Fungicidal oxadiazoles

Abstract

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, tautomers, N-oxides, and salts thereof, wherein R 1 , L, and J are as defined in the disclosure. Also disclosed are compositions comprising the compounds of Formula 1 and methods for controlling plant diseases caused by fungal pathogens comprising applying an effective amount of a compound or composition of the invention.

Description

[0001] This application is a divisional application of Chinese patent application 201880032035.X, filed on April 5, 2018, entitled "Antidazole for Fungal Killing". Technical Field

[0002] This invention relates to certain oxadiazoles, their N-oxides, salts and compositions, and methods of using them as fungicides. Background Technology

[0003] Preventing plant diseases caused by fungal plant pathogens is crucial for achieving high crop efficiency. Damage to ornamental crops, vegetable crops, field crops, cereal crops, and fruit crops can lead to significant yield reductions, resulting in increased costs for consumers. Many products are commercially available for these purposes, but there is still a need for new compounds that are more effective, cheaper, less toxic, more environmentally safer, or have different sites of action.

[0004] PCT patent publications WO 2017 / 118689 and WO 2017 / 085100 disclose oxadiazole derivatives and their use as fungicides. Summary of the Invention

[0005] This invention relates to compounds of formula 1 (including all stereoisomers), their N-oxides, hydrates (and solvates thereof), and salts, agricultural compositions comprising them, and their use as fungicides:

[0006]

[0007] in

[0008] R 1 A benzene ring optionally substituted with up to 3 substituents, said substituents being independently selected from R 2 ;or

[0009] R 1 It is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 3 substituents, wherein the substituents are independently selected from R 2 ;or

[0010] R 1The ring is a 3- to 7-membered non-aromatic ring or an 8- to 11-membered bicyclic ring system, each ring or ring system comprising a ring member selected from carbon atoms and optionally up to 4 heteroatoms, wherein the heteroatoms are independently selected from up to 2 O atoms, up to 2 S atoms, and up to 4 N atoms, wherein the up to 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring or ring system is optionally substituted by up to 3 substituents, wherein the substituents are independently selected from R 2 ;

[0011] L represents O, NR 3 NR 3 CH2, CH2NR 3 NR 3 CH2CH2, CH2CH2NR 3 、(CR 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O, or CH2OCH2, where the atom on the left is attached to R. 1 And the atom on the right is attached to J, and each carbon atom is optionally substituted by up to 2 substituents, which are independently selected from halogen, cyano, hydroxy, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

[0012] J is a benzene ring or naphthalene ring system, each optionally substituted by up to two substituents, said substituents being independently selected from R. 5 Or a 3- to 7-membered carbon ring, wherein at most 3 ring members are independently selected from C (=O) and C (=S), and each ring is optionally substituted by at most 2 substituents, said substituents being independently selected from R. 5 ;or

[0013] J is a 5- to 6-membered heterocycle, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R. 5 ;

[0014] Each R 2 Independently, it can be halogen, cyano, hydroxyl, nitro, thioyl, -SF5, -CH(=O), -C(=O)OH, or -NR. 3a R 3b -C(=O)NR 3a R 3b -C(=O)C(=O)NR 3aR 3b -C(=S)NR 3a R 3b -C(R) 6 ) = NR 7 -N=CR 8 NR 9a R 9b Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminosulfinyl, C2-C6 dialkylaminosulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl The group consists of a C4-C7 cycloalkoxycarbonyl group, a C3-C6 alkoxycarbonylcarbonyl group, a C2-C6 alkylcarbonyloxy group, a C4-C7 cycloalkylcarbonyloxy group, a C2-C6 alkoxycarbonyloxy group, a C4-C7 cycloalkoxycarbonyloxy group, a C2-C6 alkylaminocarbonyloxy group, a C4-C7 cycloalkylaminocarbonyloxy group, a C2-C6 alkylcarbonylamino group, a C4-C7 cycloalkylcarbonylamino group, a C2-C6 alkoxycarbonylamino group, a C4-C7 cycloalkoxycarbonylamino group, a C2-C6 alkylaminocarbonylamino group, a C4-C7 cycloalkylaminocarbonylamino group, or a C2-C6 diekoxyphosphonoyl group, each optionally substituted with up to three substituents, said substituents being independently selected from R. 10 ;

[0015] Each R 3 and R 3a Independently, it can be H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C5 alkoxy, C2-C4 alkoxyalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylthioalkyl, 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 dialkylaminocarbonyl;

[0016] Each R 3bIndependently, it can be H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C4-C 10 Alkyl cycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 Halogenated cycloalkyl alkyl, C6-C 14 cycloalkyl, C5-C 10 Alkylcycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C4-C 10 Cycloalkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfinylalkyl, C2-C6 alkylsulfonylalkyl, C2-C6 alkylaminoalkyl, C2-C6 haloalkylaminoalkyl, C3-C8 dialkylaminoalkyl or C4-C 10 Cycloalkylaminoalkyl groups, each optionally substituted with at most one substituent selected from cyano, hydroxy, nitro, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C4 alkylcarbonyl, C4-C4 alkylcarbonyl, C5-C6 alkylcarbonyl, C6-C6 alkylcarbonyl, C7-C6 alkylcarbonyl, C8-C6 alkylcarbonyl, C9-C9 alkylcarbonyl, C9-C 15 Trialkylsilyl and C3-C 15 Halogenated trialkylsilyl; or

[0017] A pair of R 3a and R 3b Substituents are combined with the nitrogen atom to which they are attached to form a 4- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to two heteroatoms in addition to the connecting nitrogen atom. The heteroatoms are independently selected from up to two O atoms, up to two S atoms, and up to two N atoms. Each ring is optionally substituted by up to three substituents, which are independently selected from halogens and C1-C3 alkyl groups.

[0018] Each R 4a and R 4b Independently, it is H, halogen, cyano, hydroxyl, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy; or

[0019] A pair of R atoms attached to the same carbon atom 4a and R 4b The substituents are combined to form a C3-C5 cycloalkyl ring, which is optionally substituted by up to two substituents, said substituents being independently selected from halogen, methyl, methoxy and methylthio;

[0020] Each R 5It can be independently hydroxyl, cyano, nitro, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl or C1-C4 alkoxy;

[0021] Each R 6 It can be independently H, cyano, halogen, methyl, methoxy, methylthio, or methoxycarbonyl;

[0022] Each R 7 Independently hydroxyl or NR 11a R 11b ; or C1-C4 alkoxy, C2-C4 alkenoxy, C2-C4 alkynoxy, C2-C4 alkyl carbonyloxy, C2-C5 alkoxy carbonyloxy, C2-C5 alkylamino carbonyloxy or C3-C5 dialkylamino carbonyloxy, each optionally substituted with at most one substituent selected from halogen, cyano, hydroxyl and -C(=O)OH;

[0023] Each R 8 It can be independently H, methyl, methoxy, or methylthio;

[0024] Each R 9a and R 9b Independently H or C1-C4 alkyl; or

[0025] A pair of R 9a and R 9b Substituents are combined with the nitrogen atom to which they are attached to form a 5- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms in addition to the connecting nitrogen atom, the ring member being independently selected from up to 2 O atoms, up to 2 S atoms and up to 2 N atoms, each ring optionally being substituted by up to 2 methyl groups;

[0026] Each R 10 Independently, it is a halogen, amino, cyano, hydroxyl, nitro, thioyl, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C1-C6 alkylamino, C2-C6 dialkylamino, C2-C5 alkylaminocarbonyl, C3-C5 dialkylaminocarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C 15 Trialkylsilyl, C3-C 15 Halogenated trialkylsilyl, -C(R) 13 ) = NOR 14 or -C(R)15 ) = NR 16 ;

[0027] Each U is independently a direct bond, C(=O)O, C(=O)NR. 17 Or C(=S)NR 18 The atom on the left is connected to R. 1 And the atom on the right is connected to V;

[0028] Each V is independently a direct bond; or a C1-C6 alkylene, C2-C6 alkenylene, C3-C6 ynylene, C3-C6 cycloalkylene, or C3-C6 cycloalkenylene, each optionally substituted by up to three substituents independently selected from halogens, cyano, nitro, hydroxyl, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy.

