare each H.
[0297] Embodiment 34. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 33 wherein in Formula 1, when R2aand R2bare separate (i.e. not taken together to form a ring), then one of R2aand R2bis (CR4aR4b)p-OH, (CR4aR4b)p-SH, (CR4aR4b)p-Cl or (CR4aR4b)p-Br, and the other is H.
[0298] Embodiment 35. The composition of Embodiment 34 wherein one of R2aand R2bis (CR4aR4b)p-Cl or (CR4aR4b)p-Br, and the other is H.
[0299] Embodiment 36. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 35 wherein in Formula 1, R2aand R2bare each independently H, methyl, (CR4aR4b)p-OH, (CR4aR4b)p-Cl or (CR4aR4b)p-Br; or R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 2 carbon atom ring members are independently selected from C(=0) and C(=S), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members.
[0300] Embodiment 37. The composition of Embodiment 36 wherein R2aand R2bare each independently H or methyl; or R2aand R2bare taken together with the atoms X and
[0301] Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(=0), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members.
[0302] Embodiment 38. The composition of Embodiment 37 wherein R2aand R2bare each independently H or methyl; or R2aand R2bare taken together with the atoms X and
[0303] Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, cyano and methyl on carbon atom ring members.
[0304] Embodiment 39. The composition of Embodiment 38 wherein R2aand R2bare each H; or R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected methyl on a carbon atom ring member.
[0305] Embodiment 40. The composition of Embodiment 39 wherein R2aand R2bare each H; or R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
[0306] Embodiment 41. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 40 wherein in Formula 1, when R2aand R2bare taken together to form a ring (i.e. not separate), then R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(=0), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members.
[0307] Embodiment 42. The composition of Embodiment 41 wherein R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl and methoxy on carbon atom ring members.
[0308] Embodiment 43. The composition of Embodiment 42 wherein R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member.
[0309] Embodiment 44. The composition of Embodiment 43 wherein R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
[0310] Embodiment 45. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 44 wherein in Formula 1, R2cis C1-C3 alkyl, C3-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 alkynyl or C2-C3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano, hydroxy, SCºN and C3-C2alkoxy.
[0311] Embodiment 46. The composition of Embodiment 45 wherein R2cis C3-C2alkyl, C3-C2haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 alkynyl or C2-C3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano and methoxy.
[0312] Embodiment 46a. The composition of Embodiment 46 wherein R2cis C3-C2alkyl, C3-C2haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl or C2-C3 alkynyl.
[0313] Embodiment 47. The composition of Embodiment 46a wherein R2cis C3-C2alkyl, C2-C3 alkenyl or C2-C3 alkynyl. Embodiment 48. The composition of Embodiment 47 wherein R2cis methyl or ethyl.
[0314] Embodiment 48a. The composition of Embodiment 48 wherein R2cis ethyl.
[0315] Embodiment 49. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 48a wherein in Formula 1, R2dis H, cyano, halogen or C1-C2 alkyl.
[0316] Embodiment 49a. The composition of Embodiment 49 wherein R2dis H, cyano, Cl, F or methyl.
[0317] Embodiment 50. The composition of Embodiment 49a wherein R2dis H or methyl.
[0318] Embodiment 51. The composition of Embodiment 50 wherein R2dis H.
[0319] Embodiment 52. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 51 wherein in Formula 1, each R4aand R4bis independently H or C1-C2 alkyl.
[0320] Embodiment 53. The composition of Embodiment 52 wherein each R4aand R4bis independently H or methyl.
[0321] Embodiment 54. The composition of Embodiment 53 wherein each R4aand R4bis H.
[0322] Embodiment 55. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 54 wherein in Formula 1, p is 2.
[0323] Embodiment 56. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 54 wherein in Formula 1, p is 3.
[0324] Embodiment 57. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 56 wherein in Formula 1, wherein A1is CR6cR6d, O or S.
[0325] Embodiment 58. The composition of Embodiment 57 wherein A1is CR6cR6dor O.
[0326] Embodiment 59. The composition of Embodiment 58 wherein A1is CR6cR6d.
[0327] Embodiment 60. The composition of Embodiment 58 wherein A1is O.
[0328] Embodiment 61. The composition comprising components (a) and (b) described in the
[0329] Summary of the Invention or any one of Embodiments 1 through 60 wherein in Formula 1, A1is CH2, NH, O or S.
[0330] Embodiment 62. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 61 wherein in Formula 1, A1is N(R7a).
[0331] Embodiment 63. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 63 wherein in Formula 1, A2is a direct bond, CR6eR6f, O or S.
[0332] Embodiment 64. The composition of Embodiment 63 wherein A2is a direct bond, CR6eR6for O.
[0333] Embodiment 65. The composition of Embodiment 64 wherein A2is a direct bond or O.
[0334] Embodiment 66. The composition of Embodiment 65 wherein A2is a direct bond.
[0335] Embodiment 67. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 62 wherein in Formula 1, A2is a direct bond, CH2, NH, O or S.
[0336] Embodiment 67a. The composition of Embodiment 67 wherein A2is a direct bond, CH2 or
[0337] O.
[0338] Embodiment 68. The composition of Embodiment 67a wherein A2is a direct bond or O.
[0339] Embodiment 69. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 62 wherein in Formula 1, A2is N(R7b).
[0340] Embodiment 70. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 69 wherein in Formula 1, when A is A1-A2-CR6aR6b, then A1-A2-CR6aR6bis selected from OCH2, OCH(Me), CH(OH)CH2, CH2CH2, SCH2, OCF2and CH2OCH2.
[0341] Embodiment 71. The composition of Embodiment 70 wherein A1-A2-CR6aR6bis selected from OCH2, OCH(Me) and CH2CH2.
[0342] Embodiment 72. The composition of Embodiment 71 wherein A1-A2-CR6aR6bis selected from OCH2and CH2CH2.
[0343] Embodiment 73. The composition of Embodiment 72 wherein A1-A2-CR6aR6bis OCtl· .
[0344] Embodiment 74. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 74 wherein in Formula 1, when A is A^A2, then A'-A2is selected from O, CH2, OCtl· and
[0345] CH2O.
[0346] Embodiment 75. The composition of Embodiment 74 wherein A'-A2is selected from O, CH2and CH20.
[0347] Embodiment 76. The composition of Embodiment 75 wherein A'-A2is selected from O and Ctl· .
[0348] Embodiment 77. The composition of Embodiment 76 wherein A'-A2is O.
[0349] Embodiment 78. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 77 wherein in Formula 1, R6a, R6b, R6c, R6d, R6eand R6fare each independently H, cyano, hydroxy, Br, Cl, F or methyl.
[0350] Embodiment 79. The composition of Embodiment 78 wherein R6a, R6b, R6c, R6d, R6eand R6fare each independently H, cyano hydroxy or methyl.
[0351] Embodiment 80. The composition of Embodiment 79 wherein R6a, R6b, R6c, R6d, R6eand R6fare each independently H or methyl.
[0352] Embodiment 8E The composition of Embodiment 80 wherein R6a, R6b, R6c, R6d, R6eand R6fare each H.
[0353] Embodiment 82. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 81 wherein in Formula 1, R7aand R7bare each independently H, C1-C2 alkyl or C2-C3 alkylcarbonyl.
[0354] Embodiment 83. The composition of Embodiment 82 wherein R7aand R7bare each independently H or C1-C2 alkyl.
[0355] Embodiment 84. The composition of Embodiment 83 wherein R7aand R7bare each H.
[0356] Embodiment 85. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 84 wherein in Formula 1, when T is T-l or T-2, then A is A1-A2-CH2-
[0357] Embodiment 86. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 85 wherein in Formula 1, when T is T-l or T-2, then A is OCH2, SCH2, NHCH2, CH2CH2, OCH2CH2, SCH2CH2, NHCH2CH2, CH2OCH2, CH2SCH2or CH2NHCH2.
[0358] Embodiment 87. The composition of Embodiment 86 wherein when T is T-l or T-2, then A is OCH2, SCH2, CH2CH2, OCH2CH2, SCH2CH2, CH2OCH2or CH2SCH2.
[0359] Embodiment 88. The composition of Embodiment 87 wherein when T is T-l or T-2, then A is OCH2or CH2CH2.
[0360] Embodiment 89. The composition of Embodiment 88 wherein when T is T-l or T-2, then A is OCH2.
[0361] Embodiment 90. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 89 wherein in Formula 1, when T is T-3, then A is O, OCH2, SCH2, NHCH2, CH2, CH2CH2, CH20, CH2S or CH2NH.
[0362] Embodiment 91. The composition of Embodiment 82 wherein when T is T-3, then A is O, CH2or OCH2.
[0363] Embodiment 92. The composition of Embodiment 91 wherein when T is T-3, then A is O or CH2.
[0364] Embodiment 93. The composition of Embodiment 92 wherein when T is T-3, then A is O.
[0365] Embodiment 94. The composition comprising components (a) and (b) described in the
[0366] Summary of the Invention or any one of Embodiments 1 through 93 wherein in Formula 1, J is J-l through J-3, J-6 through J- 10 or J- 14.
[0367] Embodiment 95. The composition of Embodiment 94 wherein J is J-l, J-2, J-3, J-6 or J- 14.
[0368] Embodiment 96. The composition of Embodiment 95 wherein J is J-l, J-6 or J- 14.
[0369] Embodiment 97. The composition of Embodiment 96 wherein J is J-l or J-6.
[0370] Embodiment 97a. The composition of Embodiment 96 wherein J is J- 14.
[0371] Embodiment 98. The composition of Embodiment 97 wherein J is J-l.
[0372] Embodiment 99. The composition of Embodiment 97 wherein J is J-6.
[0373] Embodiment 100. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 99 wherein in Formula 1, each R8is independently F, Cl or methyl.
[0374] Embodiment 100a. The composition of Embodiment 100 wherein each R8is independently F or Cl.
[0375] Embodiment 101. The composition of Embodiment 100 wherein each R8is independently F or methyl.
[0376] Embodiment 101a. The composition of Embodiment 101 wherein each R8is F.
[0377] Embodiment 102. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 101a wherein in Formula 1, q is 0 or 1.
[0378] Embodiment 102a. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 101a wherein in Formula 1, q is 3 or 4.
[0379] Embodiment 102b. The composition of Embodiment 102a wherein in Formula 1, q is 4.
[0380] Embodiment 103. The composition of Embodiment 102 wherein q is 0.
[0381] Embodiment 103a. The composition of Embodiment 102 wherein q is 1.
[0382] Embodiment 104. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 103a wherein in Formula 1, each R9aand R9bis independently H, halogen, C|-C3 alkyl, C1-C3 haloalkyl, C3-C3 alkoxy or C3-C3 haloalkoxy. Embodiment 105. The composition of Embodiment 104 wherein each R9aand R9bis independently H, halogen, Ci-C2alkyl or Ci-C2haloalkyl.
[0383] Embodiment 106. The composition of Embodiment 105 wherein each R9aand R9bis independently H, halogen or methyl.
[0384] Embodiment 107. The composition of Embodiment 106 wherein each R9aand R9bis independently H or methyl.
[0385] Embodiment 108. The composition of Embodiment 107 wherein each R9aand R9bis H.
[0386] Embodiment 109. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 108 wherein in Formula 1, n is 0, 1 or 2.
[0387] Embodiment 109a. The composition of Embodiment 109 wherein n is 1 or 2.
[0388] Embodiment 110. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 109a wherein in Formula 1, n is 0 or 1.
[0389] Embodiment 111. The composition of Embodiments 109, 109a or 110 wherein n is 1.
[0390] Embodiment 112. The composition of Embodiments 109 or 110 wherein n is 0.
[0391] Embodiment 113. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 112 wherein in Formula 1, L is a direct bond, CH2, CH(Me) or CH2CH2.
[0392] Embodiment 113a. The composition of Embodiment 113 wherein L is a direct bond, CH2 or CH2CH2.
[0393] Embodiment 114. The composition of Embodiment 113a wherein L is a direct bond or
[0394] CH2.
[0395] Embodiment 115. The composition of Embodiment 114 wherein L is CH2.
[0396] Embodiment 115a. The composition of Embodiment 114 wherein L is a direct bond.
[0397] Embodiment 116. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 115a wherein in Formula 1, E is E1.
[0398] Embodiment 116a. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 116 wherein in Formula 1, when L is a direct bond, then E is E1.
[0399] Embodiment 117. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 116a wherein in Formula 1, E1is cyano, nitro, C(=0)H, C(=0)OH or SON; or C^-C^ alkoxy, C2-C6 alkenyloxy, C^-C^ alkylsulfonyl, C2-C6 alkenylsulfonyl, C^- ^ alkynylsulfonyl, CrC6alkylsulfonylamino, alkenylsulfonylamino, alkynylsulfonylamino, C|-C^ alkylaminosulfonyl, C2-C6 dialkylaminosulfonyl, C2-C6 alkenylaminosulfonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, CyC^ alkenylaminocarbonyl, C^-C^ alkynylaminocarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl or C2-C6 alkoxycarbonylamino, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b.
[0400] Embodiment 118. The composition of Embodiment 117 wherein E1is cyano, nitro, C(=0)H, C(=0)OH or SON; or CrC6alkoxy, C2-C6alkenyloxy, CrC6alkylsulfonyl, C^-C^ alkylsulfonylamino, C2-C6 alkenylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, CyC^ alkenyloxycarbonyl or CyC^ alkynyloxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from RlOb.
[0401] Embodiment 119. The composition of Embodiment 118 wherein E1is C^-C^ alkoxy, C|- C, alkylsulfonyl, C2-C6 alkylcarbonyl or C2-C6 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b.
[0402] Embodiment 120. The composition of Embodiment 119 wherein E1is C1-C3 alkoxy,
[0403] C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b.
[0404] Embodiment 120a. The composition of Embodiment 120 wherein E1is C1-C3 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a.
[0405] Embodiment 121. The composition of Embodiment 120 wherein E1is C1-C2 alkoxy, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b.
[0406] Embodiment 121a. The composition of Embodiment 120 wherein E1is C1-C2 alkoxy, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a.
[0407] Embodiment 121b. The composition of Embodiment 121a wherein E1is methoxy optionally substituted with up to 1 substituent selected from R10a.
[0408] Embodiment 121c. The composition of Embodiment 121a wherein E1is methoxy substituted with 1 substituent selected from R10a.
[0409] Embodiment 122. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 121c wherein in Formula 1, R10ais phenyl optionally substituted with up to 3 substituents independently selected from Rlla; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from Rllaon carbon atom ring members and Rl lbon nitrogen atom ring members.
[0410] Embodiment 123. The composition of Embodiment 122 wherein R10ais phenyl optionally substituted with up to 2 substituents independently selected from Rl la; or a 5- to 6- membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members and Rllbon nitrogen atom ring members.
[0411] Embodiment 123a. The composition of Embodiment 123 wherein R10ais a 5-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O and up to 3 N atoms, each ring optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members.
[0412] Embodiment 123b. The composition of Embodiment 123a wherein R10ais pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members.
[0413] Embodiment 123c. The composition of Embodiment 123b wherein R10ais pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members.
[0414] Embodiment 123d. The composition of Embodiment 123c wherein R10ais pyrazolyl optionally substituted with up to 1 substituent selected from Rl laon a carbon atom ring member.
[0415] Embodiment 124. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 123c wherein in Formula 1, each R10bis independently cyano, halogen, hydroxy, C4-C4alkyl, C4-C4haloalkyl, CyC^ cycloalkyl, C1-C4alkoxy, C4-C4haloalkoxy, C1-C4alkylsulfonyl, C4-C4haloalkylsulfonyl, C1-C4alkylamino, C2-C4dialkylamino, C2-C4alkylcarbonyl or C2-C5 alkoxycarbonyl.
[0416] Embodiment 125. The composition of Embodiment 124 wherein each R10bis independently halogen, hydroxy, C4-C4alkyl, C4-C4haloalkyl, C1-C4alkoxy,
[0417] C4-C4haloalkoxy, C4-C4alkylsulfonyl, C2-C4alkylcarbonyl or C2-C5 alkoxycarbonyl.
[0418] Embodiment 125a. The composition of Embodiment 125 wherein each R10bis independently halogen, C4-C2alkyl, C4-C2haloalkyl, C4-C2alkoxy or C2-C4alkoxycarbonyl.
[0419] Embodiment 126. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 125a wherein in Formula 1, each Rl lais independently halogen, C4-C4alkyl, C4-C4haloalkyl, C%- C4alkenyl, C2-C4alkynyl, C4-C4alkoxy, C4-C4haloalkoxy, C2-C4alkenyloxy, C%- C4alkynyloxy, C2-C4alkoxyalkyl, alkylcarbonyloxy, C1-C4alkylsulfonyl,
[0420] C4-C4haloalkylsulfonyl, C4-C4alkylsulfonyloxy, C2-C4alkylcarbonyl, C3-C5 alkenylcarbonyl, C3-C5 alkynylcarbonyl, alkoxycarbonyl, C3-C7alkenyloxycarbonyl, C3-C7alkynyloxycarbonyl, alkylaminocarbonyl, CyC^ alkenylaminocarbonyl, CyC^ alkynylaminocarbonyl or C3-C8 dialkylaminocarbonyl.
[0421] Embodiment 127. The composition of Embodiment 126 wherein each Rllais independently halogen, C4-C4alkyl, C4-C4haloalkyl, C2-C4alkenyl, C1-C4alkoxy, C4-C4haloalkoxy, C2-C4alkenyloxy, C2-C4alkoxyalkyl, C2-C4alkylcarbonyl, C2- C, alkoxycarbonyl, C3-C7alkenyloxycarbonyl or C2-C6 alkylaminocarbonyl.
[0422] Embodiment 128. The composition of Embodiment 127 wherein each Rllais independently halogen, C4-C4alkyl, C4-C4haloalkyl, C1-C4alkoxy, C4-C4haloalkoxy, C2-C4alkenyloxy, C2-C4alkylcarbonyl, C2-C4alkoxycarbonyl or C3- C5 alkenyloxycarbonyl.
[0423] Embodiment 128a. The composition of Embodiment 128 wherein each Rl lais independently halogen, C4-C2alkyl, C4-C2haloalkyl, C1-C2alkoxy or C2-C3 alkoxycarbonyl.
[0424] Embodiment 128b. The composition of Embodiment 128a wherein each R1 lais independently methoxy carbonyl or ethoxycarbonyl. Embodiment 128c. The composition of Embodiment 128b wherein each Rl lais ethoxycarbonyl.
[0425] Embodiment 129. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 128c wherein in Formula 1, each Rl lbis independently C1-C2alkyl, C1-C2alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl.
[0426] Embodiment 130. The composition of Embodiment 129 wherein each Rllbis independently methyl, methoxy, methylcarbonyl or methoxycarbonyl.
[0427] Embodiment 13 E The composition of Embodiment 130 wherein each Rllbis independently methyl or methoxy.
[0428] Embodiment 132. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 131 wherein in Formula 1, E is E2.
[0429] Embodiment 133. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 132 wherein in Formula 1, G is phenyl optionally substituted with up to 3 substituents independently selected from R13; or a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R13; or a 3- to 7-membered nonaromatic ring or an 8- to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=0), S(=0) and S(=0)2, each ring or ring system optionally substituted with up to 3 substituents independently selected from R13.
[0430] Embodiment 134. The composition of Embodiment 133 wherein G is selected from G-l through G-l 18 as shown in Exhibit A.
[0431] Exhibit A
[0432] G-l G-2 G-3 G-4
[0433] G-25 G-26 G-27 G-28
[0434] G-49 G-50 G-51 G-52
[0435] G-73 G-74 G-75 G-76
[0436] G-97 G-98 G-99 G-100
[0437] G-117 G-118 wherein the floating bond is connected to Z in Formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3.
[0438] Embodiment 135. The composition of Embodiment 134 wherein G is G-l through G-16, G-20, G-22 through G-30, G-36 through G-42, G-54 through G-60, G-85, G-86, G- 108, G-110 or G-lll.
[0439] Embodiment 136. The composition of Embodiment 135 wherein G is G-l through G-16, G-22, G-24, G-25, G-26, G-28, G-29, G-30, G-36, G-37, G-38, G-41, G-42, G-54, G-57, G-58, G-59, G-60, G-85, G-86, G-108, G-110 or G-lll.
[0440] Embodiment 137. The composition of Embodiment 136 wherein G is G-l through G-13, G-22, G-24, G-25, G-26, G-28, G-29, G-41, G-42, G-54, G-57, G-58, G-59 or G-60.
[0441] Embodiment 138. The composition of Embodiment 137 wherein G is G-l, G-2, G-3, G-7, G-8, G-9, G-10, G-12, G-13, G-22, G-29, G-42, G-54 or G-58.
[0442] Embodiment 139. The composition of Embodiment 138 wherein G is G-l, G-3, G-12, G- 13, G-22 or G-42.
[0443] Embodiment 140. The composition of Embodiment 139 wherein G is G-l, G-3, G-12, G- 13 or G-22.
[0444] Embodiment 141. The composition of Embodiment 140 wherein G is G-l, G-3, G-12 or G-
[0445] 22.
[0446] Embodiment 142. The composition of Embodiment 141 wherein G is G-l or G-12.
[0447] Embodiment 143. The composition of Embodiment 142 wherein G is G-l.
[0448] Embodiment 144. The composition of Embodiment 142 wherein G is G-12.
[0449] Embodiment 145. The composition of Embodiment 140 wherein G is G-3.
[0450] Embodiment 146. The composition of Embodiment 140 wherein G is G-22.
[0451] Embodiment 147. The composition of Embodiment 143 wherein the 2-position of G-l is connected to Z and the 4-position is connected to R13.
[0452] Embodiment 148. The composition of Embodiment 143 wherein the 2-position of G-l is connected to Z and the 5-position is connected to R13.
[0453] Embodiment 149. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 4-position is connected to R13.
[0454] Embodiment 150. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 3-position is connected to R13.
[0455] Embodiment 151. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 3- and 5-positions are connected to R13.
[0456] Embodiment 152. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 5-position is connected to R13.
[0457] Embodiment 153. The composition of Embodiment 145 wherein the 1-position of G-3 is connected to Z and the 4-position is connected to R13.
[0458] Embodiment 154. The composition of Embodiment 146 wherein the 4-position of G-22 is connected to Z and the 2-position is connected to R13.
[0459] Embodiment 155. The composition of any one of Embodiments 147 through 154 wherein Z is a direct bond.
[0460] Embodiment 156. The composition of any one of Embodiments 147 through 155 wherein x is 1 and R13is methoxycarbonyl or ethoxycarbonyl. Embodiment 157. The composition of any one of Embodiments 134 through 155 wherein x is 1 or 2.
[0461] Embodiment 158. The composition of Embodiment 157 wherein x is 1.
[0462] Embodiment 159. The composition of Embodiment 157 wherein x is 2.
[0463] Embodiment 160. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 134 through 155 wherein in Formula 1, x is 0.
[0464] Embodiment 16 E The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 159 wherein in Formula 1, each R13is independently cyano, halogen, NR14aR14b, C(=0)NR14aR14b, C(R15)=NR16, N=CR17NR18aR18bor -U-V-Q; or CrC6alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C|-C^ alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C^-C^ alkylsulfonyl, C|-C^ alkylsulfonyloxy, C^-C^ alkylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, CyC^ alkenyloxycarbonyl, CyC^ alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy, C2-C6 alkoxycarbonyloxy, C4-C7 cycloalkoxycarbonyloxy, C2-C6 alkylaminocarbonyloxy, C2-C6 alkylcarbonylamino, C2-C6 alkoxycarbonylamino or C2-C6 alkylaminocarbonylamino, each optionally substituted with up to 3 substituents independently selected from R19.
[0465] Embodiment 162. The composition of Embodiment 161 wherein each R13is independently cyano, halogen, C(=0)NR14aR14bor -U-V-Q; or C^-C^ alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C|-C^ alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C^-C^ alkylsulfonyl, C^-C^ alkylsulfonyloxy, C|-C^ alkylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl or C2-C6 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19.
[0466] Embodiment 163. The composition of Embodiment 162 wherein each R13is independently C(=0)NR14aR14bor -U-V-Q; or CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, CrC6alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C|-C^ alkylsulfonyl, C|-C^ alkylsulfonyloxy, C^-C^ alkylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, CyC^ alkenyloxycarbonyl, CyC^ alkynyloxycarbonyl, C4-C6 cycloalkoxycarbonyl or C2-C6 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19.
[0467] Embodiment 163a. The composition of Embodiment 162 wherein each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.
[0468] Embodiment 163b. The composition of Embodiment 163a wherein each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19.
[0469] Embodiment 164. The composition of Embodiment 163a wherein each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C6 alkoxycarbonyl, CyC^ alkenyloxycarbonyl, CyC^ alkynyloxycarbonyl or C2-C6 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19.
[0470] Embodiment 164a. The composition of Embodiment 164 wherein each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C6 alkoxycarbonyl, CyC^ alkenyloxycarbonyl, or CyC^ alkynyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.
[0471] Embodiment 165. The composition of Embodiment 164a wherein each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, or C3-C5 alkynyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.
[0472] Embodiment 165a. The composition of Embodiment 165 wherein each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl or C3-C5 alkenyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.
[0473] Embodiment 166. The composition of Embodiment 165 wherein each R13is independently C2-C5 alkoxycarbonyl or C3-C5 alkenyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.
[0474] Embodiment 167. The composition of Embodiment 166 wherein each R13is independently C2-C5 alkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.
[0475] Embodiment 168. The composition of Embodiment 167 wherein each R13is independently methoxycarbonyl or ethoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.
[0476] Embodiment 169. The composition of Embodiment 168 wherein each R13is independently methoxycarbonyl or ethoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19.
[0477] Embodiment 170. The composition of Embodiment 169 wherein each R13is independently ethoxycarbonyl optionally substituted with up to 1 substituent selected from R19.