[0029] Each Q is independently phenyl or phenoxy, and each is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ;or

[0030] Each Q is independently a 5- to 6-membered heteroaromatic ring, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R. 12 ;or

[0031] Each Q is independently a 3- to 7-membered non-aromatic heterocycle, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most two substituents, wherein the substituents are independently selected from R. 12 ;

[0032] Each R 11a Independently, it is H, C1-C4 alkyl, or C2-C4 alkyl carbonyl;

[0033] Each R 11b Independently, it is H, cyano, C1-C5 alkyl, C2-C5 alkylcarbonyl, C2-C5 haloalkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl, or C3-C5 dialkylaminocarbonyl; or

[0034] A pair of R11a and R 11b Substituents are combined with the nitrogen atom to which they are attached to form a 5- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms in addition to the connecting nitrogen atom, the ring member being independently selected from up to 2 O atoms, up to 2 S atoms and up to 2 N atoms, each ring optionally being substituted by up to 2 methyl groups;

[0035] Each R 12 It can be independently a halogen, cyano, hydroxyl, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl or C2-C4 alkoxy carbonyl;

[0036] Each R 13 and R 15 The benzene ring is independently H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl or C1-C3 alkoxy; or optionally substituted with up to 2 substituents, said substituents being independently selected from halogen and C1-C3 alkyl;

[0037] Each R 14 Independently, it is H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 ynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C5 alkylcarbonyl, or C2-C5 alkoxycarbonyl; or

[0038] Each R 14 The benzene ring is optionally substituted with up to two substituents, the substituents being independently selected from halogens and C1-C3 alkyl groups; or a 5- to 6-membered fully saturated heterocycle, each ring comprising a ring member selected from carbon atoms and up to two heteroatoms, the heteroatoms being independently selected from up to two O atoms, up to two S atoms and up to two N atoms, each ring optionally substituted with up to two substituents, the substituents being independently selected from halogens and C1-C3 alkyl groups;

[0039] Each R 16 It can be independently H, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C4 alkoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;

[0040] Each R 17 and R 18 Independently, it is H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C4 alkoxycarbonyl, or C2-C4 haloalkoxycarbonyl; and

[0041] n is 1, 2, or 3;

[0042] The prerequisite is:

[0043] (a) When L is CH2 and J is an unsubstituted phenyl group, then R 1 Not 3-(methoxyimino)-1-pyrrolidinyl, 5-(methylsulfinyl)-1H-1,2,4-triazol-3-yl, 5-(ethylthio)-1H-1,2,4-triazol-3-yl, 5-(propylthio)-1H-1,2,4-triazol-3-yl, 2,3-dihydro-5-methyl-3-oxo-1H-pyrazol-1-yl, 1-piperidinyl, 4-(methoxyimino)-1-piperidinyl, 4-morpholinyl, 2,6-dimethyl-4-morpholinyl, 4-(methylsulfonyl)-1-piperazinyl, 4-thiomorpholinyl, 6-methoxy-3-pyridinyl or 1,2,3,6-tetrahydro-1,3-dimethyl-2,6-dioxo-7H-purine-7-yl;

[0044] (b) When R 1 It is a 5-membered heterocycle containing 2 to 4 nitrogen atoms, each ring optionally being substituted by up to 3 substituents, said substituents being independently selected from cyano, Br, Cl, I, CH3, C1-C2 alkoxycarbonyl and 4-chlorophenyl, and when L is CH2, then J is not pyridine;

[0045] (c) When R 1 If L is a 1H-pyrazol-1-yl group substituted with 1-2 substituents, wherein the substituents are independently selected from CH3 and CH3CH2C(=O), and J is an unsubstituted phenyl group, then L is not CH2CH2, CH2CHF or CH(CH3);

[0046] (d) When L is CH2 and J is an unsubstituted phenyl group, then R 1 It is not 1H-indazole, 2H-indazole, 1H-indole, 1H-pyrrole, 2-piperidinone or 2-pyrrolidone, each optionally substituted with up to 3 substituents, said substituents being independently selected from -CH (=O), CH3C (=O), cyano, Cl, F, CH3, (CH3)2CHCH2, CF3, CH3O and CH3OC (=O);

[0047] (e) The compound of formula 1 is not a compound of F-1.

[0048]

[0049] in

[0050] Z

[0051]

[0052]

[0053] For Z-1 to Z-9, the substituent R 1a and R 3a They can be the same or different; and

[0054] For Z-1:

[0055] m is 0; and R 2a and R 2b Each is H; or

[0056] m is 1; R 1a It is located at position 3 and is -(CH3CH2OC(=O))-2-pyridyl, Cl, CF3 or -CH(=O); and R 2a and R 2b Each is H; or

[0057] m is 1; R 1a At position 4 and being halogen, cyano, CF3, -CH (=O), OHC (=O), C2-C5 alkoxy carbonyl, NH2C (=O), CH3NHC (=O), CH3CH2NHC (=O), (CH3)2NCH2CH2OC (=O), cyclopropyl-NHC (=O), cyclopropyl-CH2NHC (=O), ((CH3)2NC (=O), (CH3CH2)2NC (=O), CH3ONHC (=O), CH3OCH2CH2NHC (=O), CH≡CCH2NHC (=O), CH3ON(CH3)C (=O), CH3ON=CH, CH3CH2ON=CH, CH3CH2CH2ON=CH, (CH3)2CHON=CH, CH≡CCH2ON=CH, phenyl-CH2ON=CH, or 4-morpholinyl carbonyl; and R 2a and R 2b Each is H; or

[0058] m is 1; R 1a It is in position 4 and is CH3CH2C (=O); R 2a For H; and R 2b For F; or

[0059] m is 1; R 1a It is located at position 4 and is Br, Cl or I; R 2a For F or Cl; and R 2b For H; or

[0060] m is 2; R 1a Positioned at positions 3 and 4 and being cyano, CF2H, CF3, CH3OCH2, C2-C3 alkoxycarbonyl, cyclopropyl, phenyl, or 4-chlorophenyl; and R2a and R 2b Each is H; or

[0061] m is 2; R 1a Positioned at positions 3 and 5 and being cyano, CH3, -CH(=O), CF2H, CF3, cyclopropyl, C2-C3 alkoxycarbonyl, 4-fluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, or 4-methoxyphenyl; and R 2a and R 2b Each is H; or

[0062] m is 2; R 1a Located at positions 3 and 5 and is CH3; R 2a For F or Cl; and R 2b For H;

[0063] or

[0064] m is 2; R 1a Located at positions 3 and 5 and is CH3; R 2a For H; and R 2b For F; or

[0065] m is 2; R 1a It is located at positions 4 and 5 and is CF2H, cyclopropyl, CH3OCH2, or C2-C3 alkoxycarbonyl; and R 2a and R 2b Each is H; or

[0066] m is 3; R 1a Positioned at positions 3, 4, and 5 and being cyano, Cl, CH3, CF3, 4-chlorophenyl, 2,4-dichlorophenyl, or 2,2-difluoro-1,3-benzodioxane-4-yl; and R 2a and R 2b Each is H; or

[0067] m is 3; R 1a Located at positions 3, 4, and 5 and being either Cl or CH3; R 2a For F; and R 2b For H;

[0068] For Z-2:

[0069] m is 0; R 2a It is H, Cl, or F; and R 2b For H; or

[0070] m is 1; R 1a It is located at position 2 and is Br, CH3, (CH3)2CH, -CH (=O), phenyl, or 4-fluorophenyl; and R 2a and R2b Each is H; or

[0071] m is 1; R 1a It is in position 2 and is CH3; R 2a For F; and R 2b For H; or

[0072] m is 1; R 1a The 4-position is occupied by a cyano group, Br, I, CH3, CF3, -CH (=O), CH3OC (=O), CH3C (=O)NHCH2CH2, phenyl, or 4-chlorophenyl; and R 2a and R 2b Each is H; or

[0073] m is 1; R 1a It is located at position 4 and is either Br or CH3; R 2a It is Cl, F, CF3 or CH3O; and R 2b For H; or

[0074] m is 1; R 1a It is in position 5 and is CH3OC (=O); R 2a and R 2b Each is H; or

[0075] m is 1; R 1a It is at position 5 and is Br; R 2a It is CH3O; and R 2b For H; or

[0076] m is 2; R 1a It is located at positions 2 and 4 and is Br, Cl, CH3, CHF2S or 4-chlorophenyl; and R 2a and R 2b Each is H; or

[0077] m is 2; R 1a Located at positions 2 and 4 and being CH3; R 2a It is Cl or F; and R 2b For H; or

[0078] m is 2; R 1a Positioned at positions 4 and 5 and being cyano, Cl, CH3, CH3CH2CH2, C2-C3 alkoxycarbonyl, or phenyl; and R 2a and R 2b Each is H; or

[0079] m is 2; R 1a Located at positions 4 and 5 and being Cl, cyano, or CH3OC (=O); R 2a For F or Cl; and R2b For H; or

[0080] m is 3; R 1a Positioned at positions 2, 4, and 5 and being Br, Cl, CF3, CF3S, CH3CH2OC(=O), or 4-chlorophenyl; and R 2a and R 2b Each is H; or

[0081] For Z-3:

[0082] m is 0; R 2a It is H, Cl, F, CF3 or CH3O; and R 2b For H; or

[0083] m is 1; R 1a The group at position 3 is cyano, CF3, CH3S, CH3CH2CH2S, CH3S(=O), CH3S(=O)2, phenyl-CH2S, CH3OC(=O), or (CH3)2N; and R 2a and R 2b Each is H; or

[0084] m is 1; R 1a It is located at position 3 and is a cyano group; R 2a For H; and R 2b For F; or

[0085] m is 1; R 1a It is in position 3 and is CH3OC (=O); R 2a For F or Cl; and R 2b For H; or

[0086] m is 1; R 1a It is located at position 5 and is a cyano group, CF3, CH3S, CH3CH2S, CH3S(=O)2, or CH3OC(=O); and R 2a and R 2b Each is H; or

[0087] m is 1; R 1a It is located at position 5 and is a cyano group; R 2a For H; and R 2b For F; or

[0088] m is 2; R 1a It is located at positions 3 and 5 and is Br, CF2H, CF3, CH3O or NH2; and R 2a and R 2b Each is H; or

[0089] For Z-4:

[0090] m is 1; R 1a Position 4 and is cyano, OHC (=O), C1-C5 alkyl, cyclopropyl, cyclopentyl, CH3CH2OCH2, C2-C4 alkoxycarbonyl, C2-C3 alkylaminocarbonyl, CH3ONHC (=O), 4-chlorophenyl-NHC (=O), 4-methoxyphenyl-NHC (=O), 4-pyridyl-NHC (=O), (CH3)2NC (=O), CH3ON(CH3)C (=O), 3-thiophene, phenyl-C(=O)NHC(Me)2, phenyl, 4-fluorophenyl, 4-methylphenyl, 4-methoxyphenyl, 2-pyridyl, 3-pyridyl, 1-ethyl-3-methyl-1H-pyrazol-4-yl, 1-ethyl-5-methyl-1H-pyrazol-4-yl, 1-methyl-1H-imidazol-5-yl, or (CH3)3Si; and R 2a and R 2b Each is H; or

[0091] m is 1; R 1a It is located at position 5 and is phenyl, CH3OC (=O), or CH3NHC (=O); and R 2a and R 2b Each is H; or

[0092] For Z-5:

[0093] k is 1 or 2; each R 3a Independently, it is Cl, Br, or CH3; and R 2a For H, Cl, or F; where for Z-6:

[0094] k is 1 or 2; each R 3a It can be Br, Cl, CH3 or -CH (=O) independently;

[0095] For Z-7:

[0096] m is 0; or

[0097] m is 1; and R 1a It is in position 5 and is CH3CH2OC (=O); or

[0098] m is 2; and R 1a It is located at positions 4 and 5 and is Cl, CH3, CF3 or 4-fluorophenoxy;

[0099] or

[0100] m is 2; and R 1a Located at positions 4 and 6 and being either Cl or CF3; or

[0101] m is 2; and R 1aLocated at positions 5 and 6 and being either Cl or 4-methoxyphenoxy; or

[0102] m is 2; and R 1a Located at bits 5 and 7 and being either Cl or CF3; or

[0103] m is 2; and R 1a Located at positions 6 and 7 and being either Cl or 4-fluorophenoxy; or

[0104] m is 3; and R 1a It is located at positions 4, 5, and 6 and is either Br or CH3;

[0105] For Z-8:

[0106] m is 0; or

[0107] m is 1; and R 1a It is in position 5 and is CH3CH2OC (=O); or

[0108] m is 2; and R 1a Located at positions 4 and 5 and being Cl, CH3, or 4-fluorophenoxy; or

[0109] m is 2; and R 1a Located at bits 4 and 6 and being either CF3 or Cl; or

[0110] m is 2; and R 1a Located at positions 5 and 6 and being either Cl or 4-methoxyphenoxy; or

[0111] m is 3; and R 1a It is located at positions 4, 5, and 6 and is either Br or CH3;

[0112] For Z-9:

[0113] m is 0; and R 2a For Cl or F; or

[0114] m is 1; R 1a It is located at position 2 and is CF3, CH3CH2, N≡CCH2 or 4-pyridyl; and R 2a For H; or

[0115] m is 1; R 1a It is at position 4 and is Cl; and R 2a For H; or

[0116] m is 1; R 1a It is at position 7 and is Cl; and R 2a For H; or

[0117] m is 2; R1a It is located at bits 2 and 5 and is CH3 or CF3; and R 2a For H; or

[0118] m is 2; R 1a It is located at positions 2 and 5 and is CH3 or F; and R 2a For F; or

[0119] m is 2; R 1a It is located at bits 2 and 6 and is CH3 or CF3; and R 2a For H; or

[0120] m is 2; R 1a It is located at positions 2 and 6 and is CH3 or F; and R 2a For F; or

[0121] m is 2; R 1a Located at bits 5 and 6 and being either Cl or F; and R 2a For H; and

[0122] (f) The compound of formula 1 is not

[0123] α-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-4-morpholine acetonitrile;

[0124] 3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3H-1,2,3-triazolo[4,5-b]pyridine;

[0125] 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-2H-1,2,3-triazolo[4,5-b]pyridine;

[0126] 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-1,2,3-triazolo[4,5-b]pyridine;

[0127] 4-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4H-1,2,3-triazolo[4,5-b]pyridine;

[0128] 5-(2,6-difluorophenyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-2H-1,2,3-triazol-4-carboxynitrile;

[0129] 3-[4-(4H-1,2,4-triazol-4-ylmethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole;

[0130] 3-[4-[[3-[(phenylmethyl)thio]-4H-1,2,4-triazol-4-yl]methyl]phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole;

[0131] 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrrolo[3,2-b]pyridine-2-carboxylonitrile;

[0132] 7-[[2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-7H-pyrrolo[2,3-b]pyridine;

[0133] 3-[3-fluoro-4-[(5-methyl-1H-imidazol-2-yl)methyl]phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole;

[0134] 5,6-Dihydro-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-cyclopentadien[c]pyrrole-4(2H)-one

[0135] 2-Methoxy-5-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]pyridine;

[0136] 3-[4-[(4,5-dihydro-5,5-dimethyl-2-oxazolyl)methyl]phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole;

[0137] N-(2,2,2-trifluoro-1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)cyclopropylamine;

[0138] 4-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrrolo[3,2-b]pyridine-2-carboxynitrile;

[0139] 3-[4-(2H-1,2,3-triazol-2-ylmethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole; or

[0140] 3-[4-(1H-1,2,3-triazol-1-ylmethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole.

[0141] More specifically, the present invention relates to compounds of Formula 1 (including all geometric isomers and stereoisomers), tautomers, N-oxides, or salts thereof.

[0142] The present invention also relates to antifungal compositions comprising (a) a compound of formula 1; and (b) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

[0143] The present invention also relates to antifungal compositions comprising (a) a compound of formula 1; and (b) at least one other antifungal agent (e.g., at least one other antifungal agent having a different site of action).

[0144] The present invention also relates to a method for preventing and controlling plant diseases caused by fungal plant pathogens, the method comprising applying to the plant or parts thereof, or to the seeds of the plant, a fungicide-effective amount of the compound of the present invention (e.g., as the composition described herein). Detailed Implementation

[0145] As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, “contains”, “containing”, “characterized by”, or any other variations thereof are intended to cover non-exclusive inclusion, which is subject to any expressly indicated limitations. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.

[0146] The transitional phrase "consisting of..." excludes any unspecified elements, steps, or ingredients. If present in a claim, this would exclude materials other than those typically associated with impurities. When the phrase "consisting of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements listed in that clause; other elements as a whole are not excluded from the claim.

[0147] The transitional phrase "consistently composed of..." is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements beyond those literally disclosed, provided that such additional materials, steps, features, components, or elements do not substantially affect one or more essential and novel features of the invention protected by the claims. The term "consistently composed of..." falls between "comprising" and "composed of...".