[0478] Embodiment 171. The composition of Embodiment 169 wherein each R13is independently methoxycarbonyl or ethoxycarbonyl.
[0479] Embodiment 172. The composition of Embodiment 171 wherein each R13is ethoxycarbonyl.
[0480] Embodiment 173. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 172 wherein in Formula 1, when each R14ais separate (i.e. not taken together with R14bto form a ring), then each R14ais independently H, cyano, hydroxy, C4-C4alkyl, C4-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C2-C4alkylcarbonyl, C2-C5 alkoxycarbonyl or C3-C5 dialkylaminocarbonyl.
[0481] Embodiment 174. The composition of Embodiment 173 wherein each R14ais independently H, cyano, C4-C4alkyl, C4-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl, C2-C4alkylcarbonyl, C2-C5 alkoxycarbonyl or C3-C5 dialkylaminocarbonyl.
[0482] Embodiment 175. The composition of Embodiment 174 wherein each R14ais independently H, C4-C2alkyl, C2-C4alkenyl, C2-C4alkynyl, C2-C4alkylcarbonyl or C2-C4alkoxycarbonyl.
[0483] Embodiment 176. The composition of Embodiment 175 wherein each R14ais independently H or C4-C2alkyl.
[0484] Embodiment 177. The composition of Embodiment 176 wherein each R14ais independently H or methyl.
[0485] Embodiment 177a. The composition of Embodiment 177 wherein each R14ais H.
[0486] Embodiment 178. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 177a wherein in Formula 1, when each R14bis separate (i.e. not taken together with R14ato form a ring), then each R14bis independently H, C|-Cf, alkyl, C|-Cf, haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C4-C IQalkylcycloalkyl, C4-C IQcycloalkylalkyl, C4-C10 halocycloalkylalkyl, C2-CQalkoxyalkyl, C2-CQhaloalkoxyalkyl, C2-CQalkylthioalkyl, C2-CQalkylsulfonylalkyl, C2-C6 alkylaminoalkyl or C3-C8 dialkylaminoalkyl, each optionally substituted with up to 1 substituent selected from cyano, hydroxy, nitro, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.
[0487] Embodiment 179. The composition of Embodiment 178 wherein each R14bis independently H, C4-C4 alkyl, C4-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkylaminoalkyl or C3-C5 dialkylaminoalkyl.
[0488] Embodiment 180. The composition of Embodiment 179 wherein each R14bis independently H, C4-C3 alkyl, C4-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl or C2-C4 alkoxyalkyl.
[0489] Embodiment 181. The composition of Embodiment 180 wherein each R14bis independently H, C4-C3 alkyl, C4-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl.
[0490] Embodiment 181a. The composition of Embodiment 181 wherein each R14bis independently H, C4-C2 alkyl, C4-C2 haloalkyl or cyclopropylmethyl.
[0491] Embodiment 181b. The composition of Embodiment 181a wherein each R14bis independently H, methyl or cyclopropylmethyl.
[0492] Embodiment 182. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 181b wherein in Formula 1, when R14aand R14bare taken together to form a 4- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
[0493] Embodiment 183. The composition of Embodiment 182 wherein R14aand R14bare taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
[0494] Embodiment 184. The composition of Embodiment 183 wherein R14aand R14bare taken together to form an azetidinyl or pyrrolidinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
[0495] Embodiment 185. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 184 wherein in Formula 1, each R15is independently H, cyano, halogen, methyl or methoxy.
[0496] Embodiment 186. The composition of Embodiment 185 wherein each R15is independently H or methyl.
[0497] Embodiment 187. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 186 wherein in Formula 1, each R16is independently hydroxy, NR20aR20b, C4-C2 alkoxy, C2-C4 alkenyloxy, C2-C4 alkylcarbonyloxy or C2-C4 alkoxycarbonyloxy.
[0498] Embodiment 188. The composition of Embodiment 187 wherein each R16is independently hydroxy, NR20aR20bor C4-C4 alkoxy.
[0499] Embodiment 189. The composition of Embodiment 188 wherein each R16is independently hydroxy, NR20aR20bor methoxy.
[0500] Embodiment 190. The composition of Embodiment 189 wherein each R16is hydroxy.
[0501] Embodiment 19 E The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 190 wherein in Formula 1, each R17is independently H or methyl.
[0502] Embodiment 192. The composition of Embodiment 191 wherein each R17is H.
[0503] Embodiment 193. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 192 wherein in Formula 1, when each R18aand R18bis separate (i.e. not taken together to form a ring), then each R18aand R18bis independently H, methyl or ethyl.
[0504] Embodiment 194. The composition of Embodiment 193 wherein each R18aand R18bis independently H or methyl.
[0505] Embodiment 195. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 194 wherein in Formula 1, when R18aand R18bare taken together to form a 5- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 methyl groups.
[0506] Embodiment 196. The composition of Embodiment 195 wherein R18aand R18bare taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.
[0507] Embodiment 197. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 196 wherein in Formula 1, each R19is independently cyano, halogen, hydroxy, C4-C3 alkyl, C|-C3 haloalkyl, CyC^ cycloalkyl, C4-C3 alkoxy, C4-C3 haloalkoxy, C2-C3 alkoxyalkoxy, C1-C3 alkylthio, C|-C3 alkylsulfinyl, C|-C3 alkylsulfonyl, C1-C3 haloalkylsulfonyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl.
[0508] Embodiment 198. The composition of Embodiment 197 wherein each R19is independently cyano, halogen, hydroxy, C3-C2 alkyl, C3-C2 haloalkyl, C3-C6 cycloalkyl, C3-C2 alkoxy, C3-C2 haloalkoxy, C3-C2 alkylthio, C3-C2 alkylsulfonyl, C3-C2 haloalkylsulfonyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, C2-C3 alkoxycarbonyl or C2-C3 alkylaminocarbonyl.
[0509] Embodiment 199. The composition of Embodiment 197 wherein each R19is independently cyano, halogen, C3-C2 alkyl, C3-C2 haloalkyl, C3-C6 cycloalkyl, C3-C2 alkoxy, C3-C2 haloalkoxy, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl or C2-C3 alkoxycarbonyl.
[0510] Embodiment 200. The composition of Embodiment 199 wherein each R19is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl.
[0511] Embodiment 200a. The composition of Embodiment 200 wherein each R19is independently cyano, halogen, cyclopropyl or methoxy.
[0512] Embodiment 200b. The composition of Embodiment 200a wherein each R19is independently cyano, Cl, F, cyclopropyl or methoxy.
[0513] Embodiment 201. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 200b wherein in Formula 1, each U is independently a direct bond, C(=0)0 or C(=0)N(R25).
[0514] Embodiment 202. The composition of Embodiment 201 wherein each U is independently a direct bond or C(=0)0.
[0515] Embodiment 203. The composition of Embodiment 202 wherein each U is C(=0)0.
[0516] Embodiment 204. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 203 wherein in Formula 1, each V is independently a direct bond; or C^-C^ alkylene, C2-C6 alkenylene or CyC^ alkynylene, each optionally substituted with up to 2 substituents independently selected from halogen, cyano, nitro, hydroxy, C3-C2 alkyl, C3-C2 haloalkyl, C3-C2 alkoxy and C3-C2 haloalkoxy.
[0517] Embodiment 205. The composition of Embodiment 204 wherein each V is independently a direct bond; or C3-C3 alkylene, each optionally substituted with up to 2 substituents independently selected from halogen, hydroxy, C3-C2 alkyl, C3-C2 alkoxy and C1-C2haloalkoxy.
[0518] Embodiment 206. The composition of Embodiment 205 wherein each V is independently a direct bond or C1-C3 alkylene.
[0519] Embodiment 207. The composition of Embodiment 206 wherein each V is independently a direct bond or CH2.
[0520] Embodiment 208. The composition of Embodiment 207 wherein each V is a direct bond.
[0521] Embodiment 209. The composition of Embodiment 207 wherein each V is independently C1-C2alkylene.
[0522] Embodiment 210. The composition of Embodiment 209 wherein each V is CH2.
[0523] Embodiment 211. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 210 wherein in Formula 1, each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R27; or a 3- to 6-membered nonaromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=0), C(=S), S(=0) and S(=0)2, each ring optionally substituted with up to 2 substituents independently selected from R27.
[0524] Embodiment 212. The composition of Embodiment 210 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl, thienyl, isoxazolinyl, piperidinyl, morpholinyl or piperazinyl, each optionally substituted with up to 2 substituents independently selected from R27.
[0525] Embodiment 213. The composition of Embodiment 212 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each optionally substituted with up to 2 substituents independently selected from R27.
[0526] Embodiment 214. The composition of Embodiment 213 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl or pyrazolyl, each optionally substituted with up to 2 substituents independently selected from R27.
[0527] Embodiment 214a. The composition of Embodiment 214 wherein each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27.
[0528] Embodiment 214b. The composition of Embodiment 214a wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27.
[0529] Embodiment 215. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 214b wherein in Formula 1, when each R20ajsseparate (i.e. not taken together with R20bto form a ring), then each R20ajsindependently H, methyl or methylcarbonyl.
[0530] Embodiment 216. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 215 wherein in Formula 1, when each R20bjsseparate (i.e. not taken together with R20ato form a ring), then each R20bjsindependently H, cyano, methyl, methylcarbonyl, methoxycarbonyl, methoxycarbonylmethyl, methylaminocarbonyl or dimethylaminocarbonyl.
[0531] Embodiment 217. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 216 wherein in Formula 1, when R20aand R20barctaken together to form a 5- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 methyl groups.
[0532] Embodiment 218. The composition of Embodiment 217 wherein R20aand R20barctaken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.
[0533] Embodiment 219. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 218 wherein in Formula 1, each R21and R23is independently H, cyano, halogen, methyl or methoxy.
[0534] Embodiment 220. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 219 wherein in Formula 1, each R22is independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl; or phenyl optionally substituted with up to 2 substituents independently selected halogen and methyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 substituents independently selected from halogen and methyl.
[0535] Embodiment 221. The composition of Embodiment 220 wherein each R22is independently H or C1-C2 alkyl.
[0536] Embodiment 222. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 221 wherein in Formula 1, each R24is independently H, cyano or Ci-C2alkyl.
[0537] Embodiment 223. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 222 wherein in Formula 1, each R25and R26is independently H, cyano, hydroxy, C4-C4 alkyl or CrC4haloalkyl.
[0538] Embodiment 224. The composition of Embodiment 223 wherein each R25and R26is independently H, cyano, hydroxy or C4-C2 alkyl.
[0539] Embodiment 225. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 224 wherein in Formula 1, each R27is independently halogen, cyano, C4-C4 alkyl, C4-C4 haloalkyl or C4-C4 alkoxy.
[0540] Embodiment 226. The composition of Embodiment 225 wherein each R27is independently halogen, cyano, C4-C2 alkyl, C4-C2 haloalkyl or C4-C2 alkoxy.
[0541] Embodiment 227. The composition of Embodiment 226 wherein each R27is independently halogen, methyl or methoxy.
[0542] Embodiment 228. The composition of Embodiment 227 wherein each R27is independently halogen.
[0543] Embodiment 229. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 228 wherein in Formula 1, Z is a direct bond, O, NH, C(=0), C(=0)NH, NHC(=0), NHC(=0)NH, OC(=0)NH, NHC(=0)0, S(=0)2NH, NHS(=0)2or NHS(=0)2NH.
[0544] Embodiment 230. The composition of Embodiment 229 wherein Z is a direct bond, O, NH, C(=0), C(=0)NH or NHC(=0).
[0545] Embodiment 231. The composition of Embodiment 230 wherein Z is a direct bond, O, NH or C(=0).
[0546] Embodiment 232. The composition of Embodiment 231 wherein Z is a direct bond. Embodiment 233. The composition of Formula 1 or any one of Embodiments 1 through 232 wherein each R28is independently H or C|-C3 alkyl. Embodiment 234. The composition of Embodiment 233 wherein each R28is independently
[0547] H or methyl.
[0548] Embodiment 235. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 234 wherein in Formula 1, m is 0 or 2. Embodiment 236. The composition of Embodiment 235 wherein m is 2.
[0549] Embodiment 237. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 236 wherein component (a) does not comprise an / V-oxide of a compound of Formula 1. Embodiment 238. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 236 wherein component (a) comprises a compound selected from the group consisting of ethyl l-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-l / / -pyrazole-4-carboxylate (Compound 1); ethyl 1 - [ [4- [ [2-(trifluoro methyl)- 1 ,3 -dioxolan-2-yl] methoxy ]phenyl] methyl] - 1 / 7-pyrazolc-4- carboxylate (Compound 32); ethyl l-[[4-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen- l-yl]oxy]phenyl]methyl]- l / / -pyrazole-4- carboxylate (Compound 64); ethyl l-[[4-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen- l-yl]oxy]phenyl]methyl]- l / / -pyrazole-3- carboxylate (Compound 231); ethyl l-[[4-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen- l-yl]oxy]-3-fluorophenyl]methyl]- IH- pyrazole-4-carboxylate (Compound 262); ethyl l-[[3-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen- l-yl]oxy]phenyl]methyl]- l / / -pyrazole-4- carboxylate (Compound 265); ethyl l-[[4-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen- l-yl]oxy]phenoxy]methyl]- 1 / 7-pyrazole- 4-carboxylate (Compound 364);
[0550] A / -(cyclopropylmethyl)-2-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]- methyl]thiazole-4-carboxamide (Compound 71);
[0551] 2-methylpropyl 1 -[ [4- [[ 2-(tri fl uoromcthy 1 )- 1 ,3-dioxolan-2-yl] methoxy] phenyl] methyl]- 1 H- pyrazole-4-carboxylate (Compound 126); cyclopropylmethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]- 177-pyrazole-4-carboxylate (Compound 127); ethyl l-[2-[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l-yl]oxy]phenyl]ethyl]-177-pyrazole-4- carboxylate (Compound 132);
[0552] 2-methoxyethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]-177- pyrazole-4-carboxylate (Compound 162);
[0553] 2-butyn-l-yl 1 - [[4-[[2-(trifluoiOmcthyl)-l ,3-dioxolan-2-ylJmcthoxyJphcnyl] methyl]- 1 H- pyrazole-4-carboxylate (Compound 163);
[0554] 3-cyanopropyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]-177- pyrazole-4-carboxylate (Compound 171); phenylmethyl 1 - [ [4- [ [( lZ)-2-ethoxy-3 ,3 ,3 -trifluoro- 1 -propen- 1 -yl] oxy ]phenyl] methyl] - 177- pyrazole-4-carboxylate (Compound 186); butyl 1 -[[4-[[(lZ)-2-cthoxy-3,3,3-trifluoro- 1 -propcn-1 -yljoxyjphcny 1] methyl J-l 77-pyrazolc-4- carboxylate (Compound 218);
[0555] 3-chloropropyl l-[[4-[[( lZ)-2-cthoxy-3, 3, 3-tnfluoro-l-piOpcn-l-yl]oxy]phcnyl] methyl]- 1 / 7- pyrazole-4-carboxylate (Compound 221); methyl 4-(3,3,3-trifluoiO-2,2-dihydiOxypiOpoxy)phcnylcarboxylatc (Compound 229); ethyl l-[[3-fluoro-4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]-177- pyrazole-4-carboxylate (Compound 263); ethyl 1 - [ [4- [ [( lZ)-2-ethoxy-3 ,3 ,3 -trifluoro- 1 -propen- 1 -yl] oxy ]phenylmethoxy] methyl] -177- pyrazole-4-carboxylate (Compound 297); methyl l-[[3-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen- l-yl]oxy]phenyl]methyl]- 177-pyrazole-
[0556] 4-carboxylate (Compound 330); and propyl l-[[3-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l-yl]oxy]phenyl]methyl]-177-pyrazole-
[0557] 4-carboxylate (Compound 331).
[0558] Embodiment 239. The composition of Embodiment 238 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 71, 126, 127, 132, 162, 163, 171, 186, 218, 229, 263, 297, 330 and 331.
[0559] Embodiment 240. The composition of Embodiment 239 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 71, 126, 127,
[0560] 132, 162, 163, 171, 218, 229 and 263.
[0561] Embodiment 241. The composition of Embodiment 240 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 126, 127, 132, 162, 163, 171 and 263. Embodiment 242. The composition of Embodiment 241 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 126, 132, 163 and 263.
[0562] Embodiment 243. The composition of Embodiment 242 wherein component (a) comprises a compound selected from the group consisting of Compounds 32 and 64.
[0563] Embodiment 243a. The composition of Embodiment 243 wherein component (a) is Compound 32.
[0564] Embodiment 243b. The composition of Embodiment 243 wherein component (a) is Compound 64.
[0565] Embodiment 244. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2- yljmcthoxy] phenyl] methyl]- 1 / / -pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof.
[0566] Embodiment 245. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof.
[0567] Embodiment 246. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l-yl]oxy]-3- fluorophcnyljmcthylj-l / 7-pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof.
[0568] Embodiment 247. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[3-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof.
[0569] Embodiment 248. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnoxy] methyl]- 1 / 7-pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof. Embodiment 249. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[2-[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljcthylj-l / 7-pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof.
[0570] Embodiment 250. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is phenylmethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljmcthylj-l / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof.
[0571] Embodiment 251. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is butyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljmcthylj-l / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof.
[0572] Embodiment 252. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is 3-chloropropyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljmcthylj-l / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof.
[0573] Embodiment 253. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnylmcthoxy] methyl]- 1 / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof.
[0574] Embodiment 254. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is methyl l-[[3-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof.
[0575] Embodiment 255. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is propyl l-[[3-[[(lZ)-2 -ethoxy-3, 3, 3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l / 7-pyrazolc-4-carboxylatc, its (^-isomer or a mixture thereof. Embodiment 256. The composition of Embodiments 238 through 255 wherein wherin component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, metconazole, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, boscalid, fluopyram, luindapyr, fluxapyroxad, isopyrazam, kresoxim-methyl, penthiopyrad, picoxystrobin, proquinazid, pyraclostrobin, quinoxyfen, sedaxane or trifloxystrobin.
[0576] Embodiment 257. The composition of Embodiments 238 through 256 wherein wherin component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, isopyrazam, picoxystrobin, pyraclostrobin, or trifloxystrobin.
[0577] Embodiment 258. The composition of Embodiment 257 wherein (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, isopyrazam, picoxystrobin, pyraclostrobin or trifloxystrobin.
[0578] Embodiments of this invention, including Embodiments 1-258 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments not only to the compositions comprising compounds of Formula 1 with at least one other fungicidal compound but also to compositions comprising compounds of Formula 1 with at least one invertebrate pest control compound or agent, and also to the compounds of Formula 1 and their compositions, and also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-258 above as well as any other embodiments described herein, and any combination thereof, pertain to the methods of the present invention. Therefore of note as a further embodiment is the composition disclosed above comprising (a) at least one compound selected from the compounds of Formula 1 described above, / V-oxides, and salts thereof; and at least one invertebrate pest control compound or agent. Combinations of Embodiments 1-258 are illustrated by:
[0579] Embodiment A. The composition comprising components (a) and (b) described Summary of the
[0580] Invention wherein component (a) comprises a compound of Formula 1 or salt thereof, wherein in Formula 1,
[0581] R1is CF3, CC13or CF2C1;
[0582] W is O;
[0583] R5aand R5bare each independently H, hydroxy or methyl;
[0584] R2aand R2bare each independently H or methyl; or
[0585] R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(=0), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members;
[0586] R2Cis C|-C2alkyl, C2-C3alkenyl or C2-C3alkynyl;
[0587] R2dis H or methyl;
[0588] A1is CR6cR6dor O;
[0589] A2is a direct bond, CR6eR6for O;
[0590] R6a, R6b, R6c, R6d, R6eand R6fare each independently H, cyano, hydroxy, Br, Cl, F or methyl;
[0591] J is J-l, J-6 or J- 14; each R8is independently F, Cl or methyl; each R9aand R9bis independently H, halogen or methyl; n is 0, 1 or 2;
[0592] E1is C^-C^ alkoxy, C^-C^ alkylsulfonyl, C2-C6 alkylcarbonyl or C2-C6 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b;
[0593] Rl°ais phenyl optionally substituted with up to 2 substituents independently selected from Rlla; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members and Rl lbon nitrogen atom ring members; each R10bis independently halogen, hydroxy, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4 haloalkoxy, C4-C4 alkylsulfonyl, C2-C4 alkylcarbonyl or C2-C5 alkoxycarbonyl; each Rl lais independently halogen, C4-C2 alkyl, C4-C2 haloalkyl, C1-C2 alkoxy or C2-C3 alkoxycarbonyl; each Rl lbis independently methyl, methoxy, methylcarbonyl or methoxycarbonyl;
[0594] G is selected from the group consisting of:
[0595] G-17 G-18 G-19 G-20
[0596] G-41 G-42 G-43 G-44 G-65 G-66 G-67 G-68
[0597] G-89 G-90 G-91 G-92
[0598] wherein the floating bond is connected to Z in Formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3; each R13is independently C(=0)NR14aR14bor -U-V-Q; or C^-Cg alkyl, alkenyl,
[0599] C2-C6alkynyl, C^-Cg alkoxy, C2-C6alkenyloxy, C2-C6alkynyloxy, C^-Cg alkylsulfonyl, C^-Cg alkylsulfonyloxy, C^-Cg alkylsulfonylamino, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, Cg-Cg alkenyloxycarbonyl, Cg-Cg alkynyloxycarbonyl, C4-C6 cycloalkoxycarbonyl or C2-Cg alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19; each R14ais independently H, C[-C2alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl; each R14bis independently H, C4-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkylaminoalkyl or C3-C5 dialkylaminoalkyl; or
[0600] R14aand R14bare taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl; each R19is independently cyano, halogen, C[-C2alkyl, C[-C2haloalkyl, C3-C6 cycloalkyl, C[-C2alkoxy, C|-C2haloalkoxy, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl or C2-C3alkoxycarbonyl; each U is independently a direct bond, C(=0)0 or C(=0)N(R25); each V is independently a direct bond; or C[-C3 alkylene, each optionally substituted with up to 2 substituents independently selected from halogen, hydroxy, C[-C2alkyl, C[-C2alkoxy and C|-C2haloalkoxy; each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each optionally substituted with up to 2 substituents independently selected from R27; each R25is independently H, cyano, hydroxy or Ci-C2alkyl; each R27is independently halogen, cyano, Ci-C2alkyl, Ci-C2haloalkyl or C1-C2 alkoxy; and
[0601] Z is a direct bond, O, NH, C(=0), C(=0)NH, NHC(=0), NHC(=0)NH, OC(=0)NH, NHC(=0)0, S(=0)2NH, NHS(=0)2or NHS(=0)2NH.
[0602] Embodiment AA. The composition of Embodiment A wherein in Formula 1,
[0603] R1is CF3;
[0604] X is O;
[0605] Y is O;
[0606] L is a direct bond or CH2; and Z is a direct bond.
[0607] Embodiment AAA. The composition of Embodiment A wherein in Formula 1,
[0608] R1is CF3;
[0609] Z is a direct bond.
[0610] Embodiment B. The composition of Embodiment A wherein in Formula 1,
[0611] T is T-2 or T-3;
[0612] R1is CF3;
[0613] X is O;
[0614] Y is O;
[0615] R2aand R2bare each independently H or methyl; or
[0616] R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member;
[0617] R2Cis methyl or ethyl;
[0618] R2dis H;
[0619] A1is O;
[0620] A2is a direct bond or CH2;
[0621] R6aand R6bare each independently H, cyano hydroxy or methyl;
[0622] J is J-l or J-6; q is 0 or 1 ; each R9aand R9bis independently H or methyl;
[0623] E1is C|-C3alkoxy, C2-C3alkylcarbonyl or C2-C3alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b;
[0624] RlOa jspyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from Rl laon carbon atom ring members; each R10bis independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C4 alkoxycarbonyl;
[0625] G is G-l, G-3, G-12 or G-22; x is 1 or 2; each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19; each R14ais independently H or C1-C2 alkyl; each R14bis independently H, C1-C3 alkyl, C|-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl; each R19is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl; each U is independently a direct bond or C(=0)0; each V is independently a direct bond or ϋ¾; each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27; each R27is independently halogen, methyl or methoxy; and Z is a direct bond, O, NH, C(=0), C(=0)NH or NHC(=0).
[0626] Embodiment BB. The composition of Embodiment B wherein in Formula 1,
[0627] L is a direct bond or CH2;
[0628] G is G-l or G-12; and Z is a direct bond.
[0629] Embodiment BBB. The composition of Embodiment B wherein in Formula 1,
[0630] Z is a direct bond.
[0631] Embodiment C. The composition of Embodiment B wherein in Formula 1,
[0632] R2aand R2bare each H; or
[0633] R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms;
[0634] A2is a direct bond; R6aand R6bare each H;
[0635] R8is F or Cl;
[0636] L is a direct bond, ϋ¾ or CEECEE ;
[0637] E1is CrC2alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a;
[0638] Rl°ais pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members; each Rl lais independently methoxycarbonyl or ethoxycarbonyl;
[0639] G is G-l and the 2-position of G-l is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1 -position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; x is 1;
[0640] R13is C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19;
[0641] R14ais H;
[0642] R14bis H, methyl or cyclopropylmethyl;
[0643] R19is cyano, halogen, cyclopropyl or methoxy;
[0644] U is C(=0)0;
[0645] V is CH2;
[0646] Q is phenyl optionally substituted with up to 2 substituents independently selected from R27; and
[0647] Z is a direct bond, O, NH or C(=0).
[0648] Embodiment CC. The composition of Embodiment C wherein in Formula 1,
[0649] L is a direct bond or CH2; and
[0650] Z is a direct bond.