[0148] If the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also using the terms “consistently composed of” or “comprises with” to describe the invention.

[0149] Furthermore, unless explicitly stated otherwise, "or" refers to an inclusive "or" and not an exclusive "or". For example, conditions A or B are satisfied by any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0150] Furthermore, the indefinite articles “a” and “an” preceding the elements or components of the present invention are intended to be non-limiting in terms of the number of instances (i.e., occurrences) of the elements or components. Therefore, “a” or “an” should be understood to include one or at least one, and the singular form of an element or component also includes the plural, unless the quantity is obviously singular.

[0151] As used in this disclosure and claims, "plant" includes members of the plant kingdom, and more specifically, seed plants (gymnosperms) at all stages of life, including young plants (e.g., germinating seeds that develop into seedlings) and mature, reproductive stages (e.g., plants that produce flowers and seeds). Parts of a plant include geotropic members, such as roots, tubers, bulbs, and corms, that typically grow below the surface of the growth medium (e.g., soil), and members that grow above the growth medium, such as leaves (including stems and leaves), flowers, fruits, and seeds.

[0152] As mentioned in this article, the term "seedling," used alone or in combination of words, refers to a young plant that develops from a seed embryo.

[0153] As mentioned in this article, the term "broadleaf" used alone or in words such as "broadleaf crop" refers to dicotyledonous plants, which is a term used to describe a group of angiosperms characterized by an embryo with two cotyledons.

[0154] As used in this disclosure, the terms "fungal pathogen" and "fungal plant pathogen" include pathogens belonging to the phyla Ascomycota, Basidiomycota, and Zygomycota, as well as fungal-like oomycetes, which are pathogens of a broad spectrum of economically important plant diseases affecting ornamental plants, turf, vegetable crops, field crops, cereal crops, and fruit crops. In the context of this disclosure, "protecting plants from diseases" or "controlling plant diseases" includes preventative actions (interrupting the fungal cycle of infection, colonization, symptom development, and spore production) and / or curative actions (inhibiting colonization of plant host tissues).

[0155] As used herein, the term “mode of action” (MOA) is defined by the Fungicide Resistance Action Committee (FRAC) and is used to differentiate fungicides based on their biochemical modes of action in the biosynthetic pathways of plant pathogens. FRAC-defined modes of action include: (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (G) sterol biosynthesis in the membrane, (H) cell wall biosynthesis, (I) melanin synthesis in the cell wall, (P) host plant defense induction, (U) unknown mode of action, (NC) unclassified, and (M) multi-site contact activity. Each mode of action (i.e., letters A through M) comprises activities based on one or more subgroups (e.g., A includes subgroups A1, A2, A3, and A4), based on a single validated target action, or, where the precise target site is unknown, based on the cross-resistance spectrum within the group or in relation to other groups. Each of these subgroups (e.g., A1, A2, A3, and A4) is assigned a FRAC code (numeric and / or alphabetic). For example, subgroup A1 has a FRAC code of 4. Further information about the target site and FRAC codes is available, for example, from publicly accessible databases maintained by FRAC.

[0156] As used herein, the term "cross-resistance" refers to the phenomenon that occurs when a pathogen develops resistance to one fungicide and simultaneously develops resistance to one or more other fungicides. These other fungicides typically, but are not always, of the same chemical class or with the same target site, or can be detoxified through the same mechanism.

[0157] Generally, when a molecular segment (i.e., a group) is represented by a series of atomic symbols (e.g., C, H, N, O, and S), the implicit one or more attachment points will be readily identifiable by those skilled in the art. In some cases herein, specifically, when alternative attachment points are possible, one or more attachment points may be explicitly indicated by a hyphen ("-"). For example, "-SCN" indicates that the attachment point is a sulfur atom (i.e., a thiocyanate ion, not an isothiocyanate ion).

[0158] As used herein, the term "alkylating agent" refers to a compound in which a carbon-containing group is bonded to a leaving group (such as a halide ion or sulfonate ion) via a carbon atom, which may be replaced by a nucleophilic substitution of the carbon atom. Unless otherwise specified, the term "alkylation" does not limit the carbon-containing group to alkyl groups; the carbon-containing group in an alkylating agent includes, for example, groups targeting R. 2 The specified number of carbon-bonded substituents.

[0159] In the above ordinal numbers, the term "alkyl" used alone or in compound terms such as "alkylthio" or "haloalkyl" includes straight-chain and branched alkanes, n-propyl, isopropyl, and various butyl, pentyl, and hexyl isomers. "Alkenyl" includes straight-chain and branched alkenes, such as vinyl, 1-propenyl, 2-propenyl, and various 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 various butynyl, pentynyl, and hexynyl isomers. "Alkynyl" may also include a moiety consisting of multiple triple bonds, such as 2,5-hexadienyl. "Alkylene" refers to a straight-chain or branched alkyl dimethyl alkane. Examples of "alkylene" include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3), and various butene isomers. "Alkenyl" refers to a straight-chain or branched alkenyl group containing one olefinic bond. Examples of "alkenyl" include CH=CH, CH2CH=CH, CH=C(CH3), and various butene isomers. The term "cycloalkylene" refers to a cycloalkane diester ring. Examples of "cycloalkylene" include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene. The term "cycloalkenyl" refers to a cycloalkenyl diester ring containing one olefinic bond. Examples of "cycloalkenyl" include cyclopropenyl and cyclopentenyl.

[0160] "Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and various butoxy, pentoxy, and hexoxy isomers. "Alkenoxy" includes straight-chain and branched alkenyl groups attached to and linked to an oxygen atom. Examples of "alkenoxy" include H₂C=CHCH₂O and CH₃CH=CHCH₂O. "Alkyneoxy" includes straight-chain and branched alkyneoxy moieties. Examples of "alkyneoxy" include HC≡CCH₂O and CH₃C≡CCH₂O.

[0161] The term "alkathioyl" includes both straight-chain and branched alkathioyl moieties, such as methylthio, ethylthio, and various propylthio and butylthio isomers. "alkylsulfinyl" includes two enantiomers of the alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(=O), CH3CH2S(=O), CH3CH2CH2S(=O), (CH3)2CHS(=O), and various butylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(=O)2, CH3CH2S(=O)2, CH3CH2CH2S(=O)2, (CH3)2CHS(=O)2, and various butylsulfonyl isomers. "Alkthioalkyl" indicates alkathioyl substitution on the alkyl group. Examples of “alkylthioalkyl” include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2SCH2 and CH3CH2SCH2CH2; “alkylsulfinylalkyl” and “alkylsulfonylalkyl” include the corresponding sulfoxide and sulfone, respectively.

[0162] "Alkylamino" refers to an NH group substituted with a straight-chain or branched alkyl group. Examples of "alkylamino" include CH3CH2NH, CH3CH2CH2NH, and (CH3)2CHCH2NH. Examples of "dialkylamino" include (CH3)2N, (CH3CH2CH2)2N, and CH3CH2(CH3)N. "Alkylaminoalkyl" indicates alkylamino substitution on an alkyl group. Examples of "alkylaminoalkyl" include CH3NHCH2, CH3NHCH2CH2, CH3CH2NHCH2, CH3CH2CH2CH2NHCH2, and CH3CH2NHCH2CH2.

[0163] "Alkyl carbonyl" refers to a straight-chain or branched alkyl group bonded to a C(=O) moiety. Examples of "alkyl carbonyl" include CH3C(=O), CH3CH2CH2C(=O), and (CH3)2CHC(=O). Examples of "alkoxy carbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O), and various butoxy carbonyl and pentoxy carbonyl isomers. Examples of "alkyl amino carbonyl" include CH3NHC(=O), CH3CH2NHC(=O), CH3CH2CH2NHC(=O), (CH3)2CHNHC(=O), and various butylamino carbonyl and pentylamino carbonyl isomers. Examples of “dialkylaminocarbonyl” include (CH3)2NC(=O), (CH3CH2)2NC(=O), CH3CH2(CH3)NC(=O), (CH3)2CH(CH3)NC(=O) and CH3CH2CH2(CH3)NC(=O).

[0164] The term "alkylcarbonylamino" refers to an alkyl group bonded to a C(=O)NH moiety. Examples of "alkylcarbonylamino" include CH3CH2C(=O)NH and CH3CH2CH2C(=O)NH. The term "alkoxycarbonylamino" refers to an alkoxy group bonded to a C(=O)NH moiety. Examples of "alkoxycarbonylamino" include CH3OC(=O)NH and CH3CH2OC(=O)NH.

[0165] "alkylsulfonylamino" refers to an NH group substituted with an alkylsulfonyl group. Examples of "alkylsulfonylamino" include CH3CH2S(=O)2NH and (CH3)2CHS(=O)2NH. The term "alkylsulfonyloxy" refers to an alkylsulfonyl group bonded to an oxygen atom. Examples of "alkylsulfonyloxy" include CH3S(=O)2O, CH3CH2S(=O)2O, CH3CH2CH2S(=O)2O, (CH3)2CHS(=O)2O, and various butylsulfonyloxy, pentylsulfonyloxy, and hexylsulfonyloxy isomers.

[0166] "Alkoxyalkyl" indicates alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2, and CH3CH2OCH2CH2. "Alkoxyalkoxy" indicates alkoxy substitution on another alkoxy group. "Alkoxyalkoxyalkyl" indicates alkoxyalkoxy substitution on an alkyl group. Examples of "alkoxyalkoxyalkyl" include CH3OCH2OCH2, CH3OCH2OCH2CH2, and CH3CH2OCH2OCH2.

[0167] The term "alkylcarbonyloxy" refers to a straight-chain or branched alkyl group bonded to a C(=O)O moiety. Examples of "alkylcarbonyloxy" include CH3CH2C(=O)O and (CH3)2CHC(=O)O. Examples of "alkoxycarbonyloxy" include CH3CH2CH2OC(=O)O and (CH3)2CHOC(=O)O. The term "alkoxycarbonylalkyl" refers to an alkoxycarbonyl group substituted on an alkyl group. Examples of "alkoxycarbonylalkyl" include CH3CH2OC(=O)CH2, (CH3)2CHOC(=O)CH2, and CH3OC(=O)CH2CH2. The term "alkylaminocarbonyloxy" refers to a straight-chain or branched alkylaminocarbonyl group attached to and connected to an oxygen atom. Examples of "alkylaminocarbonyloxy" include (CH3)2CHCH2NHC(=O)O and CH3CH2NHC(=O)O.

[0168] "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkylalkyl" indicates cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moiety bonded to a straight-chain or branched alkyl group. The term "alkylcycloalkyl" indicates alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, isopropylcyclobutyl, methylcyclopentyl, and methylcyclohexyl. "alkylcycloalkylalkyl" indicates an alkyl group substituted with an alkylcycloalkyl group. Examples of "alkylcycloalkylalkyl" include methylcyclohexylmethyl and ethylcyclopropylmethyl. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl, as well as groups having more than one double bond, such as 1,3-cyclohexadienyl or 1,4-cyclohexadienyl. The term "cycloalkylcycloalkyl" indicates cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has 3 to 7 carbon atom ring members. Examples of cycloalkyl cycloalkyl groups include cyclopropylcyclopropyl (such as 1,1'-dicyclopropyl-1-yl, 1,1'-dicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl), and cyclohexylcyclohexyl (such as 1,1'-dicyclohexyl-1-yl) and various cis and trans cycloalkyl cycloalkyl isomers (such as (1R,2S)-1,1'-dicyclopropyl-2-yl and (1R,2R)-1,1'-dicyclopropyl-2-yl).

[0169] The term "cycloalkoxy" refers to a cycloalkyl group attached to and linked to an oxygen atom, including, for example, cyclopentoxy and cyclohexyloxy. The term "cycloalkoxyalkyl" refers to cycloalkoxy substitution on an alkyl moiety. Examples of "cycloalkoxyalkyl" include cyclopropoxymethyl, cyclopentoxyethyl, and other cycloalkoxy groups bonded to straight-chain or branched alkyl moieties.

[0170] The term "cycloalkylaminoalkyl" indicates cycloalkylamino substitution on an alkyl group. Examples of "cycloalkylaminoalkyl" include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to straight-chain or branched alkyl groups.

[0171] "Cycloalkylcarbonyl" refers to a cycloalkyl group bonded to a C(=O) group, including, for example, cyclopropylcarbonyl and cyclopentylcarbonyl. "Cycloalkylcarbonyloxy" refers to a cycloalkylcarbonyl group attached to and linked to an oxygen atom. Examples of "cycloalkylcarbonyloxy" include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy. The term "cycloalkoxycarbonyl" refers to a cycloalkoxy group bonded to a C(=O) group, such as cyclopropoxycarbonyl and cyclopentoxycarbonyl. "Cycloalkylaminocarbonylamino" refers to a cycloalkylamino group bonded to a C(=O)NH group, such as cyclopentylaminocarbonylamino and cyclohexylaminocarbonylamino.

[0172] The term "halogen" includes fluorine, chlorine, bromine, or iodine, either alone or in compound terms such as "halogenated alkyl," or when used to describe a halogen-substituted alkyl group. Furthermore, when used in compound terms such as "halogenated alkyl," or to describe a halogen-substituted alkyl group, the alkyl group may be partially or completely substituted with a halogen atom, which may be the same or different. Examples of "halogenated alkyl" or "halogen-substituted alkyl" include F3C, ClCH2, CF3CH2, and CF3CCl2. The terms "halogenated alkenyl," "halogenated alkynyl," "halogenated alkoxy," "halogenated alkylsulfonyl," "halogenated cycloalkyl," etc., are defined similarly to the term "halogenated alkyl." Examples of "halogenated alkenyl" include Cl2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "halogenated alkynyl" include HC≡CCHCl, CF3C≡C, CCl3C≡C, and FCH2C≡CCH2. Examples of “haloalkoxy” include CF3O, CCl3CH2O, F2CHCH2CH2O, and CF3CH2O. Examples of “haloalkylsulfonyl” include CF3S(=O)2, CCl3S(=O)2, CF3CH2S(=O)2, and CF3CF2S(=O)2. Examples of “halocycloalkyl” include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl, and 4-chlorocyclohexyl.

[0173] "Cyanoalkyl" refers to an alkyl group substituted with a cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2, and CH3CH(CN)CH2. "Hydroxyalkyl" refers to an alkyl group substituted with a hydroxyl group. Examples of "hydroxyalkyl" include HOCH2CH2, CH3CH2(OH)CH, and HOCH2CH2CH2CH2.

[0174] The total number of carbon atoms in the substituents is determined by "C i –C j The prefix indicates that i and j are numbers from 1 to 14. For example, C1–C4 alkylsulfonyl groups represent methanesulfonyl to butanesulfonyl groups; C2 alkoxyalkyl groups represent CH3OCH2; C3 alkoxyalkyl groups represent, for example, CH3CH(OCH3), CH3OCH2CH2, or CH3CH2OCH2; and C4 alkoxyalkyl groups represent various isomers of alkyl groups substituted with alkoxy groups containing a total of four carbon atoms, examples of which include CH3CH2CH2OCH2 and CH3CH2OCH2CH2.

[0175] The term "unsubstituted" in relation to groups such as rings or cyclic systems means that the group has no substituents other than one or more linking groups with the remainder of Formula 1. The term "optionally substituted" means that the number of substituents may be zero. Unless otherwise specified, an optionally substituted group may be substituted with as many optional substituents as possible, which may be accommodated by replacing hydrogen atoms with non-hydrogen substituents on any available carbon or nitrogen atom. Typically, the number of optional substituents (when present) is in the range of 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".

[0176] The number of optional substituents can be limited by expression restrictions. For example, the phrase "optionally selected by up to 3 independently chosen R" can be construed as... 2 "Substituent substitution" means that 0, 1, 2, or 3 substituents may be present (if the number of possible connection points allows). When the range specified for the number of substituents (e.g., x is an integer from 0 to 2 in Example A) exceeds the number of positions available for substituents on the ring (e.g., 1 position available for (R) on U-7 in Example A), 2 ) x If the range is 0, then the actual upper limit of the range is considered to be the number of available positions.

[0177] When a compound is substituted by a substituent with a subscript, the subscript indicates that the number of substituents can vary (e.g., (R in Example A)). 2 ) x (where x is 1 to 2), then unless otherwise specified, the substituent is independently selected from the defined substituents. When a variable group is shown to be optionally attached to a certain position, for example, (R) in Example A 2 ) x Where x can be 0, hydrogen can be located at that position even if it is not listed in the definition of a variable group.

[0178] The naming of substituents in this disclosure uses recognized terminology, thereby providing brevity in accurately conveying the chemical structure to those skilled in the art. For brevity, positional descriptors may be omitted.