[0651] Embodiment D. The composition of Embodiment C wherein in Formula 1,
[0652] R8is F;
[0653] L is a direct bond or CH2;
[0654] E1is methoxy substituted with 1 substituent selected from R10a;
[0655] Rl°ais pyrazolyl optionally substituted with up to 1 substituent selected from Rllaon a carbon atom ring member;
[0656] G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; and
[0657] R13is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from Rl9;
[0658] R19is cyano, Cl, F, cyclopropyl or methoxy; and Z is a direct bond.
[0659] Embodiment DD. The composition of Embodiment D wherein in Formula 1,
[0660] L is a direct bond or CH2, provided that when L is a direct bond, then E is E1, and when L is CH2, then E is E2.
[0661] Embodiment E. The composition of Embodiment D wherein in Formula 1,
[0662] J is J-l; q is 0;
[0663] L is CH2;
[0664] E is E2;
[0665] G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; and
[0666] R13is methoxycarbonyl or ethoxycarbonyl.
[0667] Embodiment EE. The composition of Embodiment E wherein in Formula 1,
[0668] R2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
[0669] Embodiment F. The composition of any one of Embodiments A through EE wherein in Formula 1,
[0670] T is T-2; and
[0671] R13is ethoxycarbonyl.
[0672] Embodiment G. The composition of any one of Embodiments A through E wherein in Formula
[0673] 1,
[0674] T is T-3; and
[0675] R13is ethoxycarbonyl.
[0676] Embodiment H. The composition any one of Embodiments A through G wherein component (a) comprises a compound selected from the group consisting of: Compound 1, Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 221, Compound 229, Compound 231, Compound 262, Compound 263, Compound 265, Compound 297, Compound 330, Compound 331 and Compound 364.
[0677] Embodiment I. The composition of Embodiment H wherein component (a) comprises a compound selected from the group consisting of: Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 229, Compound 263, Compound 297, Compound 330 and Compound 331.
[0678] Embodiment J. The composition of Embodiment I wherein component (a) comprises a Compound 32.
[0679] Embodiment K. The composition of Embodiment I wherein component (a) comprises Compound 64.
[0680] Embodiment Bl. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl) methyl benzimidazole carbamate fungicides such as benomyl, carbendazim, fuberidazole thiabendazole, thiophanate and thiophanate-methyl.
[0681] Embodiment B2. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b2) dicarboximide fungicides such as chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.
[0682] Embodiment B3. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b3) demethylation inhibitor fungicides such as triforine, buthiobate, pyrifenox, pyrisoxazole fenarimol, nuarimol, triarimol econazole, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizoleazaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, ipfentrifluconazole, quinconazole, simeconazole, tebuconazole, tetraconazole triadimefon, triadimenol, triticonazole, uniconazole and uniconazole-P.
[0683] Embodiment B4. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b4) phenylamide fungicides such as metalaxyl, metalaxyl-M, benalaxyl, benalaxyl-M, furalaxyl, ofurace and oxadixyl.
[0684] Embodiment B5. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b5) amine / morpholine fungicides such as aldimorph, dodemorph, fenpropimorph, tridemorph, trimorphamide, fenpropidin, piperalin and spiroxamine.
[0685] Embodiment B6. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b6) phospholipid biosynthesis inhibitor fungicides such as edifenphos, iprobenfos, pyrazophos and isoprothiolane.
[0686] Embodiment B7. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b7) succinate dehydrogenase inhibitor fungicides such as benodanil, flutolanil, mepronil, isofetamid, fluopyram, fenfuram, carboxin, oxycarboxin thifluzamide, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne, sedaxane, flubeneteram, isoflucypram, pydiflumetofen, boscalid and pyraziflumid.
[0687] Embodiment B8. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b8) hydroxy(2- amino-)pyrimidine fungicides such as bupirimate, dimethirimol and ethirimol.
[0688] Embodiment B9. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b9) anilinopyrimidine fungicides such as cyprodinil, mepanipyrim and pyrimethanil.
[0689] Embodiment B10. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (blO) / V-phenyl carbamate fungicides such as diethofencarb.
[0690] Embodiment B 11. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl 1) fungicides quinone outside inhibitor fungicides such as azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, fluoxastrobin, famoxadone, fenamidone and pyribencarb.
[0691] Embodiment B12. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl2) phenylpyrrole fungicides compound such as fenpiclonil and fludioxonil.
[0692] Embodiment B13. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl3) azanaphthalene fungicides such as quinoxyfen and proquinazid.
[0693] Embodiment B14. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl4) cell peroxidation inhibitor fungicides such as biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolclofos-methyl and etridiazole.
[0694] Embodiment B15. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl5) melanin biosynthesis inhibitors -reductase fungicides such as fthalide, pyroquilon and tricyclazole.
[0695] Embodiment B16a. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl6a) melanin biosynthesis inhibitors-dehydratase fungicides such as carpropamid, diclocymet, and fenoxanil.
[0696] Embodiment B16b. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl6b) melanin biosynthesis inhibitor-polyketide synthase fungicides such as tolprocarb.
[0697] Embodiment B17. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl7) keto reductase inhibitor fungicides such as fenhexamid, fenpyrazamine, quinofumelin and ipflufenoquin.
[0698] Embodiment B18. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl8) squalene- epoxidase inhibitor fungicides such as pyributicarb, naftifine and terbinafine.
[0699] Embodiment B19. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl9) polyoxin fungicides such as polyoxin.
[0700] Embodiment B20. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 243 and A through K) wherein component (b) includes at least one compound selected from (b20) phenylurea fungicides such as pencycuron.
[0701] Embodiment B21. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b21) quinone inside inhibitor fungicides such as cyazofamid, amisulbrom and fenpicoxamid (Registry Number 517875-34-2).
[0702] Embodiment B22. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b22) benzamide and thiazole carboxamide fungicides such as zoxamide and ethaboxam.
[0703] Embodiment B23. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b23) enopyranuronic acid antibiotic fungicides such as blasticidin-S.
[0704] Embodiment B24. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b24) hexopyranosyl antibiotic fungicides such as kasugamycin.
[0705] Embodiment B25. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b25) glucopyranosyl antibiotic: protein synthesis fungicides such as streptomycin.
[0706] Embodiment B26. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b26) glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides such as validamycin.
[0707] Embodiment B27. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b27) cyanoacetylamideoxime fungicides such as cymoxanil.
[0708] Embodiment B28. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b28) carbamate fungicides such as propamacarb, prothiocarb and iodocarb.
[0709] Embodiment B29. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b29) oxidative phosphorylation uncoupling fungicides such as fluazinam, binapacryl, meptyldinocap and dinocap.
[0710] Embodiment B30. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b30) organo tin fungicides such as fentin acetate, fentin chloride and fentin hydroxide.
[0711] Embodiment B31. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b31) carboxylic acid fungicides such as oxolinic acid.
[0712] Embodiment B32. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b32) heteroaromatic fungicides such as hymexazole and octhilinone.
[0713] Embodiment B33. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b33) phosphonate fungicides such as phosphorous acid and its various salts, including fosetyl-aluminum. Embodiment B34. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b34) phthalamic acid fungicides such as teclofthalam.
[0714] Embodiment B35. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b35) benzotriazine fungicides such as triazoxide.
[0715] Embodiment B36. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b36) benzene- sulfonamide fungicides such as flusulfamide.
[0716] Embodiment B37. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b37) pyridazinone fungicides such as diclomezine.
[0717] Embodiment B38. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b38) thiophene- carboxamide fungicides such as silthiofam.
[0718] Embodiment B39. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b39) complex I NADH oxidoreductase inhibitor fungicides such as diflumetorim, tolfenpyrad and fenazaquin.
[0719] Embodiment B40. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b40) carboxylic acid amide fungicides such as dimethomorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalate, mandipropamid, flumorph, dimethomorph, flumorph, pyrimorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb, valifenalate and mandipropamid.
[0720] Embodiment B41. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b41) tetracycline antibiotic fungicides such as oxy tetracycline.
[0721] Embodiment B42. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b42) thiocarbamate fungicides such as methasulfocarb.
[0722] Embodiment B43. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b43) benzamide fungicides such as fluopicolide and fluopimomide.
[0723] Embodiment B44. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b44) microbial fungicides such as Bacillus amyloliquefaciens strains QST713, FZB24, MB 1600, D747, F727, TJ100 (also called strain 1 BE; known from EP2962568) and the fungicidal lipopeptides which they produce.
[0724] Embodiment B45. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b45) quinone outside inhibitor, stigmatellin binding fungicides such as ametoctradin.
[0725] Embodiment B46. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b46) plant extract fungicides such as Melaleuca alternifolia, eugenol, geraniol and thymol.
[0726] Embodiment B47. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b47) cyanoacrylate fungicides such as phenamacril.
[0727] Embodiment B48. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b48) polyene fungicides such as natamycin.
[0728] Embodiment B49. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b49) oxysterol binding protein inhibitor fungicides such as oxathiapiprolin and fluoxapiprolin.
[0729] Embodiment B50. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b50) aryl-phenyl- ketone fungicides such as metrafenone and pyriofenone.
[0730] Embodiment B5E The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b51) host plant defense induction fungicides such as acibenzolar-S-methyl, probenazole, tiadinil, isotianil, laminarin, extract from Reynoutria sachalinensis and Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS 117.
[0731] Embodiment B52. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b52) multi-site activity fungicides such as copper oxychloride, copper sulfate, copper hydroxide, Bordeaux composition (tribasic copper sulfide), elemental sulfur, ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb, ziram, folpet, captan, captafol, chlorothalonil, dichlofluanid, tolyfluanid, guazatine, iminoctadine albesilate, iminoctadine triacetate, anilazine, dithianon, quinomethionate and fluoroimide.
[0732] Embodiment B53. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b53) biological fungicides with multiple modes of action such as extract from the cotyledons of lupine plantlets.
[0733] Embodiment B54. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54) fungicides other than fungicides of component (a) and components (bl) through (b53), such as cyflufenamid, bethoxazin, neo-asozin, pyrrolnitrin, tebufloquin, dodine, flutianil, ferimzone, picarbutrazox, dichlobentiazox (Registry Number 957144-77-3), dipymetitrone (Registry Number 16114-35-5), flometoquin, tolnifanide (Registry Number 304911-98-6), / V-[4-[4- chloiO-3-(trinuoromcthyl)phcnoxyJ-2,5-dimcthylphcnylJ-A-cthyl-A- mcthylmcthani mid- amide, 5-fluoro-2- [(4-flu orophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenyl N-[l- [[[l-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate (XR-539).
[0734] Embodiment B55. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes (lS)-2,2-bis(4-fluorophenyl)-l-methylethyl / V-[[3- (acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name flory lpicoxamid) .
[0735] Embodiment B56. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes l-[2-[[[l-(4-chlorophenyl)-l -pyrazol-3-yl]oxy]methyl]- 3-mcthylphcnyl]-l ,4-dihydro-4-mcthyl-5 / 7-tctra / ol-5-onc (provisional common name mety ltetraprole) .
[0736] Embodiment B57. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5- phenylpyridazine (provisional common name pyridachlometyl).
[0737] Embodiment B58. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3- carboxylate (provisional common name aminopyrifen).
[0738] Embodiment B59. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.11) (i.e Formula b54.11) wherein
[0739] Rbl° and Rbl 1are each independently halogen; and
[0740] R6is H, halogen, C^-Cg alkyl, C^-Cg haloalkyl or Cg-Cg cycloalkyl.
[0741] Embodiment B60. The composition of Embodiment B59 wherein component (b) includes at least one fungicidal compound selected from the group consisting of methyl A- [[5- [1 -(2,6- difluoro-4-formylphenyl)-l / / -pyrazol-3-yl]-2-methylphenyl] methyl]carbamate, methyl N- [[5-[l-(4-cyclopropyl-2,6-dichlorophenyl)-l -pyrazol-3-yl]-2-methylphenyl]methyl]- carbamate, methyl A / -[[5-[l-(4-chloro-2,6-difluorophenyl)-l -pyrazol-3-yl]-2-methyl- phenyl]methyl]carbamate, methyl A / -[[5-[l-(4-cyclopropyl-2,6-difluorophenyl)-l -pyrazol- 3-yl]-2-methylphenyl]methyl]carbamate, methyl A / -[[5-[l-[2,6-difluoro-4-(l-methylethyl) phenyl]- 1 / 7-pyrazol-3-yl]-2-mcthylphcnyl]mcthyl]carbamatc and methyl / V-[[5-[l-[2,6-di fluoro-4-(trifluoromethyl)phenyl]-l -pyrazol-3-yl]-2-methylphenyl]methyl]carbamate.
[0742] Embodiment B61. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.12) (i.e Formula b54.12) b54.12 wherein Rb4is Rb6is C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl;
[0743] L is CH2 or CH2O, wherein the atom to the right is connected to the phenyl ring in Formula b54.12; and
[0744] Rb5is
[0745] Embodiment B62. The composition of Embodiment B61 wherein component (b) includes at least one fungicidal compound selected from the group consisting of N-( 2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]-4- oxazolecarboxamide and ethyl l-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenoxy] methyl]- l / -pyrazole-4-carboxylate.
[0746] Embodiment B63. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.13) (i.e Formula b54.13) wherein
[0747] Rb7, Rb8and Rb9are each independently H, halogen or cyano; and Rbl° and Rbl 1are each independently H, halogen, C[-C3 alkyl or C[-C3 methoxy Embodiment B64. The composition of Embodiment B63 wherein component (b) includes at least one fungicidal compound selected from the group consisting of 4-(2-chloro-4- fl uo ro p h c n y 1 ) - A- (2 - fl u o ro - 4 - in c t h y 1 - 6 - n i t ro p h c n y 1 ) - 1 ,3-dimethyl- l / -pyrazol-5-amine, 4-(2- chloro-4-fluorophenyl)- V-(2-fluoro-6-nitrophenyl)-l, 3-dimethyl- l / -pyrazol-5-amine, 3,5- difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]- 1,3-dimethyl- l -pyrazol-4-yl]- benzonitrile and A-(2-ch loro-4- nuoro-6-nitrophcnyl)-4-(2-ch loro-4- fluorophenyl)- 1 ,3- dimethyl- 1 / 7-pyrazol-5-aminc.
[0748] Embodiment B65. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one fungicidal compound (fungicide) selected from the group consisting of azoxystrobin, benzovindiflupyr, boscalid (nicobifen), bixafen, bromuconazole, carbendazim, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenbuconazole, fenpropidin, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluxapyroxad, hexaconazole, ipconazole kresoxim-methyl, manzate, metconazole, metominostrobin, metrafenone, myclobutanil, penconazole, penthiopyrad, picoxystrobin, prochloraz, propiconazole, proquinazid, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyriofenone quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, methyl N- [[5- [ 1 - [2,6-difluoro-4-( 1 -methylethyl)phenyl] - 1 / 7-pyrazol-3-ylJ -2- methylphenyl]methyl]carbamate, methyl A / -[[5-[l-[2,6-difluoro-4-(trifluoromethyl)phenyl]- 1 / / -pyrazol-3-ylJ-2-mcthylphcnyl] methy ljcarbamatc, / V-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, ethyl l-[[4- [5-(trifluoiOmcthyl)-l ,2, 4-oxadiazol-3-y ljphcnoxy] methy lj-l / / -pyrazolc-4-carboxy late, 4- (2-chloro-4-fluorophenyl)- V-(2-fluoro-4-methyl-6-nitrophenyl)- 1 ,3-dimethyl- 1 / / -pyrazol-5- amine, 4-(2-chloro-4-fluorophenyl)- V-(2-fluoro-6-nitrophenyl)- 1 ,3-di methyl- 1 / / -pyrazol-5- amine and 3, 5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]- 1,3-dimethyl- l -pyrazol-
[0749] 4-yl]-benzonitrile.
[0750] Embodiment B66. The composition of Embodiment B65 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenpropidin, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluxapyroxad, kresoxim-methyl, manzate, metconazole, metominostrobin, metrafenone, myclobutanil, penthiopyrad, picoxystrobin, propiconazole, proquinazid, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyriofenone, quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, methyl N- [[5- [ 1 - [2,6-difluoro-4-( 1 -methylethyl)phenyl] - l / / -pyrazol-3 -yl] -2-methylphenyl] methyl]carbamate, methyl A / -[[5-[l-[2,6-difluoro-4-(trifluoromethyl)phenyl]-l -pyrazol-3- yl]-2-methylphenyl]methyl]carbamate, A / -(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-l,
[0751] 2.4-oxadiazol-3 -yl]phenyl] methyl] -4-oxazolecarboxamide, ethyl 1 - [ [4-[5-(trifluoromethyl)-
[0752] 1.2.4-oxadiazol-3-yl]phenoxy]methyl]-l -pyrazole-4-carboxylate, 4-(2-chloro-4-
[0753] P u o ro p h c n y 1 ) - - (2 - P u o ro - 4 - m c t h y 1 - 6 - n i t ro p h c n y 1 ) - 1 ,3-dimethyl- l / / -pyrazol-5-amine, 4-(2- chloro-4-fluorophenyl)- V-(2-fluoro-6-nitrophenyl)-l, 3-dimethyl- l / / -pyrazol-5-amine and 3,
[0754] 5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]- 1,3-dimethyl- l -pyrazol-4-yl]- benzonitrile.
[0755] Embodiment B67. The composition of Embodiment B66 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, difenoconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, manzate, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole, trifloxystrobin, methyl / V-[[5-[l-[2,6-difluoro-4-(l-methylethyl)phenyl]-l / / - pyrazol-3 -yl] -2-methylphenyl]methyl] carbamate, methyl N- [ [5- [ 1 - [2,6-difluoro-4- (trifluoromethy l)pheny 1] - 1 H- pyrazol- 3 -y 1] -2 -methy lpheny 1] methy 1] carb amate, N- (2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]-4- oxazolecarboxamide, ethyl l-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenoxy] methyl]- l / / -pyrazole-4-carboxylate, 4-(2-ch loro-4- fluorophenyl )-L / -(2-P uoro-4-mcthy 1-6- nitrophenyl)- 1 ,3-dimethyl- 1 / / - p y ra zo 1 - 5 - a m i n c , 4-(2-chloro-4-fluorophenyl)- V-(2-fluoro-6- nitrophcnyl)-l ,3-dimcthyl-l / / -pyrazol-5-aminc and 3,5-difluoro-4-[5-[(4-methoxy-2- nitrophenyl)amino]- 1,3-dimethyl- l / / -pyrazol-4-yl]-benzonitrile.
[0756] Embodiment B68. The composition of Embodiment B67 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, manzate, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole, trifloxystrobin.
[0757] Of note is the composition of any one of the embodiments described herein, including any Embodiments 1 through 258, A through K, and B1 through B68, wherein reference to Formula 1 includes salts thereof but not / V-oxides thereof; therefore the phrase “a compound of Formula 1” can be replaced by the phrase “a compound of Formula 1 or a salt thereof’. In this composition of note, component (a) comprises a compound of Formula 1 or a salt thereof.
[0758] Also noteworthy as embodiments are fungicidal compositions of the present invention comprising a fungicidally effective amount of a composition of Embodiments 1 through 258, A through K, and B1 through B68, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
[0759] Embodiments of the invention further include methods for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a composition any one of Embodiments 1 through 258, A through K, and B1 through B68 (e.g., as a composition including formulation ingredients as described herein). Embodiments of the invention also include methods for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of a composition of any one of Embodiments 1 through 258, A through K, and B 1 through B68 to the plant or plant seed.
[0760] Some embodiments of the invention involve control of a plant disease or protection from a plant disease that primarily afflicts plant foliage and / or applying the composition of the invention to plant foliage (i.e. plants instead of seeds). The preferred methods of use include those involving the above preferred compositions; and the diseases controlled with particular effectiveness include plant diseases caused by fungal plant pathogens. Combinations of fungicides used in accordance with this invention can facilitate disease control and retard resistance development.
[0761] Method embodiments further include:
[0762] Embodiment Cl. A method for protecting a plant from a disease selected from rust, powdery mildew and Septoria diseases comprising applying to the plant a fungicidally effective amount of the composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 258.
[0763] Embodiment C2. The method of Embodiment Cl wherein the disease is a rust disease and component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (b5) amine / morpholine fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (b 11) quinone outside inhibitor (Qol) fungicides, (bl3) methyl benzimidazole carbamate fungicides and (b52) multi-site activity fungicides.
[0764] Embodiment C3. The method of Embodiment C2 wherein component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (b7) succinate dehydrogenase inhibitor fungicides and (b 11 ) quinone outside inhibitor (Qol) fungicides.
[0765] Embodiment C4. The method of Embodiment C3 wherein component (b) of the composition includes at least one fungicidal compound selected from the group consisting of azoxystrobin, cyproconazole, difenoconazole, epoxiconazole, fluindapyr, flutriafol, fluxapyroxad, picoxystrobin, prothioconazole, pyraclostrobin, tebuconazole and trifloxystrobin.
[0766] Embodiment C5. The method of Embodiments C2 through C4 wherein the disease is Asian soybean rust caused by Puccinia recondite.
[0767] Embodiment C6. The method of Embodiments C2 through C4 wherein the disease is wheat leaf rust caused by Phakopsora pachyrhizi.
[0768] Embodiment C7. The method of Embodiment Cl wherein the disease is a powdery mildew disease and component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (bl 1) quinine outside inhibitor (Qol) fungicides and (bl3) azanaphthalene fungicides.
[0769] Embodiment C8. The method of Embodiment C7 wherein the disease is wheat powdery mildew.
[0770] Embodiment C9. The method of Embodiment C7 wherein the disease is grape downy mildew. Embodiment CIO. The method of Embodiments C7 through C9 wherein component (b) includes at least one fungicidal compound selected from (b3) DMI fungicides.
[0771] Embodiment Cl 1. The method of Embodiment CIO wherein component (b) includes at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, prothioconazole and tebuconazole.
[0772] Embodiment C12. The method of Embodiment C 11 wherein component (b) includes at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole and prothioconazole.
[0773] Embodiment C13. The method of Embodiments C8 through CIO wherein component (b) includes at least one fungicidal compound selected from (bl 1) Qol fungicides.
[0774] Embodiment C14. The method of Embodiment C 12 wherein component (b) includes at least one fungicidal compound selected from the group consisting of azoxystrobin, picoxystrobin and pyraclostrobin.
[0775] Embodiment C15. The method of Embodiment Cl wherein the disease is a Septoria disease and component (b) of the composition includes at least one fungicidal compound selected from the group consisting of epoxiconazole, metalaxyl (including metalaxyl-M), iprovalicarb and fenpropimorph.
[0776] Embodiment Cl 6. The method of Embodiment C 15 wherein the disease is wheat leaf blotch.
[0777] Embodiment C17. The method of any one of Embodiments Cl through C16 wherein components (a) and (b) are applied in synergistically effective amounts (and in a synergistic ratio relative to each other).
[0778] Of note are embodiments that are counterparts of Embodiments Cl through C17 relating to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, a fungicidally effective amount of a fungicidal composition of the invention.
[0779] As noted in the Summary of the Invention, this invention also relates to a compound of Formula 1, or an A-oxidc or salt thereof. Also noted is that the embodiments of this invention, including Embodiments 1-258, relate also to compounds of Formula 1. Accordingly, combinations of Embodiments 1-258 are further illustrated by:
[0780] Embodiment Dl. A compound of Formula 1, or an A-oxidc or salt thereof, wherein
[0781] T is T-2;
[0782] R1is CF3;
[0783] X is O; Y is O;
[0784] R2ais H or methyl;
[0785] R2bis C3-C15 trialkylsilyl or C3-C35 halotrialkylsilyl;
[0786] A1is O;
[0787] A2is a direct bond or CH2;
[0788] R6aand R6bare each independently H, cyano hydroxy or methyl;
[0789] J is J-l or J-6; q is 0 or 1 ;
[0790] L is a direct bond or CH2;
[0791] E is E1or E2;
[0792] E1is C3-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b;
[0793] Rl°ais pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from Rl laon carbon atom ring members; each R10bis independently halogen, C3-C2 alkyl, C3-C2 haloalkyl, C3-C2 alkoxy or C2-C4 alkoxycarbonyl; each Rl lais independently methoxycarbonyl or ethoxycarbonyl;
[0794] G is G-l, G-3, G-12 or G-22; x is 1 or 2; each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19; each R14ais independently H or C3-C2 alkyl; each R14bis independently H, C3-C3 alkyl, C3-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl; each R19is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl; each U is independently a direct bond or C(=0)0; each V is independently a direct bond or ϋ¾; each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27; each R27is independently halogen, methyl or methoxy; and Z is a direct bond, O, NH, C(=0), C(=0)NH or NHC(=0). Embodiment D2. A compound of Embodiment D1 wherein
[0795] R2ais H or methyl;
[0796] R2bis trimethylsilyl or halotrimethylsilyl;
[0797] A2is a direct bond;
[0798] R6aand R6bare each H;
[0799] R8is F or Cl;
[0800] E1is CrC2alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a;
[0801] Rl°ais pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members; each Rl lais independently methoxycarbonyl or ethoxycarbonyl;
[0802] G is G-l and the 2-position of G-l is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1 -position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; x is 1;
[0803] R13is C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19;
[0804] R14ais H;
[0805] R14bis H, methyl or cyclopropylmethyl;
[0806] R19is cyano, halogen, cyclopropyl or methoxy;
[0807] U is C(=0)0;
[0808] V is CH2;
[0809] Q is phenyl optionally substituted with up to 2 substituents independently selected from R27; and
[0810] Z is a direct bond, O, NH or C(=0).
[0811] Embodiment D3. A compound of Embodiment D2 wherein
[0812] R2ais H or methyl;
[0813] R2bis trimethylsilyl;
[0814] R8is F;
[0815] E1is methoxy substituted with 1 substituent selected from R10a;
[0816] Rl°ais pyrazolyl optionally substituted with up to 1 substituent selected from Rllaon a carbon atom ring member; G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; and
[0817] R13is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from Rl9;
[0818] R19is cyano, Cl, F, cyclopropyl or methoxy; and
[0819] Z is a direct bond.
[0820] Embodiment D3. A compound of Embodiment D3 wherein
[0821] R2ais methyl;
[0822] J is J-l; q is 0;
[0823] L is CH2;
[0824] E is E2;
[0825] G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; and
[0826] R13is methoxycarbonyl or ethoxycarbonyl.
[0827] Additional embodiments include a fungicidal composition comprising: (1) a compound of any one of Embodiments D1 through D3; and (2) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Additional embodiments also include a method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of the compound of any one of Embodiments D1 through D3 to the plant (or portion thereof) or plant seed (directly or through the environment (e.g., growing medium) of the plant or plant seed). Of note are embodiments relating to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, a fungicidally effective amount of a compound of any one of Embodiments D1 through D3.
[0828] This invention also provides a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, / V-oxides, and salts thereof) (i.e. in a fungicidally effective amount), and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Of note as embodiments of such compositions are compositions comprising a compound corresponding to any of the compound embodiments described above.
[0829] One or more of the following methods and variations as described in Schemes 1-17 can be used to prepare the compounds of Formula 1. The definitions of E, L, A, A1, A2, J, T, X, Y, R1, R2a, R2b, R2c, R2d, R6a, R6band R29in the compounds of Formulae 1-14 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of Formulae la-la1, lb-lb6and lc-lc1are various subsets of Formula 1, and all substituents for Formulae la-la1, lb- lb6and lc-lc1are as defined above for Formula 1 unless otherwise noted. As the synthetic literature includes many halomethyl ketone and hydrate-forming methods, which can readily be adapted to prepare compounds of the present invention, the following methods in Schemes 1-17 are simply representative examples of a wide variety of procedures useful for the preparation of the compounds of Formula 1. For reviews of ketone and hydrate-forming methods, see, for example, Tetrahedron 1991, 47, 3207-3258 and Chem. Communications 2013, 49(95), 11133- 11148, and references cited therein. Also see the methods outlined in U.S. Patent 6,350,892.
[0830] As shown in Scheme 1, Compounds of Formula la (i.e. Formula 1 wherein T is T-l and W is O) wherein R1is CF3 can be prepared by trifluoroacetylation of organometallic compounds of Formula 2. Typically, the ethyl ester of trifluoroacetic acid (i.e. ethyl trifluoroacetate) is used as the source of the trifluoroacetyl group in this method, but trifluoroacetonitrile and various trifluoroacetate salts can also be used. Depending on the reaction conditions, double-addition on the trifluoroacetyl compound can occur. Conducting the reaction at -65 °C, or more preferably at -78 °C, can reduce the occurrence of double addition adducts to trace amounts, particularly when using organometallic species of Formula 2 wherein M is Li or MgBr. Many other organometallic species yield similar results. For reaction conditions useful in the method of Scheme 1, as well as other well-established routes for the synthesize trifluoromethyl ketones see, for example, Journal of Organic Chemistry 1987, 52(22), 5026-5030; Chemical Communications 2013, 49(95), 11133-11148; and Journal of Fluorine Chemistry 1981, 18, 117-129. Conditions described in these references can easily be modified to prepare compounds of Formula la wherein R1is other than CF3 (e.g., dihalo- or trichloro-moieties).
[0831] Scheme 1
[0832] M is, wherein R1is CF3
[0833] Compounds of Formula la (i.e. Formula 1 wherein T is T-l and W is O) wherein R1is CF3 can also be prepared via alkylation of ethyl 4,4,4-trifluoroacetoacetate (ETFAA) with compounds of Formula 3 wherein Lais a leaving group such as halogen (e.g., Cl, Br) or sulfonate (e.g., mesylate). In this method ETFAA is first treated with a base such as sodium hydride in a polar aprotic solvent such tetrahydrofuran (THF), THF / hexamethylphosphoramide (HMPA) or acetone. The ETFAA anion then displaces the leaving group in compounds of Formula 3 to give an intermediate ester which undergoes hydrolysis and decarboxylation in the presence of lithium chloride (LiCl) and N, / V-dimethylformamide (DMF) to give the ketone compound of Formula la. For reaction conditions see Journal Chemical Society, Chemical Communications 1989, (2), 83- 84; Chemical Communications 2013, 49(95), 11133-11148; and Journal of Fluorine Chemistry 1989, 44, 377-394.
[0834] Scheme 2
[0835] 3 wherein is CF3 3. LiCl, DMF wherein R1is CF3
[0836] Lais a leaving group such as Cl, Br or OMs As shown in Scheme 3, compounds of Formula la (i.e. Formula 1 wherein T is T-l and W is O) wherein R1is CF3 can also be prepared by trifluoromethylation of an ester of Formula 5 with trifluoromethyltrimethylsilane (TMS-CF3). The reaction is run in the present of a fluoride initiator such as tetrabutylammonium fluoride, and in an anhydrous solvent such as toluene or dichloromethane at about -78 °C (for reaction conditions see, for example, Angew. Chem., Int. Ed. 1998, 37(6), 820-821). Cesium fluoride can also be used as an initiator in a solvent such as 1,2-dimethoxy ethane (glyme) at room temperature (for reaction conditions see, for example, J. Org. Chem., 1999, 64, 2873). The reaction proceeds through a trimethylsilicate intermediate, which is hydrolyzed with aqueous acid to give the desired trifluoromethyl ketone compound of Formula la. Weinreb amides may also be used in place of the starting esters (see, for example, Chem. Commun. 2012, 48, 9610).
[0837] Scheme 3 As shown in Scheme 4, compounds of Formula la1(i.e. Formula la wherein A is Ai-A2- CR6aR6b) wherein R1is CF3 and at least one R6aor R6bis H can be prepared by reacting acid chlorides of Formula 6 with trifluoroacetic anhydride (TFAA) and pyridine in a solvent such as dichloromethane or toluene at a temperature between about 0 to 80 °C followed by aqueous hydrolysis (for reaction conditions see, for example, Tetrahedron 1995, 51, 2573-2584). Compounds of Formula 6 can be prepared from compounds of Formula 5 by ester hydrolysis to the corresponding carboxylic acid and treatment with oxalyl chloride, as known to one skilled in the art.
[0838] Scheme 4
[0839] 6 wherein at least one Rbaor Rbbis H wherein R1is CF3 and at least one Rbaor R6bis H
[0840] As shown in Scheme 5, compounds of Formula lb (i.e. Formula 1 wherein T is T-2) wherein R2aX and R2bY are OH can be prepared by oxidation of alcohols of Formula 4 to the corresponding dihydroxy. The oxidation reaction can be performed by a variety of means, such as by treatment of the alcohols of Formula 4 with manganese dioxide, Dess-Martin periodinane, pyridinium chlorochromate or pyridinium dichromate. For typical reaction conditions, see present Example 6, Step F and Example 8, Step F.
[0841] Scheme 5 lb
[0842] 4 wherein R2aX and RbY are both OH
[0843] Scheme 6 illustrates a specific example of the general method of Scheme 5 for the preparation of a compound of Formula lb1(i.e. Formula lb wherein L is CH2, J is phenyl (i.e. J-l), A is OCH2 and R1is CF3). In this method a compound of Formula 4a (i.e. Formula 4 wherein L is CH2, J is phenyl (i.e. J-l), A is OCH2 and R1is CF3) is reacted with an oxidizing reagent such as Dess-Martin periodinane in a solvent such as dichloromethane at a temperature between about 0 to 80 °C. Present Example 1, Step C illustrates the method of Scheme 6.
[0844] Scheme 6
[0845] As shown in Scheme 7, compounds of Formula 4 can be prepared by reaction of compounds of Formula 2 with RiCHO. For reactions conditions see, Tetrahedron Fetters 2007, 48, 6372-6376.
[0846] Scheme 7
[0847] 2 4
[0848] M is, e.g., Li, Na, K, Cs or MgBr As shown in Scheme 8, compounds of Formula 4b (i.e. Formula 4 wherein A is
[0849] OCR6aR6b) can be prepared by reacting a compound of Formula 7 with an epoxide of Formula 8. The reaction is typically carried out in a solvent such as acetonitrile with a catalytic amount of a base such as cesium or potassium carbonate at a temperature between about 20 to 80 °C; or in a solvent such as dichloromethane with a catalytic amount of a Fewis acid such as boron trifluoride etherate at a temperature between about 0 to 40 °C. Present Example 8, Step E illustrates the method of Scheme 8. One skilled in the art will recognize that the method of Scheme 8 can also be performed when A is SCR6aR6bor N(R^a)CR6aR6b, thus providing other compounds of Formula 4b.
[0850] Compounds of Formulae 7 and 8 are available from commercial sources and can easily be prepared using commercial precursors and known methods. Present Example 1, Step A, Example 6, Step D and Example 8, Step D illustrate the preparation of a compound of Formula 7.
[0851] Scheme 8
[0852] Scheme 9 illustrates a specific example of the general method of Scheme 8 for the preparation of a compound of Formula 4b1(i.e. Formula 4b wherein L is CH2, J is phenyl (i.e. J-l), R6aand R6bare H and R1is CF3) In this method a compound of Formula 7a (i.e. Formula 7 wherein L is CH2and J is phenyl (i.e. J-l)) is reacted with 2-(trifluoromethyl)oxirane (i.e. Formula 8a) in the presence of cesium carbonate in a solvent such as acetonitrile at a temperature between about 60 to 80 °C. Present Example 1, Step B illustrates the method of Scheme 9.
[0853] Scheme 9 As illustrated in Scheme 10, ketones of Formula la (i.e. Formula 1 wherein T is T-l and
[0854] W is O) may exist in equilibrium with their corresponding ketone hydrates (i.e. dihydroxy) of Formula lb (i.e. Formula 1 wherein T is T-2) wherein R2aX and R2bY are OH. The predominance of Formula la or Formula lb is dependent upon several factors, such as environment and structure. For example, in an aqueous environment ketones of Formula la can react with water to give ketone hydrates (also known as 1,1-geminal diols) of Formula lb. Conversion back to the keto-form can usually be achieved by treatment with a dehydrating agent such as magnesium sulfate or molecular sieves. When the ketone moiety is in close proximity to an electron- withdrawing group, such as when R1is a trifluoromethyl group, the equilibrium typically favors the dihydrate form. In these cases, conversion back to the keto-form may require a strong dehydrating agent, such as phosphorus pentoxide (P205). For reaction conditions see, for example, Eur. J. Org. Chem. 2013, 3658-3661; and Chemical Communications 2013, 49(95), 11133-11148, and references cited therein. Scheme 10 wherein are both OH
[0855] As shown in Scheme 11, ketones of Formula la may also exist in equilibrium with their hemiketals, hemithioketals and hemiaminals of Formula lb2(i.e. Formula lb wherein R2bY is OH and R2ais other than H) along with their ketals, thioketals aminals of Formula lb wherein R2aand R2bare other than H. Compounds of Formula lb2can be prepared by reacting a compound of Formula la with a compound of formula R2aX-H (e.g., alcohols for X being O, thiols for X being S or amines for X being NR5a), usually in the presence of an catalysis, such as a Bronsted (i.e. protic) acid or Lewis acid (e.g. BF3), (see, for example, Master Organic Chemistry (Online), On Acetals and Hemiacetals, May 28, 2010, www.masterorganic- chemistry.com / 2010 / 05 / 28 / on-acetals-and-hemiacetals). In a subsequent step, compounds of Formula lb2can be treated with a compound of formula R2bY-H (e.g., alcohols for Y being O, thiols for Y being S or amines for Y being NR5b) under dehydrating conditions, or other means of water removal that will drive the equilibrium in the reaction to the right, to provide compounds of Formula lb wherein R2aand R2bare other than H. Alternatively, ketones of Formula la can initially be treated with two equivalents (or an excess amount) of an alcohol, thiol or amine typically in the presence of a catalysis together with a dehydrating agent to provide compounds of Formula lb directly (see, for example, the preparation of the dimethylketals using methanol and trimethyl orthoformate in US 6,350,892).
[0856] Scheme 11 wherein R2ais other than H wherein R2aand R2bare other than H
[0857] As illustrated in Scheme 12, cyclic ketals of Formula lb3(i.e. Formula lb wherein X and Y are O, and R2aand R2bare taken together to form a 5- to 7-membered ring) can be prepared by treating the corresponding ketones of Formula la with haloalcohols (e.g., 2-chloroethanol or 2- bromopropanol) in the presence of a base such as potassium carbonate or potassium ieri-butoxide and in as solvent such as acetonitrile or / V, / V-dimethylformamide (DMF). For reactions conditions see, Organic Letters 2006 8(17), 3745-3748.
[0858] Scheme 12 ase lb 3 la wherein R*1is halogen wherein X and Y are O, and R2aand R2*3are taken togher to fom a ring
[0859] The method of Scheme 12 is also useful for preparing cyclic ketals stating from the corresponding ketone hydrate form. Scheme 13 illustrates a specific example where a ketone hydrate of Formula lb4(i.e. Formula lb wherein L is CH2, J is phenyl (i.e. J-l), A is OCH2, R2aX and R2bY are OH and R1is CF3) is reacted with 2-chloroethanol in the presence of potassium carbonate in acetonitrile at a temperature between about 25 to 70 °C to provide a compound of Formula lb5(i.e. Formula lb wherein L is CH2, J is phenyl (i.e. J-l), A is OCH2, X and Y are O, R2aand R2bare taken together to form a 5-membered ring and R1is CF3). Present Example 2 illustrates the method of Scheme 13.
[0860] Scheme 13 As shown in Scheme 14, Compounds of Formula lb6(i.e. compounds of Formula lb wherein A is A1-A2-CR6aR6b) wherein A1is N(R7a), O or S and A2is a direct bond, or wherein A1is CR6cR6dand A2is N(R7b), O or S can be prepared by reacting compounds of Formula 9 wherein A1is O, S or N(R7a) and A2is a direct bond, or where A1is CR6cR6dand A2is O, S or N(R7b) with compounds of Formula 10. The reaction is typically run in a solvent such N,N- dimethylformamide (DMF) or dimethyl sulfoxide with a base such as cesium or potassium carbonate or sodium hydride at a temperature between about 20 to 80 °C. The method of Scheme 14 is illustrated in Example 4, Step D. Scheme 14 wherein A1is N(R7a), O or S and A2wherein A1isN(R7a), O or S and A2is a direct is a direct bond, or wherein A1is bond, or wherein A1is CR6cR6dand A2is N(R7b), CR6cR6dand A2is N(R7b), O or S O or S
[0861] Compounds of Formula 10 can be prepared using commercial precursors and known methods. For example, as shown in Scheme 15, compounds of Formula 10a (i.e. Formula 10 wherein R6aand R6bare H, X and Y are O and R2aand R2bare taken together to form a 5- membered ring) can be prepared reacting compounds of Formula 11 with haloalcohols (e.g., 2- chloroethanol or 3-bromopropanol) under basic conditions (e.g., potassium ieri-butoxide in a solvent such as A, A-di methyl formamidc or tetrahydrofuran) to provide compounds of Formula 12. A variety of methods are disclosed in the chemical literature for the conversion of ketones to cyclic ketals and can be readily adapted to prepare compounds of Formula 12 (see, for example, G. Hilgetag and A. Martini, Ed., Preparative Organic Chemistry, pp 381-387: Wiley, New York, 1972, and references sited therein; also see present Example 4, Step A). The ester moiety of the resulting cyclic ketal of Formula 12 can be reduced to the corresponding alcohol of Formula 13 by standard methods known to one skilled in the art (Example 4, Step B illustrates a typical procedure). The hydroxy moiety in the compounds of Formula 13 can then be converted to a wide variety of R29groups to provide compounds of Formula 10a. For example, a mesylate or tosylate group can be installed by treating the alcohol with methanesulfonyl chloride (mesyl chloride) or 4-toluenesulfonyl chloride (tosyl chloride) in the presence of a base such as triethylamine at a temperature between about 0 to 40 °C and in a solvent such as dichloromethane. A triflate group can be installed by treating the alcohol with triflic anhydride (CFgSC^^O as illustrated in Example 4, Step C. Compounds of Formula 11 are known and can be prepared by methods known to one skilled in the art. Scheme 15
[0862] Compounds of Formula lc (i.e. Formula 1 wherein T is T-3 and X is O) can be prepared by reacting a compound of Formula la (i.e. Formula 1 wherein T is T-l and W is O) wherein at least one of R6aand R6bis H with a compound of Formula 14 in the presence of a base, as illustrated in Scheme 16. Suitable bases include cesium or potassium carbonate in a solvent such as A,A-di methyl formamidc (DMF) or dimethyl sulfoxide at temperatures from about 20 to 80 °C. In some cases, the method of Scheme 16 results in a mixture of O-alkylated product (typically as a mixture of ( E )- and (Z)-isomers), along with C-alkylated product. Purification can be achieved using standard techniques such as column chromatography (see Magnetic Resonance in Chemistry 1991, 29, 675-678). Compounds of Formula 14 are commercially available and can be easily synthesized by general methods known to one skilled in the art.
[0863] Scheme 16 wherein at least oneL& is aleaving group such as of R6aand R6bis H Cl, Br, I, OMs, OTs or OTf The method of Scheme 16 is also useful for preparing compounds of Formula lc stating from the corresponding ketone hydrate. Scheme 17 illustrates a specific example where a ketone hydrate of Formula lb4(i.e. Formula lb wherein L is CH2, J is phenyl (i.e. J-l), A is OCH2, R2aX and R2bY are OH and R1is CF3) is reacted with iodoethane in the presence of cesium carbonate in dimethyl sulfoxide at a temperature between about 25 to 75 °C to provide a compound of Formula lc1(i.e. Formula lc wherein L is ϋ¾, J is phenyl (i.e. J-l), A is O, R2dis H, XR2cis OCH2CH3 and R1is CF3). Present Example 5 illustrates the method of Scheme 17.
[0864] Scheme 17
[0865] Compounds of Formula 1 wherein T is T-l and W is S can be prepared from the corresponding compounds wherein W is O by treatment with phosphorus pentasulfide or 2,4- bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2, 4-disulfide (Lawesson’s reagent) in solvents such as toluene, xylene or tetrahydrofuran. One skilled in the art will also recognize that the compounds of Formula 1 wherein T is T-l and W is NR3can be prepared from the compounds of Formula 1 wherein T is T-l and W is O or S by treatment with an amine of Formula R3NH2under dehydrating conditions.
[0866] The E-L- moieties present in the compounds of Formula 1 and the intermediate compounds of Formulae 2 through 7 and 9 are common organic functional groups whose methods of preparation have been documented in the literature. One skilled in the art will recognize that these well-known chemistry classes (esters, amides, sulfonamides, sulfones, ethers, carbamates, ureas, heterocycles) can be readily prepared by a variety of methods (see, for example, WO 2018 / 080859, WO 2018 / 118781, WO 2018 / 187553 and WO 2019 / 010192).
[0867] It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection / deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 2nded.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula 1.
[0868] One skilled in the art will also recognize that compounds of Formula 1 and the intermediates Ill described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
[0869] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated.1H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” means singlet, “br s” means broad singlet, “d” means doublet, “dd” means doublet of doublets, “t” means triplet, “q” means quartet and “m” means multiplet.19F NMR spectra are reported in ppm using trichlorofluoromethane as the reference.
[0870] EXAMPLE 1
[0871] Preparation of ethyl l-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-l -pyrazole-
[0872] 4-carboxylate (Compound 1)
[0873] Step A: Preparation of ethyl l-[(4-hydroxyphenyl)methyl]-l / / -pyrazole-4-carboxylate
[0874] A mixture of ethyl 1 / 7-pyrazolc-4-carboxylatc (1.40 g, 10 mmol), 4-(chloromethyl)phenyl acetate (2.0 g, 11 mmol) and potassium carbonate (1.6 g, 11 mmol) in A, A-di methyl formamidc (10 mL) was stirred at room temperature for 16 h. Ethanol (10 mL) was added and the reaction mixture was heated at 65 °C for 16 h, cooled, and poured into ice water. The resulting precipitate was collected by filtration, washed with water and air dried. The resulting solid (2.0 g) was crystalized from acetonitrile to provide the title compound as a white solid melting at 113-115 °C. in NMR (CDCI3): d 1.32 (t, 3H), 3.10 (d, 1H), 4.10-4.40 (m, 5H), 5.24 (s, 2H), 6.91 (d, 2H), 7.22 (d, 2H), 7.83 (s, 1H), 7.93 (s, 1H).
[0875] Step B: Preparation of ethyl l-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-177- pyrazole-4-carboxylate
[0876] A mixture of ethyl 1 -[(4-hydroxyphcnyl)mcthylJ-l A-pyrazolc-4-carboxylatc (i.e. the product of Step A) (2.36 g, 9.6 mmol), 2-(trifluoromethyl)oxirane (1.3 g, 11.6 mmol) and cesium carbonate (50 mg, 0.15 mmol) in acetonitrile (20 mL) was heated at 65 °C. After 3 days, the reaction mixture was cooled and concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 50% ethyl acetate in hexanes) to provide the title compound as a white solid (2.46 g).lH NMR (CDCI3): d 1.33 (t, 3H), 4.29 (q, 2H), 5.21 (s, 2H), 5.95 (br s, 1H), 6.76 (d, 2H), 7.09 (d, 2H), 7.84 (s, 1H), 7.95 (s, 1H).
[0877] 19F NMR (CDCI3): d -77.54.
[0878] Step C: Preparation of ethyl 1 - [[4-(3, 3, 3-trifluoro-2, 2-dihydiOxypropoxy)phcny 1] methyl J-
[0879] 1 / 7-pyrazolc-4-carboxylatc
[0880] A mixture of ethyl 1 -[[4-(3, 3, 3-trifluoiO-2-hydiOxypiOpoxy)phcnylJ methyl J- 1 / 7-pyrazolc- 4-carboxylate (i.e. the product of Step B) (1.23 g, 3.4 mmol) and Dess-Martin periodinane (2.2 g, 5.2 mmol) in dichloromethane (20 mL) was stirred at room temperature for 16 h, and then concentrated under reduced pressure. The resulting material was dissolved in ethyl acetate and washed with sodium bisulfite solution (2 M aqueous solution), followed by saturated aqueous sodium bicarbonate solution. The organic layer was dried, filtered and the filtrate was concentrated under reduced pressure. The resulting tan solid (1.77 g) was crystalized from acetonitrile to provide the title compound, a compound of the present invention, as solid needles melting at 120-123 °C.in NMR (CDCI3): d 1.32 (t, 3H), 3.80 (br s, 1.7H), 4.18 (s, 2H), 4.28 (q, 2H), 5.25 (s, 2H), 6.95 (d, 2H), 7.22 (d, 2H), 7.82 (s, 1H), 7.95 (s, 1H).
[0881] 19F NMR (CDCI3): d -84.92.
[0882] EXAMPLE 2
[0883] Preparation of ethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]-177- pyrazole-4-carboxylate (Compound 32)
[0884] A mixture of ethyl l-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-177- pyrazole-4-carboxylate (i.e. the product of Example 1) (1.07 g, 3.0 mmol), 2-chloroethanol (0.24 g, 3.0 mmol) and potassium carbonate (0.5 g, 3.6 mmol) in A, A-di methyl formamidc (3.5 mL) was stirred at room temperature for 16 h, and then heated at 65 °C (briefly). After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The resulting material was diluted with diethyl ether and washed with saturated aqueous sodium chloride solution. The organic layer was dried, filtered and the filtrate was concentrated under reduced pressure to provide the title compound, a compound of the present invention, as a colorless oil (1.06 g).in NMR (CDCI3): d 1.32 (t, 3H), 4.21 (s, 4H), 4.23 (s, 2H), 4.27 (q, 2H), 5.24 (s, 2H), 6.94 (d, 2H), 7.20 (d, 2H), 7.81 (s, 1H), 7.93 (s, 1H).
[0885] 19F NMR (CDCI3): d -81.39. EXAMPLE 3
[0886] Preparation of ethyl l-[[4-[[4,4-dimethyl-2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]- phcnyljmcthylj-l / / -pyrazolc-4-carboxylatc (Compound 12)
[0887] The title compound was prepared by a procedure analogous to Example 2.in NMR (CDCI3): d 1.32 (t, 3H), 1.13 (s, 3H), 1.45 (s, 3H), 3.95 (d, 1H), 4.00 (d, 1H), 4.18 (m, 2H), 4.27 (q, 2H), 5.24 (s, 2H), 6.94 (d, 2H), 7.20 (d, 2H), 7.81 (s, 1H), 7.93 (s, 1H).
[0888] 19F NMR (CDCI3): d -81.01.
[0889] EXAMPLE 4
[0890] Alternative preparation of ethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]- mcthylj- 1 / 7-pyrazolc-4-carboxylatc (Compound 32)
[0891] Step A: Preparation of methyl 2-(trifluoromethyl)-l,3-dioxolane-2-carboxylate
[0892] To a mixture of methyl 3 ,3 ,3-tri IΊ uoro-2-oxopropanoatc (31.2 g, 200 mmol) in petroleum ether (100 mL) was added 2-bromoethanol (25.0 g, 200 mmol) over a period of 15 minutes. The reaction mixture was stirred at room temperature for 30 minutes, then cooled to 5 °C and potassium carbonate (28 g, 200 mmol) was added with vigorous stirring. Stirring was continued for an additional 4 h at 5 °C, and then the reaction mixture was allowed to warm to room temperature, diluted with diethyl ether (100 mL) and filtered. The filtrate was concentrated under reduced pressure, and the resulting material was dissolved in diethyl ether (200 mL) and washed with saturated aqueous sodium chloride solution (3x). The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to provide the title compound as a colorless oil (29 g).in NMR (CDCI3): d 3.80 (s, 3H), 4.30 (m, 4H).