[0179] Unless otherwise specified, as a component of Equation 1 (e.g., R) 1 The "ring" or "ring system" in J) refers to a carbon ring or heterocycle. The term "ring system" indicates two or more linked rings. The term "spirocyclic ring system" indicates a ring system consisting of two rings linked at a single atom (therefore the rings share a common single atom). The term "bicyclic ring system" indicates a ring system consisting of two rings sharing two or more common atoms. In a "fused bicyclic ring system," the common atoms are adjacent, so the rings share two adjacent atoms and the bonds connecting them.

[0180] The term "ring member" refers to the atom (e.g., C, O, N, or S) or other part (e.g., C(=O), C(=S), S(=O), and S(=O)2) that forms the framework of a ring or ring system. The term "aromatic" indicates that each atom in the ring is substantially in the same plane and has p-orbitals perpendicular to the ring plane, and (4n+2)π electrons (where n is a positive integer) are associated with the ring to obey Hückel's law.

[0181] The term "carbon ring" refers to a ring in which the atoms forming the ring skeleton are selected only from carbon. Unless otherwise specified, a carbon ring can be saturated, partially unsaturated, or fully unsaturated. When a fully unsaturated carbon ring satisfies Hückel's rule, the ring is also called an "aromatic ring." A "saturated carbon ring" is a ring having a skeleton composed of carbon atoms connected to each other by single bonds; unless otherwise specified, the remaining carbon valence is occupied by hydrogen atoms.

[0182] As used herein, the terms “partially unsaturated ring” or “partially unsaturated heterocycle” refer to a ring that contains unsaturated ring atoms and one or more double bonds but is not aromatic.

[0183] The term "heterocyclic ring" or "heterocycle" refers to a ring in which at least one of the atoms forming the ring skeleton is not carbon. Unless otherwise specified, a heterocyclic ring can be saturated, partially unsaturated, or fully unsaturated. When a fully unsaturated heterocyclic ring satisfies Hückel's rule, it is also called a "heteroaromatic ring" or aromatic heterocyclic ring. A "saturated heterocyclic ring" is a heterocyclic ring containing only single bonds between its ring members.

[0184] Unless otherwise specified, heterocyclic and cyclic systems are attached to the remainder of Formula 1 by replacing the hydrogen atom on the carbon or nitrogen atom with any available carbon or nitrogen atom.

[0185] The compounds of the present invention can exist in the form of one or more stereoisomers. Stereoisomers are isomers having the same composition but different spatial arrangements of their atoms, and include enantiomers, diastereomers, cis and trans isomers (also called geometric isomers), and blocked isomers. Blocked isomers are caused by restricted rotation around a single bond, wherein the rotational energy barrier is high enough to allow the isomer species to be separated. Those skilled in the art will understand that a stereoisomer may be more active and / or exhibit beneficial effects when enriched relative to other stereoisomers, or when separated from other stereoisomers. Furthermore, those skilled in the art know how to separate, enrich, and / or 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.

[0186] Because rotation around the amide bond (e.g., C(=O)-N) in Formula 1 is restricted, the compounds of the present invention can exist in one or more conformational isomers. The present invention includes mixtures of conformational isomers. Furthermore, the present invention includes compounds rich in one conformational isomer relative to other substances.

[0187] This invention includes all stereoisomers, conformational isomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.

[0188] Those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides, as a lone pair of electrons is required to oxidize nitrogen to an oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize tertiary amines that can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art, and these methods involve oxidizing heterocycles and tertiary amines with peroxy acids (such as peracetic acid and m-chloroperoxybenzoic acid (MCPBA)), hydrogen peroxide, alkyl hydrogen peroxides (such as tert-butyl hydrogen peroxide), sodium perborate, and peroxide ketones (such as dimethyl peroxide ketone). These methods for preparing N-oxides have been extensively described and reviewed in the literature, see, for example: T.L. Gilchrist, Comprehensive Organic Synthesis, Vol. 7, pp. 748-750, edited by SV Ley, Pergamon Press; M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20, edited by A.J. Boulton and A. McKillop, Pergamon Press; M.R. Grimemett and B.R. Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161, edited by A.R. Katritzky, Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, Vol. 9, pp. 285-291, edited by A.R. Katritzky and A.J. Boulton, Academic Press; and GW.H. Heeseman and E.S. GWerstiuk, Advances in Heterocyclic Chemistry, Vol. 22, pp. 390-392, edited by A.R. Katritzky and A.J. Boulton, Academic Press.

[0189] Those skilled in the art recognize that, because the salts of compounds are in equilibrium with their corresponding non-salt forms under environmental and physiological conditions, the salts share the biological benefits of the non-salt forms. Therefore, various salts of compounds of Formula 1 can be used to control plant diseases caused by fungal plant pathogens (i.e., agriculturally suitable). Salts of compounds of Formula 1 include acid addition salts with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. When a compound of Formula 1 contains an acidic moiety (such as a carboxylic acid), its salts also include those formed with an organic or inorganic base such as pyridine, triethylamine, or ammonia, or amides, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium, or barium. Therefore, the present invention includes salts, solvates, and hydrates selected from Formula 1, its N-oxides, and agriculturally suitable salts.

[0190] Compounds selected from Formula 1, its stereoisomers, tautomers, N-oxides, and salts generally exist in more than one form, and therefore Formula 1 includes all crystalline and amorphous forms of the compounds represented by Formula 1. Amorphous forms include embodiments in solid form (such as waxes and gums) and embodiments in liquid form (such as solutions and melts). Crystalline forms include embodiments that substantially represent a single crystal form and embodiments that represent a mixture of polymorphs (i.e., different crystal forms). The term "polymorph" refers to a specific crystalline form of a chemical compound that can crystallize in different crystalline forms, having different molecular arrangements and / or molecular conformations in the crystal lattice. Although polymorphs may have the same chemical composition, they may differ in composition due to the presence or absence of co-crystallization water or other molecules that may be weakly or strongly bound in the crystal lattice. Polymorphs may differ in chemical, physical, and biological properties (such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate, and bioavailability). Those skilled in the art will understand that polymorphs of compounds represented by Formula 1 may exhibit beneficial effects (e.g., suitability for preparing useful formulations, improved biological properties) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1. The preparation and isolation of specific polymorphs of compounds of Formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using a selected solvent and temperature. For a comprehensive discussion of polymorphism, see R. Hilfiker (ed.), *Polymorphism in the Pharmaceutical Industry*, Wiley-VCH, Weinheim, 2006.

[0191] The compounds described herein and their agriculturally acceptable salts can exist as a solid continuum ranging from completely amorphous to completely crystalline. They can also exist in both non-solventized and solvated forms. The term "solvent" describes a molecular complex comprising the compound and one or more agriculturally acceptable solvent molecules (e.g., EtOH). The term "hydrate" is a solvate in which water is the solvent. Agriculturally acceptable solvates include those in which the solvent can be isotopically substituted (e.g., DD2O, d6-acetone, d6-DMSO).

[0192] The currently accepted classification system for solvates and hydrates of organic compounds distinguishes between solvates and hydrates with separation sites, channels, and metal ion coordination. See, for example, K.M. Morris (edited by H.G. Brittain), Polymorphism in Pharmaceutical Solids (1995). Separation site solvates and hydrates are those in which solvent (e.g., water) molecules avoid direct contact with each other by interfering with the molecules of the organic compound. In channel solvates, solvent molecules are located in lattice channels where they are adjacent to other solvent molecules. In metal ion coordinated solvates, solvent molecules are bonded to metal ions.

[0193] The embodiments of the invention described in the summary include those described below. In the following embodiments, Formula 1 includes its stereoisomers, N-oxides, hydrates, and salts, and unless otherwise defined in the embodiments, references to "compounds of Formula 1" include the definitions of substituents specified in the summary.

[0194] Implementation Scheme 1: A compound of Formula 1, wherein R 1 Selected from U-1 to U-118, as shown in Example A.

[0195] Example A

[0196]

[0197]

[0198]

[0199]

[0200]

[0201] The floating bond is connected to L in Formula 1 via any available carbon or nitrogen atom in the ring or ring system shown; and x is 0, 1, or 2.

[0202] Implementation Scheme 2: The compound described in Implementation Scheme 1, wherein R 1 Be U-1 to U-16, U-20, U-22, U-24, U-25, U-26, U-28, U-29, U-30, U-37, U-38, U-42 ​​to U-47 or U-71 to U-114.

[0203] Implementation Scheme 3: The compound described in Implementation Scheme 2, wherein R 1 For U-12, U-24, U-26, U-28, U-29, U-30, U-37, U-38, U-42 ​​to U-46, U-71, U-74, U-76, U-77, U-78, U-82, U-83, U-84 to U-91, U-93 to U-96, U-99 or U-101 to U-114.

[0204] Implementation Scheme 4: The compound described in Implementation Scheme 3, wherein R 1 For U-12, U-24, U-26, U-28, U-29, U-30, U-42 ​​to U-46, U-71, U-76, U-77, U-78 , U-82, U-83, U-84, U-89, U-90, U-91, U-93, U-103, U-104 or U-109 to U-112.

[0205] Implementation Scheme 5: The compound described in Implementation Scheme 4, wherein R 1 Be U-12, U-26, U-29, U-30, U-42 ​​through U-46, U-71, U-76, U-77, U-78, U-82, U-83, U-89, U-90, U-103 or U-104.

[0206] Implementation Scheme 6: The compound described in Implementation Scheme 5, wherein R 1 Be U-104U-12, U-29, U-42, U-43, U-71, U-76, U-77, U-89, U-90, U-103 or U-104.

[0207] Implementation Scheme 7: The compound described in Implementation Scheme 6, wherein R 1 Be U-12, U-29, U-89 or U-90.

[0208] Implementation Scheme 8: The compound described in Implementation Scheme 7, wherein R 1 It is U-89.

[0209] Implementation Scheme 9: The compound described in Implementation Scheme 7, wherein R 1 It is U-90.

[0210] Implementation Scheme 10: The compound described in Implementation Scheme 1, wherein R 1 Be U-1, U-2, U-4, U-5, U-8, U-12, U-29, U-58, U-69, U-79, U-80, U-104, U-115, U-116, U-117 or U-118.

[0211] Implementation Scheme 11: The compound described in Implementation Scheme 10, wherein R 1 Be U-1, U-2, U-4, U-5, U-12 or U-29.

[0212] Implementation Scheme 12: The compound described in Implementation Scheme 11, wherein R 1 Be U-1, U-2, U-12 or U-29.

[0213] Implementation Scheme 13: The compound described in Implementation Scheme 12, wherein R 1 It is either U-2 or U-12.

[0214] Implementation Scheme 14: The compound described in Implementation Scheme 12, wherein R 1 It is U-1.

[0215] Implementation Scheme 14a: The compound of Implementation Scheme 14, wherein U-1 is linked to L at its 2 position.

[0216] Implementation Scheme 14b: The compound described in Implementation Scheme 14, wherein U-1 is linked to L at its 5 position.

[0217] Implementation Scheme 15: The compound described in Implementation Scheme 12, wherein R 1 It is U-2.

[0218] Implementation Scheme 15a: The compound of Implementation Scheme 15, wherein U-2 is linked to L at its 2 position.

[0219] Implementation Scheme 15b: The compound described in Implementation Scheme 15, wherein U-2 is linked to L at its 4 position.

[0220] Implementation scheme 15c: The compound of implementation scheme 15, wherein U-2 is linked to L at its 5 position.

[0221] Implementation Scheme 16: The compound described in Implementation Scheme 12, wherein R 1 It is U-12.

[0222] Implementation Scheme 16a: The compound of Implementation Scheme 16, wherein U-12 is linked to L at its 1 position.

[0223] Implementation Scheme 16b: The compound of Implementation Scheme 16, wherein U-12 is linked to L at its 3 position.

[0224] Implementation Scheme 16c: The compound of Implementation Scheme 16, wherein U-12 is linked to L at its 4 position.

[0225] Implementation Scheme 17: The compound described in Implementation Scheme 12, wherein R 1 It is U-29.

[0226] Implementation Scheme 17a: The compound described in Implementation Scheme 17, wherein U-29 is linked to L at its 5 position.

[0227] Implementation Scheme 18: The compound of any one of Implementation Schemes 1 to 17a, wherein x is 1 or 2.

[0228] Implementation Scheme 19: The compound described in Implementation Scheme 18, wherein x is 1.

[0229] Implementation Scheme 20: The compound described in Implementation Scheme 18, wherein x is 2.

[0230] Implementation Scheme 21: A compound of Formula 1 or any one of Implementation Schemes 1 to 20, wherein L is O, (CR 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O, or CH2OCH2, where the atom on the left is attached to R. 1 And the atom on the right is connected to J, and each carbon atom is optionally substituted by up to 2 substituents, which are independently selected from halogen, cyano, hydroxyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

[0231] Implementation Scheme 22: The compound described in Implementation Scheme 21, wherein L is (CR 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O, or CH2OCH2, where the atom on the left is attached to R. 1 Furthermore, the atom on the right is connected to J, and each carbon atom is optionally substituted by at most one substituent, which is independently selected from halogen, cyano, hydroxy, methyl, halomethyl or methoxy.

[0232] Implementation Scheme 23: The compound described in Implementation Scheme 22, wherein L is (CR 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O, or CH2OCH2, where the atom on the left is attached to R. 1 And the atom on the right is connected to J.

[0233] Implementation Scheme 24: A compound of Formula 1 or any one of Implementation Schemes 1 to 21, wherein L is (CR 4a R 4b ) n , OCH2 or CH2O, where the atom on the left is attached to R. 1 And the atom on the right is connected to J, and each carbon atom is optionally substituted by up to 2 substituents, which are independently selected from halogen, cyano, hydroxyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

[0234] Implementation Scheme 25: The compound described in Implementation Scheme 24, wherein L is (CR 4a R 4b ) n , OCH2 or CH2O, where the atom on the left is attached to R. 1 And the atom on the right is connected to J, and each carbon atom is optionally substituted by at most one substituent selected from halogen, cyano, hydroxyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

[0235] Implementation Scheme 26: The compound described in Implementation Scheme 25, wherein L is (CR 4a R 4b ) n , OCH2 or CH2O, where the atom on the left is attached to R. 1 And the atom on the right is connected to J.

[0236] Implementation Scheme 27: The compound described in Implementation Scheme 25, wherein L is (CR 4a R 4b ) n .

[0237] Implementation Scheme 28: A compound of Formula 1 or any one of Implementation Schemes 1 to 27, wherein n is 1 or 2.

[0238] Implementation Scheme 29: The compound described in Implementation Scheme 28, wherein n is 1.

[0239] Implementation Scheme 30: The compound described in Implementation Scheme 28, wherein n is 2.

[0240] Implementation Scheme 31: The compound of Formula 1 or any one of Implementation Schemes 1 to 27, wherein n is 3.

[0241] Scheme 32: A compound of Formula 1 or any one of Schemes 1 to 31, wherein J is a benzene ring optionally substituted with up to two substituents, said substituents being independently selected from R. 5Or a 3- to 7-membered carbon ring, wherein at most two ring members are independently selected from C (=O) and C (=S), and each ring is optionally substituted by at most two substituents, said substituents being independently selected from R. 5 Or a 5- or 6-membered heterocycle, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C (=O) and C (=S), and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R 5 .

[0242] Implementation Scheme 33: A compound of Formula 1 or any one of Implementation Schemes 1 to 32, wherein J is selected from J-1 to J-93 as shown in Example B.

[0243] Example B

[0244]

[0245]

[0246]

[0247]

[0248]

[0249] The bonds extending to the left are bonded to L, and the bonds extending to the right are bonded to the oxadiazole ring in Formula 1; and each R 5a Independently for H or R 5 The prerequisite is that there are at most two Rs. 5a The substituent is not H.

[0250] Implementation Scheme 34: The compound described in Implementation Scheme 33, wherein J is J-1 to J-5, J-17, J-18, J-37 to J-41, J-60, J-63 to J-71, J-73, J-74, J-75 or J-77 to J-85.

[0251] Implementation Scheme 35: The compound described in Implementation Scheme 34, wherein J is J-4, J-5, J-18, J-37, J-40, J-41, J-63 to J-69, J-73 or J-77 to J-85.

[0252] Implementation Scheme 36: The compound described in Implementation Scheme 35, wherein J is J-4, J-18, J-37, J-40, J-63 to J-69 or J-73.

[0253] Implementation Scheme 37: The compound described in Implementation Scheme 36, wherein J is J-37, J-40, or J-63 to J-67.

[0254] Implementation Scheme 38: The compound described in Implementation Scheme 37, wherein J is J-37.

[0255] Implementation Scheme 39: The compound described in Implementation Scheme 37, wherein J is J-40.