[0893] 19F NMR (CDCI3): d -80.52.
[0894] Step B : Preparation of 2-(trifluoromethyl)- 1 ,3-dioxolane-2-methanol
[0895] To a mixture of methyl 2-(trifluoromethyl)-l,3-dioxolane-2-carboxylate (i.e. the product of Step A) (5 g, 25 mmol) in tetrahydrofuran (75 mL) was added sodium bis(2-methoxy- ethoxy)aluminum hydride (60% in toluene) (12.2 mL, 37.5 mmol). The reaction mixture was heated at 40 °C for 1.5 h, and then cooled to room temperature and a solution of ethyl acetate (3.30 g, 37.5 mmol) in tetrahydrofuran (15 mL) was added dropwise over a period of 15 minutes. The reaction mixture was stirred for 45 minutes and then concentrated under reduced pressure. The resulting material was diluted with diethyl ether (400 mL), washed with saturated aqueous sodium chloride solution (2x), dried over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to provide the title compound as an oil (3.8 g).lH NMR (CDCI3): d 2.59 (t, 1H), 3.82 (d, 2H), 4.19 (m, 4H).
[0896] 19F NMR (CDCI3): d -81.50.
[0897] Step C: Preparation of [2-(trifluoromethyl)-l,3-dioxolan-2-yl]methyl 1,1,1-trifluoro- methanesulfonate
[0898] A mixture of 2-(trifluoromethyl)-l,3-dioxolane-2-methanol (i.e. the product of Step B) (1.67 g, 9.70 mmol) and triethylamine (1.5 mL, 10.8 mmol) in dichloromethane (50 mL) was cooled to -78 °C, and then a solution of trifluoromethanesulfonic anhydride (1.81 mL, 10.8 mmol) in dichloromethane (50 mL) was added over a period of 30 minutes. The reaction mixture was stirred at -78 °C for 1.5 h, and then water (50 mL) was added dropwise while allowing the reaction to warm to room temperature. The resulting mixture was partitioned between dichloromethane-water, and the organic layer washed with water, dried over magnesium sulfate and filtered. The filtrated was concentrated under reduced pressure to provide the title compound as a colorless solid (3.0 g). in NMR (CDCI3): d 4.24 (m, 4H), 4.60 (br s, 2H).
[0899] 19F NMR (CDCI3): d -74.84, -81.50.
[0900] Step D: Preparation of ethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]- phenyl] methyl] - 1 / 7-pyrazolc-4-carboxylatc
[0901] To a mixture of ethyl l-[(4-hydroxyphenyl)methyl]-17 / -pyrazole-4-carboxylate (i.e. the product of Example 1, Step A) (16.85 g, 68.0 mmol) and cesium carbonate (53.53 g, 164.5 mmol) in A, A-di methyl formamidc (100 mL) was added [2-(trifluoro methyl)- 1, 3 -dioxolan-2-yl] methyl 1,1,1-trifluoromethanesulfonate (i.e. the product of Step C) (24.9 g, 82.0 mmol). The reaction mixture was stirred for 24 h at room temperature, and then diluted with diethyl ether. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 60% ethyl acetate in hexanes) to provide the title compound, a compound of the present invention, as a white solid (23 g) melting at 59-60 °C. in NMR (CDCI3): d 1.32 (t, 3H), 4.21 (s, 4H), 4.23 (s, 2H), 4.27 (q, 2H), 5.24 (s, 2H), 6.94 (d, 2H), 7.20 (d, 2H), 7.81 (s, 1H), 7.93 (s, 1H).
[0902] 19F NMR (CDCI3): d -81.39. EXAMPLE 5
[0903] Preparation of ethyl l-[[4-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1-propen- l-yl]oxy]phenyl]methyl]- 1 / / -pyrazolc-4-carboxylatc (Compound 64)
[0904] A mixture of ethyl 1 -[[4-(3, 3, 3-trifluoiO-2,2-dihydiOxypiOpoxy)phcnyl] methyl]- 1 H- pyrazole-4-carboxylate (i.e. the product of Example 1) (1.0 g, 2.67 mmol), iodoethane (2.5 g, 16 mmol) and cesium carbonate (1.75 g, 5.37 mmol) in dimethyl sulfoxide (10 mL) was heated at 40 °C for 45 minutes. The reaction mixture was diluted with diethyl ether, washed with water and saturated aqueous sodium chloride solution, dried and filtered. The filtrate was concentrated under reduced pressure to provide the title compound, a compound of the present invention, as a white solid (0.80 g). A portion of the solid was further purified by silica gel chromatography (eluting with a gradient of 0 to 50% ethyl acetate in hexanes) to provide a solid melting at 59- 60 °C. A nuclear Overhauser effect (NOE) was observed between the trifluoromethyl moiety and the vinyl proton indicating a c / .s-con figuration. in NMR (CDCI3): d 1.30-1.40 (m, 6H), 4.17 (q, 2H), 4.27 (q, 2H), 5.28 (s, 2H), 6.78 (q, 1H), 7.05 (m, 2H), 7.29 (m, 2H), 7.86 (s, 1H), 7.94 (s, 1H).
[0905] 19F NMR (CDCI3): d -70.13.
[0906] EXAMPLE 6
[0907] Preparation of ethyl l-[[3-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-17 / -pyrazole-
[0908] 4-carboxylate (Compound 266)
[0909] Step A: Preparation of 3-(bromomethyl)phenol
[0910] A mixture of l-(bromomethyl)-3-methoxybenzene (15.48 g, 76.99 mmol) in dichloromethane (150 mL) was cooled to -78 °C, and then boron tribromide (1 M solution in dichloromethane) was added dropwise. The reaction mixture was allowed to warm to room temperature, stirred for 2 h, and then cooled to -20 °C and methanol (150 mL) was added dropwise. After warming to room temperature, the reaction mixture was concentrated under reduced pressure and the resulting material was diluted with dichloromethane and washed with saturated aqueous sodium bicarbonate solution. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (14.16 g). in NMR (CDCI3): d 4.44 (s, 2H), 4.89 (s, 1H), 6.76 (dd, 1H), 6.87 (s, 1H), 6.95 (d, 1H), 7.19- 7.23 (t, 1H). Step B: Preparation of 3-(bromomethyl)phenyl acetate
[0911] A solution of 3-(bromomethyl)phenol (i.e. the product of Step A) (14.16 g, 75.7 mmol) in dichloromethane (130 mL) was cooled to 0 °C, and then acetic anhydride was added (12.96 g, 12 mL, 126.9 mmol), followed by concentrated sulfuric acid (5 drops). The reaction mixture was allowed to warm to room temperature, stirred for 1 h, and then saturated aqueous sodium bicarbonate solution (300 mL, 318 mmol) was added. The organic layer was separated, washed with water, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to provide the title compound as a solid (16.68 g). in NMR (CDCI3): d 4.47 (s, 2H), 7.02-7.04 (m, 1H), 7.14 (s, 1H), 7.25 (m, 1H), 7.35 (t, 1H). Step C: Preparation of ethyl 1 -[[3-(accty loxy)phcnylJ methyl J-l / 7-pyrazolc-4-carboxy late
[0912] To a mixture of 3-(bromomethyl)phenyl acetate (i.e. the product of Step B) (16.68 g, 72.8 mmol) in acetonitrile (300 mL) was added ethyl 1 / 7-pyrazolc-4-carboxylatc (10.61 g, 75.7 mmol) followed by potassium carbonate (19.35 g, 140 mmol). The reaction mixture was heated at 70 °C overnight, cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure to provide the title compound as a yellow oil (20.5 g). in NMR (CDCI3): d 2.30 (s, 3H), 4.47 (s, 2H), 7.02 (dd, 1H), 7.15 (s, 1H), 7.25 (m, 1H).
[0913] Step D: Preparation of ethyl l-[(3-hydroxyphenyl)methyl]-17 / -pyrazole-4-carboxylate
[0914] To a mixture of ethyl 1 -[[3-(acctyloxy)phcnyl]mcthyl]-l / 7-pyrazolc-4-carboxylatc (i.e. the product of Step C) (20.5 g, 72.8 mmol) in ethanol was added potassium carbonate (10.1 g, 73 mmol). The reaction mixture was heated at reflux for 3 h, cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure and the resulting material was purified by MPLC silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (10.02 g). in NMR (CDCI3): d 1.33 (t, 3H) 4.29 (q, 2H), 5.20 (br s, 1H), 5.25 (s, 2H), 6.66 (m, 1H), 6.78- 6.81 (m, 2H), 7.21-7.24 (m, 1H), 7.87 (s, 1H), 7.94 (s, 1H).
[0915] Step E: Preparation of ethyl l-[[3-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-177- pyrazole-4-carboxylate
[0916] To a mixture of ethyl l-[(3-hydroxyphenyl)methyl]-17 / -pyrazole-4-carboxylate (i.e. the product of Step D) (2.38 g 9.66 mmol) in acetonitrile (100 mL) was added 3-bromo-l,l,l- trifluoro-2-propanol (1.93 g, 1.04 mL, 10 mmol) followed by potassium carbonate (2.86 g, 20.7 mmol). The reaction mixture was heated at reflux for 48 h, cooled to room temperature, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by MPLC silica gel chromatography, (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound as a solid (2.75 g).lH NMR (CDCI3): d 1.33 (q, 3H), 4.1-4.4 (m, 5H), 5.27 (s, 2H), 6.80 (m, 1H), 6.87-6.89 (m, 2H), 7.28-7.31 (m, 1H), 7.88 (s, 1H), 7.94 (s, 1H).
[0917] 19F NMR (CDCI3): d -77.53.
[0918] Step F: Preparation of ethyl 1 - [[3-(3, 3, 3-trifluoiO-2,2-dihydiOxypiOpoxy)phcnyl] methyl J-
[0919] 1 / 7-pyrazolc-4-carhoxylatc
[0920] To a mixture of ethyl 1 -[[ 3-(3, 3, 3-tnfluoiO-2-hydiOxypropoxy)phcnyl] methyl]- 1 H- pyrazole-4-carboxylate (i.e. the product of Step E) (5.7 g, 14.9 mmol) in dichloromethane (300 ruL) was added Dess-Martin periodinane (9.13 g, 20.3 mmol) in one portion. After 3 h, the reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate and washed with sodium bisulfite solution (10% aqueous solution), saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was triturated with 1-chlorobutane to provide the title compound, a compound of the present invention, as a white solid (4.89 g). in NMR (DMSO-6): d 1.27 (t, 3H), 4.01 (s, 2H), 4.20 (m, 2H), 5.33 (s, 2H), 6.86-6.92 (m, 3H), 7.26-7.29 (m, 1H), 7.31 (s, 2H,), 7.87 (s, 1H), 8.48 (s, 1H).
[0921] 19F NMR (DMSO-6): d -81.82.
[0922] EXAMPLE 7
[0923] Preparation of ethyl l-[[3-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1-propen- l-yl]oxy]phenyl]methyl]- 1 / 7-pyrazolc-4-carboxylatc (Compound 265)
[0924] To a mixture of ethyl l-[[3-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-177- pyrazole-4-carboxylate (i.e. the product of Example 6) (2.94 g, 7.85 mmol) in dimethyl sulfoxide (24 ruL) was added iodoethane (2.39 g, 15.3 mmol). The reaction mixture was heated at 65 °C, and then cesium carbonate (4.21 g, 12.92 mmol) was added. After 45 minutes, the reaction mixture was cooled to room temperature, and poured into diethyl ether / water (400 ruL, 1:1 ratio). The organic layer was separated and washed with water, saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound, a compound of the present invention, as a white solid (2.59 g) melting at 41-43 °C. in NMR (CDCI3): d 1.32 (m, 6H), 4.16 (m, 2H,), 4.30 (m, 2H,), 5.31 (s, 2H,), 6.76 (s, 1H), 6.93 (m, 1H), 7.00-7.03 (m, 2H), 7.34-7.37 (m, 1H), 7.90 (s, 1H), 7.95 (s, 1H).
[0925] 19F NMR (CDCI3): d -70.09. EXAMPLE 8
[0926] Preparation of ethyl 1 - [[4-(3, 3, 3-trifluoiO-2,2-dihydiOxypiOpoxy)phcnoxy] methyl]- 1 H- pyrazole-4-carboxylate (Compound 366)
[0927] Step A: Preparation of ethyl 1 -(hydroxymethyl)- 1 / / -pyrazolc-4-carboxylatc
[0928] A mixture of ethyl 1 / / -pyrazolc-4-carboxylatc (6.0 g, 43 mmol), formaldehyde (37% aqueous solution, 12 ruL) and ethanol (50 mL) was heated at reflux overnight. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The resulting material was triturated with 1-chlorobutane to provide the title compound as a white solid (6.2 g). in NMR (DMSO-6): d 1.27 (t, 3H) 4.22 (q, 2H), 5.41 (s, 2H), 7.89 (s, 1H), 8.36 (s, 1H).
[0929] Step B: Preparation of ethyl 1 -(chloromcthyl)- 1 / / -pyrazolc-4-carboxylatc
[0930] To a mixture of ethyl 1 -(hydroxymethyl)- lA-pyrazole-4-carboxylate (i.e. the product of Step A) (6.2 g, 36 mmol) in dichloroethane (100 mL) was added A, A-di methyl formamidc (2 drops), followed by thionyl chloride (5.3 mL, 73 mmol) dropwise. After 3 h, the reaction mixture, was concentrated under reduced pressure to provide the title compound as a yellow solid
[0931] (6.2 g). in NMR (CDCI3): d 1.35 (t, 3H), 4.31 (q, 2H), 5.85 (s, 2H), 7.99 (s, 1H), 8.11 (s, 1H).
[0932] Step C: Preparation of ethyl 1 -[(4-mcthoxyphcnoxy)mcthylJ- 1 A-pyrazolc-4-carboxylatc
[0933] A mixture of ethyl 1 -(chloromcthyl)- 1 A-pyrazolc-4-carboxylatc (i.e. the product of Step B) (2.0 g, 11 mmol), 4-methoxyphenol (1.24 g, 10 mmol), potassium carbonate (2.8 g, 20 mmol) and A,A-dimethylformamide (25 mL) was stirred at room temperature. After 3 days, the reaction mixture was poured into ice water (150 mL) and extracted with diethyl ether (2 x 100 mL). The combined organic layers were washed with water (50 mL), saturated aqueous sodium chloride solution (25 mL), dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 10 to 100% ethyl acetate in hexanes) to provide the title compound as a colorless oil (2.7 g). in NMR (CDCI3): d 1.34 (t, 3H), 3.78 (s, 3H), 4.29 (q, 2H), 5.90 (s, 2H), 6.80-6.84 (m, 2H), 6.88- 6.91 (m, 2H), 7.96 (s, 1H), 8.05 (s, 1H).
[0934] Step D: Preparation of ethyl 1 -[(4-hydiOxyphenoxy)methylJ- 1 A-pyrazole-4-carboxy late
[0935] To a mixture of ethyl 1 -[(4-mcthoxyphcnoxy)mcthylJ- 1 A-pyrazole-4-carboxylate (i.e. the product of Step C) (1.7 g, 6.2 mmol) in dichloromethane (3 mL) was added boron tribromide solution (1 M in dichloromethane, 12.4 mL, 12.4 mmol). After 4 h, saturated aqueous ammonium chloride solution (25 mL) was added to the reaction mixture and stirring was continued for another 15 minutes. The reaction mixture was diluted with dichloromethane (25 mL) and saturated aqueous ammonium chloride solution (25 mL). The organic layer was separated and washed with saturated aqueous sodium bicarbonate solution (25 mL) and saturated aqueous sodium chloride solution (25 mL), drying over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to provide the title compound as a solid (1.65 g). in NMR (DMSO-6): d 1.26 (t, 3H), 4.21 (q, 2H), 5.76 (s, 1H), 5.96 (s, 2H), 6.62-6.71 (m, 2H), 6.82-6.88 (m, 2H), 7.93 (d, 1H), 8.48 (d, 1H).
[0936] Step E: Preparation of ethyl l-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenoxy]methyl]-
[0937] 1 / / -pyrazolc-4-carboxylatc
[0938] To a mixture of ethyl l-[(4-hydroxyphenoxy)methyl]-17 / -pyrazole-4-carboxylate (i.e. the product of Step D) (6.2 mmol) in acetonitrile (20 mL) was added 2-(trifluoromethyl)oxirane (0.62 mL, 7.6 mmol) and cesium carbonate (approximately 10 mg). The reaction mixture was heated at 75 °C overnight, and then cooled to room temperature and concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 10 to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (0.95 g). in NMR (DMSO-6): d 1.26 (t, 3H), 3.96-4.08 (m, 1H), 4.12 (dd, 1H), 4.22 (q, 2H), 4.33-4.36 (m, 1H), 6.04 (s, 2H), 6.62 (d, 1H), 6.88-6.97 (m, 2H), 7.00-7.03 (m, 2H), 7.95 (s, 1H), 8.54 (s, 1H).
[0939] Step L: Preparation of ethyl l-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenoxy]- mcthylj- 1 / / -pyrazolc-4-carboxylatc
[0940] To a mixture of ethyl l-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenoxy]methyl]-177- pyrazole-4-carboxylate (i.e. the product of Step E) (0.95 g, 2.5 mmol) in dichloromethane (25 mL) was added Dess-Martin periodinane (1.5 g, 3.5 mmol) in one portion. The reaction mixture was stirred for 2.5 h, and then saturated aqueous sodium thiosulfate solution (30 mL) was added and the mixture was concentrated under reduced pressure. The resulting mixture was extracted with ethyl acetate (150 mL) and the combined organic layers were washed with saturated aqueous sodium thiosulfate solution (50 mL), saturated aqueous sodium bicarbonate solution (50 mL) and saturated aqueous sodium chloride solution (25 mL), drying over magnesium sulfate and filtered. The filtered was concentrated under reduced pressure and the resulting material was triturated with dichloromethane to provide the title compound, a compound of the present invention, as a solid (0.65 g). in NMR (DMSO-i / 6): d 1.26 (t, 3H), 3.98 (s, 2H), 4.21 (q, 2H), 6.03 (s, 2H), 6.86-6.94 (m, 2H), 6.95-7.06 (m, 2H), 7.27 (s, 2H), 7.94 (s, 1H), 8.53 (s, 1H).
[0941] EXAMPLE 9
[0942] Preparation of ethyl l-[[4-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1-propen- l-yl]oxy]phenoxy]methyl]- 1 / 7-pyrazolc-4-carboxylatc (Compound 364)
[0943] A mixture of iodoethane (2.7 mL, 34 mmol), potassium carbonate (0.84 g, 6.1 mmol) and dimethyl sulfoxide (7 mL) was stirred at room temperature for 20 minutes, and then a solution of ethyl l-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenoxy]methyl]-17 / -pyrazole-4-carboxylate (i.e. the product of Example 8) (0.64 g, 1.6 mmol) in dimethyl sulfoxide (7 mL) was added portionwise over 20 minutes. After stirring at room temperature for 1.5 hours, the reaction mixture was poured into ice water (150 mL) and extracted with ethyl acetate (125 mL). The organic layer was washed with water (2 x 50 mL) and saturated aqueous sodium chloride solution (50 mL), drying over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and the resulting material was purified by silica gel chromatography (eluting with a gradient of 10 to 100% ethyl acetate in hexanes) to provide the title compound, a compound of the present invention, as a colorless oil (0.46 g). in NMR (DMSO-6): d 1.23-1.27 (m, 6H), 4.11 (q, 2H), 4.22 (q, 2H), 6.10 (s, 2H), 7.07-7.24 (m, 4H) 7.95 (s, 1H) 8.58 (s, 1H).
[0944] By the procedures described herein, together with methods known in the art, the following compounds of Tables 1, 1A-48A, 2, and 1B-48B can be prepared. The following abbreviations are used in the Tables: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, z-Pr means isopropyl, c-Pr means cyclopropyl, Bu means butyl, z'-Bu means isobutyl, z-Bu means tert- butyl, and Ph means phenyl.
[0945] Table 1
[0946] In the above formula, E is equal to E , E is equal G-Z-, and G is optionally substituted with lC T The definitions of G are as defined Exhibit A in the above Embodiments. In the column G, the number in parentheses refers to the attachment point of the G-ring to Z. The (R^)xcolumn refers to the substituent(s) attached to the G-ring as shown in Exhibit A above. A dash in the (R^)xcolumn means that no R^ substituent is present and the remaining valences on the G-ring are occupied by hydrogen atoms.
[0947] J is J-l, L is CH2 and Z is a direct bond. H2 and Z is a direct bond.
[0948] G _ (R13)X(R13)X
[0949] G-l (4)
[0950] G-l (4) 2-Me 4-Me -l, F is CH2and Z is a direct bond. H2and Z is a direct bond.
[0951] G (R13)X (R13)X
[0952] G-l (4) 2-Et 4-Et G-l (4) 2-n-Pr 4-n-Pr G-l (4) 2- / -Pr 4- / -Pr G-l (4) 2-oPr 4-oPr G-l (4) 2-n-Bu 4-n-Bu G-l (4) 2- / -Bu 4- / -Bu G-l (4) 2-f-Bu 4-f-Bu G-l (4) 2-F 4-F G-l (4) 2-Cl 4-Cl G-l (4) 2-Br 4-Br G-l (4) 2-CE3 4-CF3 G-l (4) 2-HO 4-HO G-l (4) 2-NºC 4-NºC G-l (4) 2-NºCCH24-NºCCH2G-l (4) 2-(MeO) 4-(MeO) G-l (4) 2-(MeOCH2) 4-(MeOCH2) G-l (4) 2-(EtOCH2) 4-(EtOCH2) G-l (4) 2-(CH(=0)) 4-(CH(=0)) G-l (4) 2-(H0C(=0)) 4-(H0C(=0)) G-l (4) 2-(Me0C(=0)) 4-(Me0C(=0)) G-l (4) 2-(Et0C(=0)) 4-(Et0C(=0)) G-l (4) 2-( / -Pr0C(=0)) 4-( / -Pr0C(=0)) G-l (4) 2-(n-Pr0C(=0)) 4-(n-Pr0C(=0)) G-l (4) 2-(Bu0C(=0)) 4-(Bu0C(=0)) G-l (4) 2-( / -Bu0C(=0)) 4-( / -Bu0C(=0)) G-l (4) 2-(f-Bu0C(=0)) 4-(f-Bu0C(=0)) G-l (4) 2-(CF3CH20C(=0) 4-(CF3CH20C(=0) G-l (4) 2-(CH2=CH0C(=0)) 4-(CH2=CH0C(=0)) G-l (4) 2-(CH2=CHCH20C(=0)) 4-(CH2=CHCH20C(=0)) G-l (4) 2-(CH2=CBrCH20C(=0)) 4-(CH2=CBrCH20C(=0)) G-l (4) 2-(CH2=CHCF20C(=0)) 4-(CH2=CHCF20C(=0)) G-l (4) 2-(Me2C=CHCH20C(=0)) 4-(Me2C=CHCH20C(=0)) -l, L is CH2 and Z is a direct bond. H2and Z is a direct bond.
[0953] G (R13)X (R13)X
[0954] G-l (4) 2-(CH2=C(Me)CH20C(=0)) 4-(CH2=C(Me)CH20C(=0)) G-l (4) 2-(CHºCCH20C(=0)) 4-(CHºCCH20C(=0)) G-l (4) 2-(NºCCH20C(=0)) 4-(NºCCH20C(=0)) G-l (4) 2-(MeNHC(=0)) 4-(MeNHC(=0)) G-l (4) 2-(Me2NC(=0)) 4-(Me2NC(=0)) G-l (4) 2-(MeNHC(=0)) 4-(MeNHC(=0)) G-l (4) 2-(EtNHC(=0)) 4-(EtNHC(=0)) G-l (4) 2-(PrNHC(=0)) 4-(PrNHC(=0)) G-l (4) 2-( / -PrNHC(=0)) 4-( / -PrNHC(=0)) G-l (4) 2-(BuNHC(=0)) 4-(BuNHC(=0)) G-l (4) 2-(f-BuNHC(=0)) 4-(f-BuNHC(=0)) G-l (4) 2-( / -BuNHC(=0)) 4-( / -BuNHC(=0)) G-l (4) 2-(CF3CH2NHC(=0)) 4-(CF3CH2NHC(=0)) G-l (4) 2-(c-PrCH2NHC(=0)) 4-(oPrCH2NHC(=0)) G-l (4) 2-(Me0CH2NHC(=0)) 4-(Me0CH2NHC(=0)) G-l (4) 2-(Me0CH2CH2NHC(=0)) 4-(Me0CH2CH2NHC(=0)) G-l (4) 2-(CH2=CHCH2NHC(=0)) 4-(CH2=CHCH2NHC(=0)) G-l (4) 2-(NºCCH2NHC(=0)) 4-(NºCCH2NHC(=0)) G-l (4) 2-(OH-N=CH) 4-(OH-N=CH) G-l (4) 2-(Me2NN=CH) 4-(Me2NN=CH) G-l (4) 2-(Me0C(=0)NHN=CH) 4-(Me0C(=0)NHN=CH) G-l (4) 2-(0HC(=0)CH20N=CH) 4-(0HC(=0)CH20N=CH) G-l (2) 5-Me, 3-(Et0C(=0)) G-l (2) 4-Me 3 -Me G-l (2) 4-Et 3-Et G-l (2) 4-n-Pr 3-n-Pr G-l (2) 4- / -Pr 3- / -Pr G-l (2) 4-oPr 3-oPr G-l (2) 4-n-Bu 3-n-Bu G-l (2) 4- / -Bu 3- / -Bu G-l (2) 4-f-Bu 3-f-Bu G-l (2) 4-F 3-F -l, L is CH2and Z is a direct bond. H2and Z is a direct bond.
[0955] G (R13)X (R13)X
[0956] G-l (2) 4-Cl 3-Cl G-l (2) 4-Br 3-Br G-l (2) 4-CE3 3-CF3 G-l (2) 4-HO 3 -HO G-l (2) 4-NºC 3-NºC G-l (2) 4-NºCCH23-NºCCH2G-l (2) 4-(MeO) 3-(MeO) G-l (2) 4-(MeOCH2) 3-(MeOCH2) G-l (2) 4-(EtOCH2) 3-(EtOCH2) G-l (2) 4-(CH(=0)) 3-(CH(=0)) G-l (2) 4-(H0C(=0)) 3-(H0C(=0)) G-l (2) 4-(Me0C(=0)) 3-(Me0C(=0)) G-l (2) 4-(Et0C(=0)) 3-(Et0C(=0)) G-l (2) 4-( / -Pr0C(=0)) 3-( / -Pr0C(=0)) G-l (2) 4-(n-Pr0C(=0)) 3-(n-Pr0C(=0)) G-l (2) 4-(Bu0C(=0)) 3-(Bu0C(=0)) G-l (2) 4-( / -Bu0C(=0)) 3-( / -Bu0C(=0)) G-l (2) 4-(f-Bu0C(=0)) 3-(f-Bu0C(=0)) G-l (2) 4-(CF3CH20C(=0) 3-(CF3CH20C(=0) G-l (2) 4-(CH2=CH0C(=0)) 3-(CH2=CH0C(=0)) G-l (2) 4-(CH2=CHCH20C(=0)) 3-(CH2=CHCH20C(=0)) G-l (2) 4-(CH2=CBrCH20C(=0)) 3-(CH2=CBrCH20C(=0)) G-l (2) 4-(CH2=CHCF20C(=0)) 3-(CH2=CHCF20C(=0)) G-l (2) 4-(Me2C=CHCH20C(=0)) 3-(Me2C=CHCH20C(=0)) G-l (2) 4-(CH2=C(Me)CH20C(=0)) 3-(CH2=C(Me)CH20C(=0)) G-l (2) 4-(CHºCCH20C(=0)) 3-(CHºCCH20C(=0)) G-l (2) 4-(NºCCH20C(=0)) 3-(NºCCH20C(=0)) G-l (2) 4-(MeNHC(=0)) 3-(MeNHC(=0)) G-l (2) 4-(Me2NC(=0)) 3-(Me2NC(=0)) G-l (2) 4-(MeNHC(=0)) 3-(MeNHC(=0)) G-l (2) 4-(EtNHC(=0)) 3-(EtNHC(=0)) G-l (2) 4-(PrNHC(=0)) 3-(PrNHC(=0)) -l, L is CH2and Z is a direct bond. H2and Z is a direct bond.
[0957] G (R13)X (R13)X
[0958] G-l (2) 4-( / -PrNHC(=0)) 3-( / -PrNHC(=0)) G-l (2) 4-(BuNHC(=0)) 3-(BuNHC(=0)) G-l (2) 4-(f-BuNHC(=0)) 3-(f-BuNHC(=0)) G-l (2) 4-( / -BuNHC(=0)) 3-( / -BuNHC(=0)) G-l (2) 4-(CF3CH2NHC(=0)) 3-(CF3CH2NHC(=0)) G-l (2) 4-(c-PrCH2NHC(=0)) 3-(c-PrCH2NHC(=0)) G-l (2) 4-(Me0CH2NHC(=0)) 3-(Me0CH2NHC(=0)) G-l (2) 4-(Me0CH2CH2NHC(=0)) 3-(Me0CH2CH2NHC(=0)) G-l (2) 4-(CH2=CHCH2NHC(=0)) 3-(CH2=CHCH2NHC(=0)) G-l (2) 4-(NºCCH2NHC(=0)) 3-(NºCCH2NHC(=0)) G-l (2) 4-(OH-N=CH) 3-(OH-N=CH) G-l (2) 4-(Me2NN=CH) 3-(Me2NN=CH) G-l (2) 4-(Me0C(=0)NHN=CH) 3-(Me0C(=0)NHN=CH) G-l (2) 4-(0HC(=0)CH20N=CH) 3-(0HC(=0)CH20N=CH) G-3 (1) G-3 (1) 4-Me 5 -Me G-3 (1) 4-Et 5-Et G-3 (1) 4-n-Pr 5-n-Pr G-3 (1) 4-i-Pr 5- / -Pr G-3 (1) 4-oPr 5-oPr G-3 (1) 4-n-Bu 5-n-Bu G-3 (1) 4-i-Bu 5- / -Bu G-3 (1) 4-f-Bu 5-f-Bu G-3 (1) 4-F 5-F G-3 (1) 4-Cl 5-Cl G-3 (1) 4-Br 5-Br G-3 (1) 4-CF3 5-CF3 G-3 (1) 4-HO 5 -HO G-3 (1) 4-NºC 5-NºC G-3 (1) 4-NºCCH25-NºCCH2G-3 (1) 4-(MeO) 5-(MeO) G-3 (1) 4-(MeOCH2) 5-(MeOCH2) -l, L is CH2and Z is a direct bond. H2and Z is a direct bond.
[0959] G (R13)X (R13)X
[0960] G-3 (1) 4-(EtOCH2) 5-(EtOCH2) G-3 (1) 4-(CH(=0)) 5-(CH(=0)) G-3 (1) 4-(H0C(=0)) 5-(H0C(=0)) G-3 (1) 4-(Me0C(=0)) 5-(Me0C(=0)) G-3 (1) 4-(Et0C(=0)) 5-(Et0C(=0)) G-3 (1) 4-( / -Pr0C(=0)) 5-( / -Pr0C(=0)) G-3 (1) 4-(n-Pr0C(=0)) 5-(n-Pr0C(=0)) G-3 (1) 4-(Bu0C(=0)) 5-(Bu0C(=0)) G-3 (1) 4-( / -Bu0C(=0)) 5-( / -Bu0C(=0)) G-3 (1) 4-(f-Bu0C(=0)) 5-(f-Bu0C(=0)) G-3 (1) 4-(CF3CH20C(=0) 5-(CF3CH20C(=0) G-3 (1) 4-(CH2=CH0C(=0)) 5-(CH2=CH0C(=0)) G-3 (1) 4-(CH2=CHCH20C(=0)) 5-(CH2=CHCH20C(=0)) G-3 (1) 4-(CH2=CBrCH20C(=0)) 5-(CH2=CBrCH20C(=0)) G-3 (1) 4-(CH2=CHCF20C(=0)) 5-(CH2=CHCF20C(=0)) G-3 (1) 4-(Me2C=CHCH20C(=0)) 5-(Me2C=CHCH20C(=0)) G-3 (1) 4-(CH2=C(Me)CH20C(=0)) 5-(CH2=C(Me)CH20C(=0)) G-3 (1) 4-(CHºCCH20C(=0)) 5-(CHºCCH20C(=0)) G-3 (1) 4-(NºCCH20C(=0)) 5-(NºCCH20C(=0)) G-3 (1) 4-(MeNHC(=0)) 5-(MeNHC(=0)) G-3 (1) 4-(Me2NC(=0)) 5-(Me2NC(=0)) G-3 (1) 4-(MeNHC(=0)) 5-(MeNHC(=0)) G-3 (1) 4-(EtNHC(=0)) 5-(EtNHC(=0)) G-3 (1) 4-(PrNHC(=0)) 5-(PrNHC(=0)) G-3 (1) 4-( / -PrNHC(=0)) 5-( / -PrNHC(=0)) G-3 (1) 4-(BuNHC(=0)) 5-(BuNHC(=0)) G-3 (1) 4-(f-BuNHC(=0)) 5-(f-BuNHC(=0)) G-3 (1) 4-( / -BuNHC(=0)) 5-( / -BuNHC(=0)) G-3 (1) 4-(CF3CH2NHC(=0)) 5-(CF3CH2NHC(=0)) G-3 (1) 4-(c-PrCH2NHC(=0)) 5-(c-PrCH2NHC(=0)) G-3 (1) 4-(Me0CH2NHC(=0)) 5-(Me0CH2NHC(=0)) G-3 (1) 4-(Me0CH2CH2NHC(=0)) 5-(Me0CH2CH2NHC(=0)) -l, L is CH2and Z is a direct bond. H2and Z is a direct bond.
[0961] G (R13)X (R13)X
[0962] G-3 (1) 4-(CH2=CHCH2NHC(=0)) 5-(CH2=CHCH2NHC(=0)) G-3 (1) 4-(NºCCH2NHC(=0)) 5-(NºCCH2NHC(=0)) G-3 (1) 4-(OH-N=CH) 5-(OH-N=CH) G-3 (1) 4-(Me2NN=CH) 5-(Me2NN=CH) G-3 (1) 4-(Me0C(=0)NHN=CH) 5-(Me0C(=0)NHN=CH) G-3 (1) 4-(0HC(=0)CH20N=CH) 5-(0HC(=0)CH20N=CH) G-9 (1) G-9 (1) 3 -Me 4-Me G-9 (1) 3-Et 4-Et G-9 (1) 3-n-Pr 4-n-Pr G-9 (1) 3-i-Pr 4- / -Pr G-9 (1) 3-oPr 4-oPr G-9 (1) 3-n-Bu 4-n-Bu G-9 (1) 3-i-Bu 4- / -Bu G-9 (1) 3-f-Bu 4-f-Bu G-9 (1) 3-F 4-F G-9 (1) 3-Cl 4-Cl G-9 (1) 3-Br 4-Br G-9 (1) 3-CF3 4-CE3 G-9 (1) 3 -HO 4-HO G-9 (1) 3-NºC 4-NºC G-9 (1) 3-NºCCH24-NºCCH2G-9 (1) 3-(MeO) 4-(MeO) G-9 (1) 3-(MeOCH2) 4-(MeOCH2) G-9 (1) 3-(EtOCH2) 4-(EtOCH2) G-9 (1) 3-(CH(=0)) 4-(CH(=0)) G-9 (1) 3-(H0C(=0)) 4-(H0C(=0)) G-9 (1) 3-(Me0C(=0)) 4-(Me0C(=0)) G-9 (1) 3-(Et0C(=0)) 4-(Et0C(=0)) G-9 (1) 3-( -Pr0C(=0)) 4-( / -Pr0C(=0)) G-9 (1) 3-(n-Pr0C(=0)) 4-(n-Pr0C(=0)) G-9 (1) 3-(Bu0C(=0)) 4-(Bu0C(=0)) J is J-l, L is CH2 and Z is a direct bond. H2and Z is a direct bond.
[0963] G _ (R13)X_ (R13)X_
[0964] G-9 (1) 3-( / -Bu0C(=0)) 4-( / -Bu0C(=0))
[0965] G-9 (1) 3-(f-Bu0C(=0)) 4-(f-Bu0C(=0))
[0966] G-9 (1) 3-(CF3CH20C(=0) 4-(CF3CH20C(=0)
[0967] G-9 (1) 3-(CH2=CH0C(=0)) 4-(CH2=CH0C(=0))
[0968] G-9 (1) 3-(CH2=CHCH20C(=0)) 4-(CH2=CHCH20C(=0))
[0969] G-9 (1) 3-(CH2=CBrCH20C(=0)) 4-(CH2=CBrCH20C(=0))
[0970] G-9 (1) 3-(CH2=CHCF20C(=0)) 4-(CH2=CHCF20C(=0))
[0971] G-9 (1) 3-(Me2C=CHCH20C(=0)) 4-(Me2C=CHCH20C(=0))
[0972] G-9 (1) 3-(CH2=C(Me)CH20C(=0)) 4-(CH2=C(Me)CH20C(=0))
[0973] G-9 (1) 3-(CHºCCH20C(=0)) 4-(CHºCCH20C(=0))
[0974] G-9 (1) 3-(NºCCH20C(=0)) 4-(NºCCH20C(=0))
[0975] G-9 (1) 3-(MeNHC(=0)) 4-(MeNHC(=0))
[0976] G-9 (1) 3-(Me2NC(=0)) 4-(Me2NC(=0))
[0977] G-9 (1) 3-(MeNHC(=0)) 4-(MeNHC(=0))
[0978] G-9 (1) 3-(EtNHC(=0)) 4-(EtNHC(=0))
[0979] G-9 (1) 3-(PrNHC(=0)) 4-(PrNHC(=0))
[0980] G-9 (1) 3-( / -PrNHC(=0)) 4-( / -PrNHC(=0))
[0981] G-9 (1) 3-(BuNHC(=0)) 4-(BuNHC(=0))
[0982] G-9 (1) 3-(f-BuNHC(=0)) 4-(f-BuNHC(=0))
[0983] G-9 (1) 3-( / -BuNHC(=0)) 4-( / -BuNHC(=0))
[0984] G-9 (1) 3-(CF3CH2NHC(=0)) 4-(CF3CH2NHC(=0))
[0985] G-9 (1) 3-(c-PrCH2NHC(=0)) 4-(oPrCH2NHC(=0))
[0986] G-9 (1) 3-(Me0CH2NHC(=0)) 4-(Me0CH2NHC(=0))
[0987] G-9 (1) 3-(Me0CH2CH2NHC(=0)) 4-(Me0CH2CH2NHC(=0))
[0988] G-9 (1) 3-(CH2=CHCH2NHC(=0)) 4-(CH2=CHCH2NHC(=0))
[0989] G-9 (1) 3-(NºCCH2NHC(=0)) 4-(NºCCH2NHC(=0))
[0990] G-9 (1) 3-(OH-N=CH) 4-(OH-N=CH)
[0991] G-9 (1) 3-(Me2NN=CH) 4-(Me2NN=CH)
[0992] G-9 (1) 3-(Me0C(=0)NHN=CH) 4-(Me0C(=0)NHN=CH)
[0993] G-9 (1) 3-(0HC(=0)CH20N=CH) 4-(0HC(=0)CH20N=CH)
[0994] The present disclosure also includes Tables 1A through 48A, each of which is constructed the same as Table 1 above, except that the row heading in Table 1 (i.e. “J is J-l, L is CH2 and Z s a direct bond”) is replaced with the respective row headings shown below.
[0995] Table Row Heading Table Row Heading
[0996] 1A J is J-l, L is CH2CH2 and Z is a direct bond. 25A J is J- 10, L is CH2 and Z is a direct bond.
[0997] 2A J is J-l, L is CH2(Me) and Z is a direct bond. 26A J is J- 10, L is CH2CH2 and Z is a direct bond.
[0998] 3 A J is J-l, L is (CH2)3 and Z is a direct bond. 27A J is J- 10, L is CH2(Me) and Z is a direct bond.
[0999] 4A J is J-l, L is CH2 and Z is O. 28A J is J- 10, L is (CH2)3 and Z is a direct bond.
[1000] 5A J is J-2, L is CH2 and Z is a direct bond. 29A J is J-10, L is CH2 and Z is O.
[1001] 6A J is J-2, L is CH2CH2 and Z is a direct bond. 30A J is J- 14, L is CH2 and Z is a direct bond.
[1002] 7A J is J-2, L is CH2(Me) and Z is a direct bond. 31A J is J- 14, L is CH2CH2 and Z is a direct bond.
[1003] 8A J is J-2, L is (CH2)3 and Z is a direct bond. 32A J is J- 14, L is CH2(Me) and Z is a direct bond. 9A J is J-2, L is CH2 and Z is O. 33A J is J- 14, L is (CH2)3 and Z is a direct bond.
[1004] 10A J is J-6, L is CH2 and Z is a direct bond. 34A J is J-14, L is CH2 and Z is O.
[1005] 11 A J is J-6, L is CH2CH2 and Z is a direct bond. 35A J is J-3, L is CH2 and Z is a direct bond.
[1006] 12A J is J-6, L is CH2(Me) and Z is a direct bond. 36A J is J-3, L is CH2CH2 and Z is a direct bond.
[1007] 13A J is J-6, L is (CH2)3 and Z is a direct bond. 37A J is J-3, L is CH2(Me) and Z is a direct bond. 14A J is J-6, L is CH2 and Z is O. 38A J is J-3, L is (CH2)3 and Z is a direct bond.
[1008] 15A J is J-7, L is CH2 and Z is a direct bond. 39A J is J-3, L is CH2 and Z is O.
[1009] 16A J is J-7, L is CH2CH2 and Z is a direct bond. 40A J is J-4, L is CH2 and Z is a direct bond.
[1010] 17A J is J-7, L is CH2(Me) and Z is a direct bond. 41 A J is J-4, L is CH2CH2 and Z is a direct bond.
[1011] 18A J is J-7, L is (CH2)3 and Z is a direct bond. 42A J is J-4, L is CH2(Me) and Z is a direct bond. 19A J is J-7, L is CH2 and Z is O. 43A J is J-4, L is (CH2)3 and Z is a direct bond.
[1012] 20A J is J-8, L is CH2 and Z is a direct bond. 44A J is J-4, L is CH2 and Z is O.
[1013] 21 A J is J-8, L is CH2CH2 and Z is a direct bond. 45A J is J-5, L is CH2 and Z is a direct bond.
[1014] 22A J is J-8, L is CH2(Me) and Z is a direct bond. 46A J is J-5, L is CH2CH2 and Z is a direct bond.
[1015] 23A J is J-8, L is (CH2)3 and Z is a direct bond. 47A J is J-5, L is CH2(Me) and Z is a direct bond. 24A J is J-8, L is CH2 and Z is O. 48A J is J-5, L is (CH2)3 and Z is a direct bond.
[1016] Table 2
[1017] In the above formula, E is equal to E^, E^ is equal G-Z-, and G is optionally substituted with R ^ . The definitions of G are as defined Exhibit A in the above Embodiments. In the column G, the number in parentheses refers to the attachment point of the G-ring to Z. The (R^3)xcolumn refers to the substituent(s) attached to the G-ring as shown in Exhibit A above. A dash in the (R^3)xcolumn means that no R *3substituent is present and the remaining valences on the G-ring are occupied by hydrogen atoms. is -l, L is CH2 and Z is a direct bond. H2and Z is a direct bond.
[1018] G (R13)X (R13)X
[1019] G-l (4) 2-(CH2=CH0C(=0)) 4-(CH2=CH0C(=0)) G-l (4) 2-(CH2=CHCH20C(=0)) 4-(CH2=CHCH20C(=0)) G-l (4) 2-(CH2=CBrCH20C(=0)) 4-(CH2=CBrCH20C(=0)) G-l (4) 2-(CH2=CHCF20C(=0)) 4-(CH2=CHCF20C(=0)) G-l (4) 2-(Me2C=CHCH20C(=0)) 4-(Me2C=CHCH20C(=0)) G-l (4) 2-(CH2=C(Me)CH20C(=0)) 4-(CH2=C(Me)CH20C(=0)) G-l (4) 2-(CHºCCH20C(=0)) 4-(CHºCCH20C(=0)) G-l (4) 2-(NºCCH20C(=0)) 4-(NºCCH20C(=0)) G-l (4) 2-(MeNHC(=0)) 4-(MeNHC(=0)) G-l (4) 2-(Me2NC(=0)) 4-(Me2NC(=0)) G-l (4) 2-(MeNHC(=0)) 4-(MeNHC(=0)) G-l (4) 2-(EtNHC(=0)) 4-(EtNHC(=0)) G-l (4) 2-(PrNHC(=0)) 4-(PrNHC(=0)) G-l (4) 2-( / -PrNHC(=0)) 4-( / -PrNHC(=0)) G-l (4) 2-(BuNHC(=0)) 4-(BuNHC(=0)) G-l (4) 2-(f-BuNHC(=0)) 4-(f-BuNHC(=0)) G-l (4) 2-( / -BuNHC(=0)) 4-( / -BuNHC(=0)) G-l (4) 2-(CF3CH2NHC(=0)) 4-(CF3CH2NHC(=0)) G-l (4) 2-(c-PrCH2NHC(=0)) 4-(oPrCH2NHC(=0)) G-l (4) 2-(Me0CH2NHC(=0)) 4-(Me0CH2NHC(=0)) G-l (4) 2-(Me0CH2CH2NHC(=0)) 4-(Me0CH2CH2NHC(=0)) G-l (4) 2-(CH2=CHCH2NHC(=0)) 4-(CH2=CHCH2NHC(=0)) G-l (4) 2-(NºCCH2NHC(=0)) 4-(NºCCH2NHC(=0)) G-l (4) 2-(OH-N=CH) 4-(OH-N=CH) G-l (4) 2-(Me2NN=CH) 4-(Me2NN=CH) G-l (4) 2-(Me0C(=0)NHN=CH) 4-(Me0C(=0)NHN=CH) G-l (4) 2-(0HC(=0)CH20N=CH) 4-(0HC(=0)CH20N=CH) G-l (2) 5-Me, 3-(Et0C(=0)) G-l (2) 4-Me 3 -Me G-l (2) 4-Et 3-Et G-l (2) 4-n-Pr 3-n-Pr G-l (2) 4- / -Pr 3- / -Pr -l, L is CF12and Z is a direct bond. H and Z is a direct bond.
[1020] G (R13)X (R13)X
[1021] G-l (2) 4-oPr 3-oPr G-l (2) 4-n-Bu 3-n-Bu G-l (2) 4- / -Bu 3- / -Bu G-l (2) 4-f-Bu 3-f-Bu G-l (2) 4-F 3-F G-l (2) 4-Cl 3-Cl G-l (2) 4-Br 3-Br G-l (2) 4-CE3 3-CF3 G-l (2) 4-HO 3-HO G-l (2) 4-NºC 3-NºC G-l (2) 4-NºCCH23-NºCCH2G-l (2) 4-(MeO) 3-(MeO) G-l (2) 4-(MeOCH2) 3-(MeOCH2) G-l (2) 4-(EtOCH2) 3-(EtOCH2) G-l (2) 4-(CH(=0)) 3-(CH(=0)) G-l (2) 4-(H0C(=0)) 3-(H0C(=0)) G-l (2) 4-(Me0C(=0)) 3-(Me0C(=0)) G-l (2) 4-(Et0C(=0)) 3-(Et0C(=0)) G-l (2) 4-( / -Pr0C(=0)) 3-( / -Pr0C(=0)) G-l (2) 4-(n-Pr0C(=0)) 3-(n-Pr0C(=0)) G-l (2) 4-(Bu0C(=0)) 3-(Bu0C(=0)) G-l (2) 4-( / -Bu0C(=0)) 3-( / -Bu0C(=0)) G-l (2) 4-(f-Bu0C(=0)) 3-(f-Bu0C(=0)) G-l (2) 4-(CF3CH20C(=0) 3-(CF3CH20C(=0) G-l (2) 4-(CH2=CH0C(=0)) 3-(CH2=CH0C(=0)) G-l (2) 4-(CH2=CHCH20C(=0)) 3-(CH2=CHCH20C(=0)) G-l (2) 4-(CH2=CBrCH20C(=0)) 3-(CH2=CBrCH20C(=0)) G-l (2) 4-(CH2=CHCF20C(=0)) 3-(CH2=CHCF20C(=0)) G-l (2) 4-(Me2C=CHCH20C(=0)) 3-(Me2C=CHCH20C(=0)) G-l (2) 4-(CH2=C(Me)CH20C(=0)) 3-(CH2=C(Me)CH20C(=0)) G-l (2) 4-(CHºCCH20C(=0)) 3-(CHºCCH20C(=0)) G-l (2) 4-(NºCCH20C(=0)) 3-(NºCCH20C(=0)) -l, L is CH2and Z is a direct bond. H2and Z is a direct bond.
[1022] G (R13)X (R13)X
[1023] G-l (2) 4-(MeNHC(=0)) 3-(MeNHC(=0)) G-l (2) 4-(Me2NC(=0)) 3-(Me2NC(=0)) G-l (2) 4-(MeNHC(=0)) 3-(MeNHC(=0)) G-l (2) 4-(EtNHC(=0)) 3-(EtNHC(=0)) G-l (2) 4-(PrNHC(=0)) 3-(PrNHC(=0)) G-l (2) 4-( / -PrNHC(=0)) 3-( / -PrNHC(=0)) G-l (2) 4-(BuNHC(=0)) 3-(BuNHC(=0)) G-l (2) 4-(f-BuNHC(=0)) 3-(f-BuNHC(=0)) G-l (2) 4-( / -BuNHC(=0)) 3-( / -BuNHC(=0)) G-l (2) 4-(CF3CH2NHC(=0)) 3-(CF3CH2NHC(=0)) G-l (2) 4-(c-PrCH2NHC(=0)) 3-(c-PrCH2NHC(=0)) G-l (2) 4-(Me0CH2NHC(=0)) 3-(Me0CH2NHC(=0)) G-l (2) 4-(Me0CH2CH2NHC(=0)) 3-(Me0CH2CH2NHC(=0)) G-l (2) 4-(CH2=CHCH2NHC(=0)) 3-(CH2=CHCH2NHC(=0)) G-l (2) 4-(NºCCH2NHC(=0)) 3-(NºCCH2NHC(=0)) G-l (2) 4-(OH-N=CH) 3-(OH-N=CH) G-l (2) 4-(Me2NN=CH) 3-(Me2NN=CH) G-l (2) 4-(Me0C(=0)NHN=CH) 3-(Me0C(=0)NHN=CH) G-l (2) 4-(0HC(=0)CH20N=CH) 3-(0HC(=0)CH20N=CH) G-3 (1) G-3 (1) 4-Me 5 -Me G-3 (1) 4-Et 5-Et G-3 (1) 4-n-Pr 5-n-Pr G-3 (1) 4-i-Pr 5- / -Pr G-3 (1) 4-oPr 5-oPr G-3 (1) 4-n-Bu 5-n-Bu G-3 (1) 4-i-Bu 5- / -Bu G-3 (1) 4-f-Bu 5-f-Bu G-3 (1) 4-F 5-F G-3 (1) 4-Cl 5-Cl G-3 (1) 4-Br 5-Br G-3 (1) 4-CF3 5-CF3 -l, L is CH2and Z is a direct bond. H2and Z is a direct bond.
[1024] G (R13)X (R13)X
[1025] G-3 (1) 4-HO 5 -HO G-3 (1) 4-NºC 5-NºC G-3 (1) 4-NºCCH25-NºCCH2G-3 (1) 4-(MeO) 5-(MeO) G-3 (1) 4-(MeOCH2) 5-(MeOCH2) G-3 (1) 4-(EtOCH2) 5-(EtOCH2) G-3 (1) 4-(CH(=0)) 5-(CH(=0)) G-3 (1) 4-(H0C(=0)) 5-(H0C(=0)) G-3 (1) 4-(Me0C(=0)) 5-(Me0C(=0)) G-3 (1) 4-(Et0C(=0)) 5-(Et0C(=0)) G-3 (1) 4-( / -Pr0C(=0)) 5-( / -Pr0C(=0)) G-3 (1) 4-(n-Pr0C(=0)) 5-(n-Pr0C(=0)) G-3 (1) 4-(Bu0C(=0)) 5-(Bu0C(=0)) G-3 (1) 4-( / -Bu0C(=0)) 5-( / -Bu0C(=0)) G-3 (1) 4-(f-Bu0C(=0)) 5-(f-Bu0C(=0)) G-3 (1) 4-(CF3CH20C(=0) 5-(CF3CH20C(=0) G-3 (1) 4-(CH2=CH0C(=0)) 5-(CH2=CH0C(=0)) G-3 (1) 4-(CH2=CHCH20C(=0)) 5-(CH2=CHCH20C(=0)) G-3 (1) 4-(CH2=CBrCH20C(=0)) 5-(CH2=CBrCH20C(=0)) G-3 (1) 4-(CH2=CHCF20C(=0)) 5-(CH2=CHCF20C(=0)) G-3 (1) 4-(Me2C=CHCH20C(=0)) 5-(Me2C=CHCH20C(=0)) G-3 (1) 4-(CH2=C(Me)CH20C(=0)) 5-(CH2=C(Me)CH20C(=0)) G-3 (1) 4-(CHºCCH20C(=0)) 5-(CHºCCH20C(=0)) G-3 (1) 4-(NºCCH20C(=0)) 5-(NºCCH20C(=0)) G-3 (1) 4-(MeNHC(=0)) 5-(MeNHC(=0)) G-3 (1) 4-(Me2NC(=0)) 5-(Me2NC(=0)) G-3 (1) 4-(MeNHC(=0)) 5-(MeNHC(=0)) G-3 (1) 4-(EtNHC(=0)) 5-(EtNHC(=0)) G-3 (1) 4-(PrNHC(=0)) 5-(PrNHC(=0)) G-3 (1) 4-( / -PrNHC(=0)) 5-( / -PrNHC(=0)) G-3 (1) 4-(BuNHC(=0)) 5-(BuNHC(=0)) G-3 (1) 4-(f-BuNHC(=0)) 5-(f-BuNHC(=0)) -l, L is CH2and Z is a direct bond. H2and Z is a direct bond.
[1026] G (R13)X (R13)X
[1027] G-3 (1) 4-( / -BuNHC(=0)) 5-( / -BuNHC(=0)) G-3 (1) 4-(CF3CH2NHC(=0)) 5-(CF3CH2NHC(=0)) G-3 (1) 4-(c-PrCH2NHC(=0)) 5-(c-PrCH2NHC(=0)) G-3 (1) 4-(Me0CH2NHC(=0)) 5-(Me0CH2NHC(=0)) G-3 (1) 4-(Me0CH2CH2NHC(=0)) 5-(Me0CH2CH2NHC(=0)) G-3 (1) 4-(CH2=CHCH2NHC(=0)) 5-(CH2=CHCH2NHC(=0)) G-3 (1) 4-(NºCCH2NHC(=0)) 5-(NºCCH2NHC(=0)) G-3 (1) 4-(OH-N=CH) 5-(OH-N=CH) G-3 (1) 4-(Me2NN=CH) 5-(Me2NN=CH) G-3 (1) 4-(Me0C(=0)NHN=CH) 5-(Me0C(=0)NHN=CH) G-3 (1) 4-(0HC(=0)CH20N=CH) 5-(0HC(=0)CH20N=CH) G-9 (1) G-9 (1) 3 -Me 4-Me G-9 (1) 3-Et 4-Et G-9 (1) 3-n-Pr 4-n-Pr G-9 (1) 3-i-Pr 4- / -Pr G-9 (1) 3-oPr 4-oPr G-9 (1) 3-n-Bu 4-n-Bu G-9 (1) 3-i-Bu 4- / -Bu G-9 (1) 3-f-Bu 4-f-Bu G-9 (1) 3-F 4-F G-9 (1) 3-Cl 4-Cl G-9 (1) 3-Br 4-Br G-9 (1) 3-CF3 4-CE3 G-9 (1) 3 -HO 4-HO G-9 (1) 3-NºC 4-NºC G-9 (1) 3-NºCCH24-NºCCH2G-9 (1) 3-(MeO) 4-(MeO) G-9 (1) 3-(MeOCH2) 4-(MeOCH2) G-9 (1) 3-(EtOCH2) 4-(EtOCH2) G-9 (1) 3-(CH(=0)) 4-(CH(=0)) G-9 (1) 3-(H0C(=0)) 4-(H0C(=0)) -l, F is CH2and Z is a direct bond. H2and Z is a direct bond.
[1028] G (R13)X (R13)X
[1029] G-9 (1) 3-(Me0C(=0)) 4-(Me0C(=0)) G-9 (1) 3-(Et0C(=0)) 4-(Et0C(=0)) G-9 (1) 3-( / -Pr0C(=0)) 4-( / -Pr0C(=0)) G-9 (1) 3-(n-Pr0C(=0)) 4-(n-Pr0C(=0)) G-9 (1) 3-(Bu0C(=0)) 4-(Bu0C(=0)) G-9 (1) 3-( / -Bu0C(=0)) 4-( / -Bu0C(=0)) G-9 (1) 3-(f-Bu0C(=0)) 4-(f-Bu0C(=0)) G-9 (1) 3-(CF3CH20C(=0) 4-(CF3CH20C(=0) G-9 (1) 3-(CH2=CH0C(=0)) 4-(CH2=CH0C(=0)) G-9 (1) 3-(CH2=CHCH20C(=0)) 4-(CH2=CHCH20C(=0)) G-9 (1) 3-(CH2=CBrCH20C(=0)) 4-(CH2=CBrCH20C(=0)) G-9 (1) 3-(CH2=CHCF20C(=0)) 4-(CH2=CHCF20C(=0)) G-9 (1) 3-(Me2C=CHCH20C(=0)) 4-(Me2C=CHCH20C(=0)) G-9 (1) 3-(CH2=C(Me)CH20C(=0)) 4-(CH2=C(Me)CH20C(=0)) G-9 (1) 3-(CHºCCH20C(=0)) 4-(CHºCCH20C(=0)) G-9 (1) 3-(NºCCH20C(=0)) 4-(NºCCH20C(=0)) G-9 (1) 3-(MeNHC(=0)) 4-(MeNHC(=0)) G-9 (1) 3-(Me2NC(=0)) 4-(Me2NC(=0)) G-9 (1) 3-(MeNHC(=0)) 4-(MeNHC(=0)) G-9 (1) 3-(EtNHC(=0)) 4-(EtNHC(=0)) G-9 (1) 3-(PrNHC(=0)) 4-(PrNHC(=0)) G-9 (1) 3-( / -PrNHC(=0)) 4-( / -PrNHC(=0)) G-9 (1) 3-(BuNHC(=0)) 4-(BuNHC(=0)) G-9 (1) 3-(f-BuNHC(=0)) 4-(f-BuNHC(=0)) G-9 (1) 3-( / -BuNHC(=0)) 4-( / -BuNHC(=0)) G-9 (1) 3-(CF3CH2NHC(=0)) 4-(CF3CH2NHC(=0)) G-9 (1) 3-(c-PrCH2NHC(=0)) 4-(c-PrCH2NHC(=0)) G-9 (1) 3-(Me0CH2NHC(=0)) 4-(Me0CH2NHC(=0)) G-9 (1) 3-(Me0CH2CH2NHC(=0)) 4-(Me0CH2CH2NHC(=0)) G-9 (1) 3-(CH2=CHCH2NHC(=0)) 4-(CH2=CHCH2NHC(=0)) G-9 (1) 3-(NºCCH2NHC(=0)) 4-(NºCCH2NHC(=0)) G-9 (1) 3-(OH-N=CH) 4-(OH-N=CH) J is J-l, L is CH2and Z is a direct bond. H2 and Z is a direct bond.
[1030] G (R13)X (R13)X
[1031] G-9 (1) 3-(Me2NN=CH) 4-(Me2NN=CH) G-9 (1) 3-(MeOC(=0)NHN=CH) 4-(Me0C(=0)NHN=CH) G-9 (1) 3-(0HC(=0)CH20N=CH) 4-(0HC(=0)CH20N=CH)
[1032] The present disclosure also includes Tables IB through 48B, each of which is constructed the same as Table 2 above, except that the row heading in Table 2 (i.e. “J is J-l, L is CH2, and Z is a direct bond”) is replaced with the respective row headings shown below.
[1033] Table Row Heading Table Row Heading
[1034] IB J is J-l, L is CH2CH2and Z is a direct bond. 25B J is J- 10, L is CH2and Z is a direct bond.
[1035] 2B J is J-l, L is CH2(Me) and Z is a direct bond. 26B J is J- 10, L is CH2CH2and Z is a direct bond.
[1036] 3B J is J-l, L is (CH2)3 and Z is a direct bond. 27B J is J- 10, L is CH2(Me) and Z is a direct bond. 4B J is J-l, L is CH2and Z is O. 28B J is J- 10, L is (CH2)3 and Z is a direct bond.
[1037] 5B J is J-2, L is CH2and Z is a direct bond. 29B J is J- 10, L is CH2and Z is O.
[1038] 6B J is J-2, L is CH2CH2and Z is a direct bond. 30B J is J- 14, L is CH2and Z is a direct bond.
[1039] 7B J is J-2, L is CH2(Me) and Z is a direct bond. 31B J is J- 14, L is CH2CH2and Z is a direct bond.
[1040] 8B J is J-2, L is (CH2)3 and Z is a direct bond. 32B J is J- 14, L is CH2(Me) and Z is a direct bond. 9B J is J-2, L is CH2and Z is O. 33B J is J- 14, L is (CH2)3 and Z is a direct bond.
[1041] 10B J is J-6, L is CH2and Z is a direct bond. 34B J is J- 14, L is CH2and Z is O.
[1042] 1 IB J is J-6, L is CH2CH2and Z is a direct bond. 35B J is J-3, L is CH2and Z is a direct bond.
[1043] 12B J is J-6, L is CH2(Me) and Z is a direct bond. 36B J is J-3, L is CH2CH2and Z is a direct bond.
[1044] 13B J is J-6, L is (CH2)3 and Z is a direct bond. 37B J is J-3, L is CH2(Me) and Z is a direct bond. 14B J is J-6, L is CH2and Z is O. 38B J is J-3, L is (CH2)3 and Z is a direct bond.
[1045] 15B J is J-7, L is CH2and Z is a direct bond. 39B J is J-3, L is CH2and Z is O.
[1046] 16B J is J-7, L is CH2CH2and Z is a direct bond. 40B J is J-4, L is CH2and Z is a direct bond.
[1047] 17B J is J-7, L is CH2(Me) and Z is a direct bond. 41B J is J-4, L is CH2CH2and Z is a direct bond.
[1048] 18B J is J-7, L is (CH2)3 and Z is a direct bond. 42B J is J-4, L is CH2(Me) and Z is a direct bond. 19B J is J-7, L is CH2and Z is O. 43B J is J-4, L is (CH2)3 and Z is a direct bond.
[1049] 20B J is J-8, L is CH2and Z is a direct bond. 44B J is J-4, L is CH2and Z is O.
[1050] 21B J is J-8, L is CH2CH2and Z is a direct bond. 45B J is J-5, L is CH2and Z is a direct bond.
[1051] 22B J is J-8, L is CH2(Me) and Z is a direct bond. 46B J is J-5, L is CH2CH2and Z is a direct bond.
[1052] 23B J is J-8, L is (CH2)3 and Z is a direct bond. 47B J is J-5, L is CH2(Me) and Z is a direct bond.
[1053] 24B J is J-8, L is CH2and Z is O. 48B J is J-5, L is (CH2)3 and Z is a direct bond.
[1054] Formulation / U tility A compound of Formula 1 of this invention (including A-oxidcs and salts thereof), or a mixture (i.e. composition) comprising the compound with at least one additional fungicidal compound as described in the Summary of the Invention, will generally be used as a fungicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
[1055] The mixtures of component (a) (i.e. at least one compound of Formula 1, A-oxides, or salts thereof) with component (b) (e.g., selected from (bl) to (b54) and salts thereof as described above) and / or one or more other biologically active compound or agent (i.e. insecticides, other fungicides, nematocides, acaricides, herbicides and other biological agents) can be formulated in a number of ways, including:
[1056] (i) component (a), component (b) and / or one or more other biologically active compounds or agents can be formulated separately and applied separately or applied simultaneously in an appropriate weight ratio, e.g., as a tank mix; or
[1057] (ii) component (a), component (b) and / or one or more other biologically active compounds or agents can be formulated together in the proper weight ratio.
[1058] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates and / or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspoemulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
[1059] The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
[1060] Of note is a composition embodiment wherein granules of a solid composition comprising a compound of Formula 1 (or an / V-oxide or salt thereof) is mixed with granules of a solid composition comprising component (b). These mixtures can be further mixed with granules comprising additional agricultural protectants. Alternatively, two or more agricultural protectants (e.g., a component (a) (Formula 1) compound, a component (b) compound, an agricultural protectant other than component (a) or (b)) can be combined in the solid composition of one set of granules, which is then mixed with one or more sets of granules of solid compositions comprising one or more additional agricultural protectants. These granule mixtures can be in accordance with the general granule mixture disclosure of PCT Patent Publication WO 94 / 24861 or more preferably the homogeneous granule mixture teaching of U.S. Patent 6,022,552.
[1061] Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and / or foliage through systemic uptake.
[1062] The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
[1063] Weight Percent Active
[1064] Ingredient Diluent Surfactant
[1065] Water-Dispersible and Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and Powders
[1066] Oil Dispersions, Suspensions, 1-50 40-99 0-50 Emulsions, Solutions (including Emulsifiable Concentrates)
[1067] Dusts 1-25 70-99 0-5 Granules and Pellets 0.001-95 5-99.999 0-15
[1068] High Strength Compositions 90-99 0-10 0-2
[1069] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et ah, Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
[1070] Liquid diluents include, for example, water, / V, / V-dimethylalkanamides (e.g., / V, / V-dimethylformamide), limonene, dimethyl sulfoxide, N- alky lp y rro 1 i do n c s (e.g., / V-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobomyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and g- butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n -propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hcxanol, 2- ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22X such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, com (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal -sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
[1071] The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
[1072] Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as poly ethoxylated sorbitan fatty acid esters, poly ethoxylated sorbitol fatty acid esters and poly ethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides; alkyl polysaccharides; and glucamides such as mixtures of octyl-V-mcthylglucamidc and dccy 1 -N- met h y 1 g 1 uca m i dc (e.g., products is obtainable under the Synergen® GA name from Clariant).
[1073] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as / V, / V-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfo succinate salts. Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N- alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
[1074] Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon ’s Emulsifiers and Detergents , annual American and International Editions published by McCutcheon’ s Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
[1075] Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes / pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon’ s Volume 2: Functional Materials, annual International and North American editions published by McCutcheon’ s Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03 / 024222.
[1076] The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 mih can be wet milled using media mills to obtain particles with average diameters below 3 pm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 pm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, December 4, 1967, pp 147-48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp 8-57 and following, and WO 91 / 13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
[1077] One embodiment of the present invention relates to a method for controlling fungal pathogens, comprising diluting the fungicidal composition of the present invention (a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other fungicide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the fungal pathogen or its environment with an effective amount of said diluted composition.
[1078] Although a spray composition formed by diluting with water a sufficient concentration of the present fungicidal composition can provide sufficient efficacy for controlling fungal pathogens, separately formulated adjuvant products can also be added to spray tank mixtures. These additional adjuvants are commonly known as “spray adjuvants” or “tank-mix adjuvants”, and include any substance mixed in a spray tank to improve the performance of a pesticide or alter the physical properties of the spray mixture. Adjuvants can be anionic or nonionic surfactants, emulsifying agents, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners or defoaming agents. Adjuvants are used to enhancing efficacy (e.g., biological availability, adhesion, penetration, uniformity of coverage and durability of protection), or minimizing or eliminating spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization and degradation. To obtain optimal performance, adjuvants are selected with regard to the properties of the active ingredient, formulation and target (e.g., crops, insect pests).
[1079] The amount of adjuvants added to spray mixtures is generally in the range of about 0.1 % to 2.5% by volume. The application rates of adjuvants added to spray mixtures are typically between about 1 to 5 L per hectare. Representative examples of spray adjuvants include: Adigor® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (Helena Chemical Company) polyalkyleneoxide modified heptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.
[1080] One method of seed treatment is by spraying or dusting the seed with a compound of the invention (i.e. as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment generally comprise a film former...
Claims
CLAIMSWhat is claimed is:
1. A fungicidal composition comprising:(a) at least one compound selected from the compounds of Formula 1, A-oxides, and salts thereof:1 whereinT is selected from the group consisting of:T-l T-2 T-3 wherein the bond extending to the left is attached to A;R1is CF3, CHF2, CC13, CHC12, CF2C1, CFC12or CHFC1;W is O, S or NR3;R3is H, cyano, nitro, C(=0)0H, benzyl, C|-C4alkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, OR3aor NR3bR3c;R3ais H, benzyl, C|-C4alkyl, C2-C4 alkylcarbonyl or C2-C4 haloalkylcarbonyl;R3bis H, C I -C4alkyl, C2-C4 alkylcarbonyl or C2-C4 haloalkylcarbonyl;R3cis H or C1-C4 alkyl; orR3band R3care taken together to form a 4- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups;X is O, S or NR5a;Y is O, S or NR5b;R5aand R5bare each independently H, hydroxy or C|-C4alkyl;R2aand R2bare each independently H, C|-C4alkyl, C2-C4 alkenyl, C3-C 15 trialkylsilyl, C3-C15halotrialkylsilyl, (CR4aR4b)p-OH, (CR4aR4b)p-SH, (CR4aR4b)p-Cl or (CR4aR4b)p-Br; orR2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5- to 7-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 2 carbon atomring members are independently selected from C(=0) and C(=S), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, C|-Co alkyl, C|-Co haloalkyl, C|-Co alkoxy and C|-Co haloalkoxy on carbon atom ring members;R2Cis C I -C4alkyl, C|-C4haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl or trifluoromethylsulfonyl, each optionally substituted with up 2 substituents independently selected from cyano, hydroxy, SCºN and C|-CA alkoxy;R2dis H, cyano, halogen or C|-C4alkyl; each R4aand R4bis independently H or C|-C4alkyl; p is 2 or 3 ; when T is T-l or T-2, then A is A1-A2-CRbRbb, wherein A1is connected to J, and CR6aR6bis connected to T ; when T is T-3, then A is A1-A2, wherein A1is connected to J, and A2is connected to T;A1is CR6cR6d, N(R7a), O or S;A2is a direct bond, CR6eR6f, N(R7b), O or S;R6a, R6b, R6c, R6d, R6eand R6fare each independently H, cyano, hydroxy, halogen, C(=0)0CH3or CrC4alkyl;R7aand R7bare each independently H, C(=0)H, cyano, C|-C4alkyl or C2-C4 alkylcarbonyl;J is selected from the group consisting of:J-9 J-10 J-ll J- 12J-13 J-14 wherein the bond extending to the left is attached to L, and the bond extending to the right is attached to A; each R8is independently F, Cl, I, Br, cyano, methyl, trifluoromethyl or methoxy; q is 0, 1, 2, 3 or 4;L is (CR9aR9b)n; each R9aand R9bis independently H, halogen, cyano, hydroxy, nitro, C|-C3 alkyl, C|- C3 haloalkyl, C|-C3 alkoxy or C|-C3 haloalkoxy; haloalkyl; orE1is amino, cyano, hydroxy, nitro, CH(=0), C(=0)0H, C(=0)NH2, C(=S)NH2, 0C(=0)NH2, OC(=S)NH2, NHC(=0)NH2, NHC(=S)NH2, SCºN, -CH=NNHC(=0)OCrC6alkyl or -N(0CH3)C(=0)CrC6alkyl; orE1is -Q alkoxy, Co-Q, alkenyloxy, Co-Q, alkynyloxy, C|-Q, alkylthio, Co-Q, alkenylthio, -Q, alkynylthio, C|-Q, alkylsulfinyl, Q-Q, alkenylsulfinyl, C2- Q, alkynylsulfinyl, C|-Q, alkylsulfonyl, Q-Q, alkenylsulfonyl, Co-Q, alkynylsulfonyl, C|-Q, alkylsulfonylamino, Q-Q, alkenylsulfonylamino, Q-Q, alkynylsulfonylamino, - alkylaminosulfonyl, Q-Q, dialkylaminosulfonyl, Q-Q alkenylaminosulfonyl, Q-Q, alkynylaminosulfonyl, C|-Q, alkylaminosulfonylamino, Q-Q, alkenylaminosulfonylamino, Q-Q, alkynylaminosulfonylamino, Q-Q, alkylcarbonyl, C3-Q, alkenylcarbonyl, C3-Q, alkynylcarbonyl, Q-Q, alkylaminocarbonyl, C3-Q, alkenylaminocarbonyl,Q-Q, alkynylaminocarbonyl, Q-Q, alkylcarbonylamino, C3-Q, alkenylcarbonylamino, C3-Q, alkynylcarbonylamino, Q-Q, alkylaminocarbonylamino, C3-Q, alkenylaminocarbonylamino, C3-Q, alkynylaminocarbonylamino, Co-Q, alkylcarbonyloxy, C3-Q, alkenylcarbonyloxy, Q-Q alkynylcarbonyloxy, Q-Q, alkoxy carbonyl, Q-Q alkenyloxycarbonyl, C3-Q alkynyloxycarbonyl, Q-Q, alkylaminocarbonyloxy, Q-Q, alkenylaminocarbonyloxy, Q-Q alkynylaminocarbonyloxy, Q-Q, alkoxycarbonylamino, C3-Q alkenyloxycarbonylamino, C3-Q alkynyloxycarbonylamino, Q-Q, alkylamino(thiocarbonyl)oxy, Q-Q alkenylamino(thiocarbonyl)oxy, C3-Q alkynylamino(thiocarbonyl)oxy, Co-Q, alkoxy(thiocarbonyl)amino, Q-Q alkenyloxy(thiocarbonyl)amino, Q-Qalkynyloxy(thiocarbonyl)amino, CV , alkyl (thiocarbonyl), CV , (alkylthio)carbonyl, C3-C(, alkenyl(thiocarbonyl), CyC^ (alkenylthio)carbonyl, C -C6alkynyl(thiocarbonyl), C3-C(, (alkynylthio)carbonyl, CV , alkylamino(thiocarbonyl), C3-C(, alkenylamino(thiocarbonyl), C3-C(, alkynylamino(thiocarbonyl), CV , alkyl(thiocarbonyl)amino, CV , (alkylthio)carbonylamino, C3-C(, alkenyl(thiocarbonyl)amino, C3-C(, (alkenylthio)carbonylamino, C3-C(, alkynyl(thiocarbonyl)amino, C3-C(, (alkynylthio)carbonylamino, CV , alkylamino(thiocarbonyl)amino, C3-C(, alkenylamino(thiocarbonyl)amino or C3-C(, alkynylamino(thiocarbonyl)amino, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10aand up to 3 substituents independently selected from R10b; RlOa jsphenyl optionally substituted with up to 3 substituents independently selected from Rl la; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon atom ring members are independently selected from C(=0) and C(=S), and sulfur atom ring members are independently S(=0)u(=NR12)v, each ring optionally substituted with up to 3 substituents independently selected from Rllaon carbon atom ring members and Rllbon nitrogen atom ring members; each R1 ()is independently amino, cyano, halogen, hydroxy, nitro, SCºN, -SH, C|-C4alkyl, C|-C4haloalkyl, C3-C(, cycloalkyl, C3-C(, halocycloalkyl, C|-C4alkoxy, C1-C4 haloalkoxy, C|-C4alkylthio, C|-C4alkylsulfinyl, C|-C4alkylsulfonyl, C|- C4 haloalkylsulfonyl, C|-C4alkylamino, C2-C4 dialkylamino, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C2-C5 haloalkoxycarbonyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl; each Rl lais independently halogen, hydroxy, cyano, amino, nitro, C|-C4alkyl, C|-C4haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C|-C4hydroxyalkyl, C3-C(, cycloalkyl, C4-C7 cycloalkylalkyl, C|-C4alkoxy, C|-C4haloalkoxy, C2-C4 alkenyloxy, C2- C4 alkynyloxy, C2-C4 alkoxyalkyl, C2-C(, alkylcarbonyloxy, C|-C4alkylthio, C|- C4 haloalkylthio, C2-C(, alkylcarbonylthio, C|-C4alkylsulfinyl, C|-C4haloalkylsulfinyl, C|-C4alkylsulfonyl, C|-C4haloalkylsulfonyl, C|-C4alkylsulfonyloxy, C|-C4alkylamino, C2~Cg dialkylamino, C3-C(, cycloalkylamino, C2-C4 alkylcarbonyl, C3-C5 alkenylcarbonyl, C3-C5 alkynylcarbonyl, C4-C7 cycloalkylcarbonyl, C3-Cg cycloalkylalkylcarbonyl, C2- C(, alkoxycarbonyl, C3-C7 alkenyloxycarbonyl, C3-C7 alkynyloxycarbonyl, C4- C7 cycloalkoxylcarbonyl, C3-Cg cycloalkylalkoxylcarbonyl, C2-C(, alkylaminocarbonyl, C3-C(, alkenylaminocarbonyl, C3-C(, alkynylaminocarbonyl, C4-C7 cycloalkylaminocarbonyl, C3-Cg cycloalkylalkylaminocarbonyl, C3-Cgdialkylaminocarbonyl or C^- , trialkylsilyl; each Rl lbis independently C(=0)H, C|-C3 alkyl, C|-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl; each R12is independently H, cyano, C|-C3 alkyl or C|-C3 haloalkyl; each u and v are independently 0, 1 or 2, provided that the sum of u and v are 0, 1 or 2;E2is G-Z, wherein Z is attached to L;G is phenyl optionally substituted with up to 3 substituents independently selected from R13; orG is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R13; or G is a 3- to 7-membered nonaromatic ring or an 8- to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=0), C(=S), S(=0) and S(=0)2, each ring or ring system optionally substituted with up to 3 substituents independently selected from R13; each R13is independently cyano, halogen, hydroxy, nitro, -SH, SF5, CH(=0),alkyl, C2-C6alkenyl, C2-Cg alkynyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C|-C(, alkoxy, C2-Cg alkenyloxy, C2-Cg alkynyloxy, C3-C7 cycloalkoxy, C|-C(, alkylthio, C|-C(, alkylsulfinyl, C|-C(, alkylsulfonyl, C|-C(, alkylaminosulfinyl, C2-C6dialkylaminosulfinyl, C|-C(, alkylsulfonyloxy, C|-C(, alkylsulfonylamino, C2-C6alkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-Cg alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C3- C(, alkoxycarbonylcarbonyl, C2-Cg alkylcarbonyloxy, C4-C7 cycloalkylcarbonyloxy, C2-Cg alkoxycarbonyloxy, C4-C7 cycloalkoxycarbonyloxy, C2-Cg alkylaminocarbonyloxy, C4-C7 cycloalkylaminocarbonyloxy, C2-Cg alkylcarbonylamino, C4-C7 cycloalkylcarbonylamino, C2-Cg alkoxycarbonylamino, C4-C7 cycloalkoxycarbonylamino, C2-Cg alkylaminocarbonylamino, C4-C7 cycloalkylaminocarbonylamino or C2-Cg dialkoxyphosphinyl, each optionally substituted with up to 3 substituents independently selected from R19; each R14ais independently H, cyano, hydroxy, C|-C4alkyl, C|-C4haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C|-C5 alkoxy, C2-C4 alkoxyalkyl, C|-C4alkylsulfonyl, C|-C4haloalkylsulfonyl, C2-C4alkylthioalkyl, C2-C4 alkylsulfinylalkyl, C2-C4 alkylsulfonylalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbony 1 ; each R14bis independently H, C|-C(, alkyl, C|-C(, haloalkyl, CV , alkenyl, CV , haloalkenyl, CV , alkynyl, CV , haloalkynyl, C|-C(, hydroxyalkyl, CV , cyanoalkyl, C3-Cg cycloalkyl, C3~Cg halocycloalkyl, C3-Cg cycloalkenyl, C3-Cg halocycloalkenyl, C4-C| ()alkylcycloalkyl, C4-C| ()cycloalkylalkyl, C4-C| ()halocycloalkylalkyl, C(,-C|4cycloalkylcycloalkyl, C5-C IQalkylcycloalkylalkyl, C2-C6alkoxyalkyl, CV , haloalkoxyalkyl, C4-C| ()cycloalkoxyalkyl, C3~Cg alkoxyalkoxyalkyl, CV , alkylthioalkyl, CV , alkylsulfinylalkyl, CV , alkylsulfonylalkyl, CV , alkylaminoalkyl, CV , haloalkylaminoalkyl, C3-Cg dialkylaminoalkyl or C4-C| ()cycloalkylaminoalkyl, each optionally substituted with up to 1 substituent selected from cyano, hydroxy, nitro, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C45 trlalkylsilyl, C3-C 15 halotrialkylsilyl and pyrimidinyl; orR14aand R14bare taken together to form a 4- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 3 substituents independently selected from halogen and C|-C3 alkyl; each R15is independently H, cyano, halogen, methyl, methoxy, methylthio or methoxycarbonyl; each R16is independently hydroxy or NR20aR20b; or C|-C4alkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 alkylcarbonyloxy, C2-C5 alkoxycarbonyloxy, C2-C5 alkylaminocarbonyloxy or C3-C5 dialkylaminocarbonyloxy, each optionally substituted with up to 1 substituent selected from cyano, halogen, hydroxy and C(=0)OH; each R17is independently H, methyl, methoxy or methylthio; each R18aand R18bis independently H or C|-C4alkyl; orR18aand R18bare taken together to form a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups; each R19is independently amino, cyano, halogen, hydroxy, nitro, -SH, C|-C4alkyl, C4-C4 haloalkyl, C3-C4, cycloalkyl, C3-C4, halocycloalkyl, C4-C4 alkoxy, C4-C4haloalkoxy, C2-C4 alkoxyalkoxy, C|-C4alkylthio, C|-C4alkylsulfinyl, C|-C4alkylsulfonyl, C|-C4haloalkylsulfonyl, C2-C4alkylcarbonyl, C2-C4haloalkylcarbonyl, C2-C5 alkoxy carbonyl, C|-C(, alkylamino, CV , dialkylamino, C2-C5 alkylaminocarbonyl, C3-C5 dialkylaminocarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C 15 trialkylsily, C3-C15 halotrialkylsilyl, C(R21)=NOR22or C(R23)=NR24; each U is independently a direct bond, C(=0)0, C(=0)N(R25) or C(=S)N(R26), wherein the atom to the left is connected to G, and the atom to the right is connected to V; each V is independently a direct bond; or Cj-Cg alkylene, CV , alkenylene, C3-C6 alkynylene, C3-C6 cycloalkylene or C3-C6 cycloalkenylene, wherein up to 1 carbon atom is C(=0), each optionally substituted with up to 3 substituents independently selected from halogen, cyano, nitro, hydroxy, C|-Co alkyl, C|-Co haloalkyl, C|-Co alkoxy and C|-Co haloalkoxy; each Q is independently phenyl or phenoxy, each optionally substituted with up to 2 substituents independently selected from R27; or each Q is independently a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R27; or each Q is independently a 3- to 7-membered nonaromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=0), C(=S), S(=0) and S(=0)2, each ring optionally substituted with up to 2 substituents independently selected from R27; each R20ais independently H, C|-C4alkyl or C2-C4alkylcarbonyl; each R20bis independently H, cyano, C|-C5 alkyl, C2-C5 alkylcarbonyl, C2-C5 haloalkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl; orR20aan(jR20baretaken together to form a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups; each R21and R23is independently H, cyano, halogen, C|-C3 alkyl, C|-C3 haloalkyl, C -C6cycloalkyl or C|-C3 alkoxy; or phenyl optionally substituted with up to 2substituents independently selected from halogen and C|-C3 alkyl; each R22is independently H, C|-C5 alkyl, C|-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C^- , halocycloalkyl, C2-C5 alkylcarbonyl or C2-C5 alkoxycarbonyl; or each R22is phenyl optionally substituted with up to 2 substituents independently selected halogen and C|-C3 alkyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 substituents independently selected from halogen and C|-C3 alkyl; each R24is independently H, cyano, C|-C3 alkyl, C|-C3 haloalkyl, C|-C4alkoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl; each R25and R26is independently H, cyano, hydroxy, C|-C4alkyl, C|-C4haloalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C4 alkoxycarbonyl or C2-C4 haloalkoxycarbonyl; each R27is independently halogen, cyano, hydroxy, nitro, C|-C4alkyl, C|-C4haloalkyl, C2-C4 alkenyl, C|-C4alkoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;Z is a direct bond, O, S(=0)m, N(R28), C(=0), C(=0)0, C(=0)N(R28), NR28C(=0), N(R28)C(=0)N(R28), N(R28)C(=S)N(R28), 0C(=0)N(R28), N(R28)C(=0)0, S(0)2N(R28), N(R28)S(=0)2or N(R28)S(0)2N(R28), wherein the atom to the right is connected to L; each R28is independently H, C|-C3 alkyl, C|-C3 alkoxy, C2-C3 alkylcarbonyl or C2- C3 alkoxycarbonyl; and m is 0, 1 or 2; and(b) at least one additional fungicidal compound; provided that:(c) when A1is N(R7a), O or S, then A2is a direct bond or CR6eR6f; and when A2is N(R7b), O or S; then A1is CR6cR6d.
2. The composition of Claim 1 wherein component (a) comprises a compound of Formula 1 or salt thereof, whereinR1is CF3, CCI3 or CF2C1;W is O;R5aand R5bare each independently H, hydroxy or methyl;R2aand R2bare each independently H or methyl; orR2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition tothe atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(=0), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members;R2Cis CrC2alkyl, C2-C3alkenyl or C2-C3alkynyl;R2dis H or methyl;A1is CR6cR6dor O;A2is a direct bond, CR6eR6for O;R6a, R6b, R6c, R6d, R6eand R6fare each independently H, cyano, hydroxy, Br, Cl, F or methyl;J is J-l, J-6 or J- 14; each R8is independently F, Cl or methyl; each R9aand R9bis independently H, halogen or methyl; n is 0, 1 or 2;E1is C I -C(, alkoxy, C|-C(, alkylsulfonyl, C2-C(, alkylcarbonyl or C2-C(, alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from Rl ()aand up to 3 substituents independently selected from R10b;RlOa is phenyl optionally substituted with up to 2 substituents independently selected from Rl la; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from Rl laon carbon atom ring members and Rl lbon nitrogen atom ring members; each Rl ()is independently halogen, hydroxy, C|-C4alkyl, C|-C4haloalkyl, C|-C4alkoxy, C|-C4haloalkoxy, C|-C4alkylsulfonyl, C2-C4 alkylcarbonyl or C2-C3alkoxycarbonyl; each Rl lais independently halogen, C|-C2alkyl, C|-C2haloalkyl, C|-C2alkoxy or C2-C3alkoxycarbonyl; each Rl lbis independently methyl, methoxy, methylcarbonyl or methoxycarbonyl;G is selected from the group consisting of:G-l G-2 G-3 G-4G-57 G-58 G-59 G-60G-85 G-86 G-87 G-88G-113 G-114 G-115 G-116G-117 G-118 wherein the floating bond is connected to Z in Formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3; each R13is independently C(=0)NR14aR14bor -U-V-Q; or C|-C(, alkyl, CV , alkenyl, Co-C(, alkynyl, C|-C(, alkoxy, CV , alkenyloxy, CV , alkynyloxy, C|-C(, alkylsulfonyl, C|-C(, alkylsulfonyloxy, C|-C(, alkylsulfonylamino, CV , alkylcarbonyl, CV , alkoxycarbonyl, C^- , alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C(, cycloalkoxycarbonyl or CV , alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from Rl9; each R14ais independently H, C|-Co alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl; each R14bis independently H, C|-C4alkyl, C|-C4haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C5 cycloalkyl, C4-C(, cycloalkylalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkylaminoalkyl or C3-C5 dialkylaminoalkyl; orR14aand R14bare taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl; each R19is independently cyano, halogen, C|-Co alkyl, C|-Co haloalkyl, C3-C4, cycloalkyl, C|-Co alkoxy, C|-Co haloalkoxy, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl or C2-C3 alkoxycarbonyl; each U is independently a direct bond, C(=0)0 or C(=0)N(R25); each V is independently a direct bond; or C|-C3 alkylene, each optionally substituted with up to 2 substituents independently selected from halogen, hydroxy, C|-Co alkyl, C|-Co alkoxy and C|-Co haloalkoxy; each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each optionally substituted with up to 2 substituents independently selected from R27; each R25is independently H, cyano, hydroxy or C|-Co alkyl; each R27is independently halogen, cyano, C|-Co alkyl, C|-Co haloalkyl or C|-Co alkoxy; andZ is a direct bond, O, NH, C(=0), C(=0)NH, NHC(=0), NHC(=0)NH, 0C(=0)NH, NHC(=0)0, S(=0)2NH, NHS(=0)2or NHS(=0)2NH.
3. The composition of Claim 2 wherein component (a) comprises a compound of Formula 1 or salt thereof, whereinT is T-2 or T-3;R1is CF3;X is O;Y is O;R2aand R2bare each independently H or methyl; orR2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member;R2Cis methyl or ethyl;R2dis H;A1is O;A2is a direct bond or CH2;R6aand R6bare each independently H, cyano hydroxy or methyl;J is J-l or J-6; q is 0 or 1 ; each R9aand R9bis independently H or methyl;E1is C I -C3alkoxy, C2-C3alkylcarbonyl or C2-C3alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R1 ()aand up to 3 substituents independently selected from R10b;RlOa is pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members; each Rl()is independently halogen, C|-C2alkyl, C|-C2haloalkyl, C|-C2alkoxy or C2-C4alkoxycarbonyl;G is G-l, G-3, G-12 or G-22; x is 1 or 2; each R13is independently C(=0)NR14aR14bor -U-V-Q; or C2-C3alkoxycarbonyl, C3-C3alkenyloxycarbonyl, C3-C3alkynyloxycarbonyl or C^-C^ cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19; each R14ais independently H or C|-C2alkyl; each R14bis independently H, C|-C3alkyl, C|-C3haloalkyl, cyclopropylmethyl or C2-C4alkoxyalkyl;each R19is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl; each U is independently a direct bond or C(=0)0; each V is independently a direct bond or CH2; each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27; each R27is independently halogen, methyl or methoxy; and Z is a direct bond, O, NH, C(=0), C(=0)NH or NHC(=0).
4. The composition of Claim 3 wherein component (a) comprises a compound of Formula 1 or salt thereof, whereinR2aand R2bare each H; orR2aand R2bare taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms;A2is a direct bond;R6aand R6bare each H;R8is F or Cl;L is a direct bond, CH2or CH2CH2;E1is Cl-C2alkoxy or C2-C2alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from Rl()a;Rl°ais pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from Rllaon carbon atom ring members; each Rllais independently methoxycarbonyl or ethoxycarbonyl;G is G- 1 and the 2-position of G- 1 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; x is 1;R13is C(=0)NR14aR14bor -U-V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C(, cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19;R14ais H;R14bis H, methyl or cyclopropylmethyl;R19is cyano, halogen, cyclopropyl or methoxy;U is C(=0)0;V is CH2;Q is phenyl optionally substituted with up to 2 substituents independently selected from R27; andZ is a direct bond, O, NH or C(=0).
5. The composition of Claim 4 wherein component (a) comprises a compound of Formula 1 or salt thereof, whereinR8is F;L is a direct bond or CH2;E1is methoxy substituted with 1 substituent selected from R10a;RlOa jspyrazolyl optionally substituted with up to 1 substituent selected from Rllaon a carbon atom ring member;G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3- position is connected to R13; andR13is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from R19;R19is cyano, Cl, F, cyclopropyl or methoxy; and Z is a direct bond.
6. The composition of Claim 5 wherein component (a) comprises a compound of Formula 1 or salt thereof, whereinJ is J-l; q is 0;L is CH2;E is E2;G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; andR13is methoxycarbonyl or ethoxycarbonyl.
7. The composition of Claim 1 wherein component (a) comprises a compound selected from the group consisting of ethyl 1 -| |4-(3,3,3-tririuoro-2,2-dihydroxypropoxy)phenyl |methyl |- 1 / / -pyrazole-4- carboxylate; ethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]-177-pyrazole- 4-carboxylate; ethyl 1 - 1 [ 4 - 11 ( lZ)-2-ethoxy-3,3,3-trinuoro- 1 -propen- 1 -yl |oxy Iphenyl |methyl \-\H- pyrazole-4-carboxylate; ethyl 1 - 1 [ 4 - 11 ( lZ)-2-ethoxy-3,3,3-trinuoro- 1 -propen- 1 -yl |oxy Iphenyl |methyl \-\H- pyrazole- 3 -carboxylate ; ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l-yl]oxy]-3-fluorophenyl]methyl]- 17 / -pyrazole-4-carboxylate;ethyl 1 -| |3-| |( lZ)-2-ethoxy-3,3,3-trinuoro- 1 -propen- 1 -yl |oxy Iphenyl |methyl \-\H- pyrazole-4-carboxylate; ethyl 1 - 1 [ 4 - 11 ( lZ)-2-ethoxy-3,3,3-trinuoro- 1 -propen- 1 -yl |oxy Iphenoxy |methyl \-\H- pyrazole-4-carboxylate; -( cyclopropyl methyl )-2-| |4-| 12-(trinuoromethyl)- 1 ,3-dioxolan-2-yl |methoxy Iphenyl |- methyl]thiazole-4-carboxamide;2-methylpropyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]- 1 / / -pyrazole-4-carboxylate; cyclopropylmethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2- yl Imethoxy Iphenyl |methyl |- 1 / / -pyrazole-4-carboxylate; ethyl 1 - 12 - 14 - 11 i lZ)-2-ethoxy-3,3,3-trinuoro- 1 -propen- 1 -yl |oxy Iphenyl |ethyl |- 1 H- pyrazole-4-carboxylate;2-methoxyethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]phenyl]methyl]- 1 / / -pyrazole-4-carboxylate;2-butyn-l-yl 1 -| |4-| 12-(tririuoromethyl)- 1 ,3-dioxolan-2-yl Imethoxy Iphenyl |methyl |- 1 H- pyrazole-4-carboxylate;3-cyanopropyl 1 - 114-| 12-(tririuoromethyl)- 1 ,3-dioxolan-2-yl Imethoxy Iphenyl | methyl |- 1 H- pyrazole-4-carboxylate; phenylmethyl l-[[4-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1-propen- l-yl]oxy]phenyl]methyl]- 1 / / -pyrazole-4-carboxylate; butyl 1 - 114- 11 ( lZ)-2-ethoxy-3,3,3-trinuoro- 1 -propen- 1 -yl |oxy Iphenyl | methyl |- 1 H- pyrazole-4-carboxylate;3-chloropropyl l-[[4-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1-propen- l-yl]oxy]phenyl]methyl]- 1 / / -pyrazole-4-carboxylate; methyl 4-(3 ,3 ,3-trifluoro-2,2-dihydroxypropoxy)phenylcarboxylate; ethyl 1 -| |3-fluoro-4-| |2-(trinuoromethyl)- 1 ,3-dioxolan-2-yl Imethoxy Iphenyl | methyl \-\H- pyrazole-4-carboxylate; ethyl l-[[4-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1 -propen- l-yl]oxy]pheny lmethoxy]methyl]- 1 / / -pyrazole-4-carhoxylate; methyl l-[[3-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1-propen- l-yl]oxy]phenyl]methyl]-l / - pyrazole-4-carboxylate; and propyl l-[[3-[[(lZ)-2-ethoxy-3, 3, 3-trifluoro- 1-propen- l-yl]oxy ]phenyl]methyl]-l / - pyrazole-4-carboxylate.
8. The composition of any one of Claims 1 through 7 wherein component (b) includes at least one fungicidal compound selected from the group consisting of:(bl) methyl benzimidazole carbamate (MBC) fungicides;(b2) dicarboximide fungicides;(b3) demethylation inhibitor (DMI) fungicides;(b4) phenylamide (PA) fungicides;(b5) amine / morpholine fungicides;(b6) phospholipid biosynthesis inhibitor fungicides;(b7) succinate dehydrogenase inhibitor (SDHI) fungicides;(b8) hydroxy(2-amino-)pyrimidine fungicides;(b9) anilinopyrimidine (AP) fungicides;(blO) iV-phenyl carbamate fungicides;(bll) quinone outside inhibitor (Qol) fungicides;(bl2) phenylpyrrole (PP) fungicides;(bl3) azanaphthalene fungicides;(bl4) cell peroxidation inhibitor fungicides;(bl5) melanin biosynthesis inhibitor-reductase (MBI-R) fungicides;(bl6a) melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides;(bl6b) melanin biosynthesis inhibitor-poly ketide synthase (MBI-P) fungicides; (bl7) keto reductase inhibitor (KRI) fungicides;(bl8) squalene-epoxidase inhibitor fungicides;(bl9) polyoxin fungicides;(b20) phenylurea fungicides;(b21) quinone inside inhibitor (Qil) fungicides;(b22) benzamide and thiazole carboxamide fungicides;(b23) enopyranuronic acid antibiotic fungicides;(b24) hexopyranosyl antibiotic fungicides;(b25) glucopyranosyl antibiotic: protein synthesis fungicides;(b26) glucopyranosyl antibiotic fungicides;(b27) cyanoacetamideoxime fungicides;(b28) carbamate fungicides;(b29) oxidative phosphorylation uncoupling fungicides;(b30) organo tin fungicides;(b31) carboxylic acid fungicides;(b32) heteroaromatic fungicides;(b33) phosphonate fungicides;(b34) phthalamic acid fungicides;(b35) benzotriazine fungicides;(b36) benzene- sulfonamide fungicides;(b37) pyridazinone fungicides;(b38) thiophene-carboxamide fungicides;(b39) complex I NADH oxido-reductase inhibitor fungicides;(b40) carboxylic acid amide (CAA) fungicides;(b41) tetracycline antibiotic fungicides;(b42) thiocarbamate fungicides;(b43) benzamide fungicides;(b44) microbial fungicides;(b45) quinone outside inhibitor, stigmatellin binding (QoSI) fungicides;(b46) plant extract fungicides;(b47) cyanoacrylate fungicides;(b48) polyene fungicides;(b49) oxy sterol binding protein inhibitor (OSBPI) fungicides;(b50) aryl-phenyl-ketone fungicides;(b51) host plant defense induction fungicides;(b52) multi-site activity fungicides;(b53) biologicals with multiple modes of action;(b54) fungicides other than fungicides of component (a) and components (bl) through (b53); and salts of compounds of (bl) through (b54).
9. The composition of Claim 8 wherein component (b) comprises at least one fungicidal compound from each of two different groups selected from (bl) through (b54).
10. The composition of any one of Claims 1 through 7 wherein component (b) includes at least one compound selected from ac i be n zo 1 ar- S- m eth y 1 , aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl-M, benodanil, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper hydroxide, copper salts, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, dithianon, dodemorph, dodine, edifenphos, enestroburin, epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluindapyr, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazol, guazatine, imazalil, imibenconazole, iminoctadine, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb,mandipropamid, maneb, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, metiram, metominostrobin, mepanipyrim, metrafenone, myclobutanil, naftifine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, penflufen, penthiopyrad, pefurazoate, phosphorous acid and salts thereof, phthalide, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, pyrrolnitrin, quinomethionate, quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, tolnifanide, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, triflumizole, tricyclazole, trifloxystrobin, triforine, trimorphamide, triticonazole, uniconazole, validamycin, valifenalate, vinclozolin, zineb, ziram, zoxamide, / V-[4-[4-chloro- 3 -(trifluoromethy l)phenoxy ] -2 , 5 -dimethy lpheny 1] - / V-ethyl-iV-methylmethanimidamide, 5-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-l-yl)[l,2,4]triazolo[l,5a]pyrimidine (DPX-B AS 600F) ,N- [2- [4- [ [3 -(4-chlorophenyl)-2-propyn- 1 -yl]oxy]-3-methoxy- phenyljethyl] -3 -methyl-2- [(methylsulfonyl)amino]butanamide, / V-[2-[4-[[3-(4-chloro- phenyl)-2-propyn- 1 -yl]oxy] -3 -methoxyphenyl]ethyl]-3 -methyl-2- [(ethylsulfonyl)amino] - butanamide, 4-fluorophenylN- [ 1 - [ [[ 1 -(4-cy anophenyl)ethyl] sulfonyl]- methyl]propyl]carbamate,N- [[(cyclopropylmethoxy) amino] [6-(difluoromethoxy)- 2,3-difluorophenyl]methylene]benzeneacetamide, a-( methoxy i mi no )- / V-methy 1-2- 1| | 1 -|3- (trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide, / V-[4-[4-chloro- 3 - (trifluoromethy l)phenoxy] -2 , 5 -dimethy lpheny 1] - / V-ethyl-iV-methylmethanimidamide, 2- [[[[3-(2,6-dichlorophenyl)-l-methyl-2-propen-l-ylidene]amino]oxy]methyl]-a- (methoxyimino)- / V-methylbenzeneacetamide and l-[(2-propenylthio)carbonyl]-2-(l-methyl- ethyl )-4-(2-methylphenyl )-5-amino- 1 / / -pyrazol-3-one, 5-ethyl-6-octyl-[l,2,4]triazolo[l,5- a]pyrimidin-7 -ylamine.
11. The composition of Claim 10 wherein component (b) includes at least one compound selected from azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, mancozeb, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole and trifloxystrobin.
12. A composition comprising: (a) at least one compound selected from the compounds of Formula 1 as defined in Claim 1, A-oxides, and salts thereof; and at least oneinvertebrate pest control compound or agent.
13. A composition comprising the composition of any one of Claims 1 through 12 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
14. A method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of the composition of any one of Claims 1 through 13 to the plant or plant seed.
15. A method for protecting a plant from a rust disease comprising applying to the plant a fungicidally effective amount of the composition of any one of Claims 1 through 13 wherein component (b) includes at least one fungicidal compound selected from (bll) quinone outside inhibitor fungicides. (b3) demethylation inhibitor fungicides, (b5) amine / morpholine fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (bll) quinone outside inhibitor (Qol) fungicides, (bl3) methyl benzimidazole carbamate fungicides and (b52) multi-site activity fungicides.