[0256] Implementation Scheme 40: The compound described in Implementation Scheme 37, wherein J is J-63 to J-65.

[0257] Implementation Scheme 41: The compound described in Implementation Scheme 40, wherein J is J-63.

[0258] Implementation Scheme 42: The compound described in Implementation Scheme 40, wherein J is J-64.

[0259] Implementation Scheme 43: The compound described in Implementation Scheme 33, wherein J is J-4, J-18, J-27, J-40, J-41, J-63, J-73 or J-93.

[0260] Implementation Scheme 44: The compound described in Implementation Scheme 43, wherein J is J-4, J-18, J-27, J-40 or J-63.

[0261] Implementation Scheme 45: The compound described in Implementation Scheme 44, wherein J is J-27, J-40 or J-63.

[0262] Implementation Scheme 45a: The compound described in Implementation Scheme 45, wherein J is J-40 or J-63.

[0263] Implementation Scheme 46: The compound described in Implementation Scheme 45, wherein J is J-27.

[0264] Implementation Scheme 47: The compound described in Implementation Scheme 45, wherein J is J-40.

[0265] Implementation Scheme 48: The compound described in Implementation Scheme 45, wherein J is J-63.

[0266] Implementation Scheme 49: A compound of any one of Implementation Schemes 33 to 48, wherein R 5a It can be H, cyano, halogen, methyl or methoxy.

[0267] Implementation Scheme 50: The compound described in Implementation Scheme 49, wherein R 5a It can be H, halogen, methyl or methoxy.

[0268] Implementation Scheme 51: The compound described in Implementation Scheme 50, wherein R 5aIt can be H, methyl, or methoxy.

[0269] Implementation Scheme 52: The compound described in Implementation Scheme 51, wherein R 5a For H.

[0270] Implementation Scheme 53: A compound of Formula 1 or any one of Implementation Schemes 1 to 52, wherein each R 2 Independently halogen, cyano, -NR 3a R 3b -C(=O)NR 3a R 3b -C(=S)NR 3a R 3b or -C(R) 6 ) = NR 7 ; or C1-C6 alkyl, C3-C7 cycloalkyl, C1-C6 alkoxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenoxycarbonyl, C3-C6 alkynoxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy C4-C7 cycloalkylcarbonyloxy, C2-C6 alkoxycarbonyloxy, C4-C7 cycloalkoxycarbonyloxy, C2-C6 alkylaminocarbonyloxy, C4-C7 cycloalkylaminocarbonyloxy, C2-C6 alkylcarbonylamino, C4-C7 cycloalkylcarbonylamino, C2-C6 alkoxycarbonylamino, C4-C7 cycloalkoxycarbonylamino, C2-C6 alkylaminocarbonylamino, or C4-C7 cycloalkylaminocarbonylamino, each optionally substituted with up to three substituents, said substituents being independently selected from R 10 .

[0271] Implementation Scheme 54: The compound described in Implementation Scheme 53, wherein each R 2 Independently cyano, -NR 3a R 3b -C(=O)NR 3a R 3b -C(=S)NR 3a R 3b or -C(R) 6 ) = NR 7; or C1-C3 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonyloxy, C1-C4 alkylsulfonylamino, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl, C3-C4 alkenoxycarbonyl, C3-C4 alkynoxycarbonyl, C4-C5 cycloalkoxycarbonyl, C2-C3 alkylcarbonyloxy, C2-C4 alkoxycarbonyloxy, C2-C4 alkylaminocarbonyloxy, C2-C4 alkylcarbonylamino, C2-C4 alkoxycarbonylamino, or C2-C4 alkylaminocarbonylamino, each optionally substituted with at most one substituent selected from R 10 .

[0272] Implementation Scheme 55: The compound described in Implementation Scheme 54, wherein each R 2 Independently for -NR 3a R 3b -C(=O)NR 3a R 3b -C(=S)NR 3a R 3b or -C(R) 6 ) = NR 7 ); or C1-C3 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkylsulfonyloxy, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl, C3-C4 alkenoxycarbonyl, C3-C4 alkynoxycarbonyl, C4-C5 cycloalkoxycarbonyl, or C2-C3 alkylcarbonyloxy, each optionally substituted with at most one substituent selected from R 10 .

[0273] Implementation Scheme 56: A compound of Formula 1 or any one of Implementation Schemes 1 to 53, wherein each R 2 Independently halogen, cyano, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy, or C2-C6 alkylcarbonylamino, each optionally substituted with up to 3 substituents, said substituents being independently selected from R 10 .

[0274] Implementation Scheme 56a: The compound described in Implementation Scheme 56, wherein each R 2 Independently halogen, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenoxy, C2-C6 alkoxy carbonyl, C3-C6 alkenoxy carbonyl, C3-C6 alkoxy carbonyl, C4-C7 cycloalkoxy carbonyl, C2-C6 alkyl carbonyloxy, or C2-C6 alkyl carbonyl amino, each optionally substituted with up to 3 substituents, said substituents being independently selected from R 10 .

[0275] Implementation Scheme 56b: The compound of Implementation Scheme 56a wherein each R 2 Independently halogen, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b or -C(R) 6 ) = NR 7 ; or C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenoxy, C2-C6 alkoxy carbonyl, C3-C6 alkenoxy carbonyl, C3-C6 alkoxy carbonyl, C4-C7 cycloalkoxy carbonyl, C2-C6

[0276] The alkyl carbonyloxy group or C2-C6 alkyl carbonyl amino group is optionally substituted with up to three substituents, each substituent being independently selected from R. 10 .

[0277] Implementation Scheme 57: The compound described in Implementation Scheme 56, wherein each R 2 Independently halogen, cyano, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy, or C2-C6 alkylcarbonylamino, each optionally substituted with up to two substituents, said substituents being independently selected from R 10 .

[0278] Implementation Scheme 58: The compound described in Implementation Scheme 57, wherein each R 2 Independently halogen, cyano, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy, or C2-C6 alkylcarbonylamino, each optionally substituted with at most one substituent, said substituent being independently selected from R 10 .

[0279] Implementation Scheme 59: The compound described in Implementation Scheme 58, wherein each R 2 Independently halogen, cyano, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl or C4-C7 cycloalkoxycarbonyl, each optionally substituted with at most one substituent, said substituent being independently selected from R 10 .

[0280] Implementation Scheme 60: The compound described in Implementation Scheme 59, wherein each R 2 Independently -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C2-C6 alkoxycarbonyl, C3-C6 alkenoxycarbonyl, or C3-C6 alkynoxycarbonyl, each optionally substituted with at most one substituent selected from R 10 .

[0281] Implementation Scheme 61: The compound described in Implementation Scheme 60, wherein each R 2 Independently -C(=O)NR 3a R 3b or -C(R) 6 ) = NR 7; or C2-C6 alkoxycarbonyl, C3-C6 alkenoxycarbonyl, or C3-C6 alkynoxycarbonyl, each optionally substituted with at most one substituent selected from R 10 .

[0282] Implementation Scheme 62: The compound described in Implementation Scheme 56, wherein each R 2 Independently -C(=O)NR 3a R 3b ; or a C2-C6 alkoxycarbonyl group, optionally substituted with up to three substituents, said substituents being independently selected from R 10 .

[0283] Implementation Scheme 63: The compound described in Implementation Scheme 62, wherein each R 2 Independently -C(=O)NR 3a R 3b ; or a C2-C6 alkoxycarbonyl group, optionally substituted with up to two substituents, said substituents being independently selected from R 10 .

[0284] Implementation Scheme 64: The compound described in Implementation Scheme 63, wherein each R 2 Independently -C(=O)NR 3a R 3b ; or a C2-C6 alkoxycarbonyl group, optionally substituted with at most one substituent selected from R 10 .

[0285] Implementation Scheme 65: The compound described in Implementation Scheme 64, wherein each R 2 Independently -C(=O)NR 3a R 3b Or C2-C6 alkoxycarbonyl.

[0286] Implementation Scheme 66: A compound of formula or any one of embodiments 1 to 65, wherein R 3 It can be H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl or C1-C4 alkoxy.

[0287] Implementation Scheme 67: The compound described in Implementation Scheme 66, wherein R 3 It can be H, cyano, hydroxyl, C1-C4 alkyl or C1-C4 alkoxy.

[0288] Implementation Scheme 68: The compound described in Implementation Scheme 67, wherein R 3 It can be H, cyano, hydroxy, methyl, or methoxy.

[0289] Implementation Scheme 69: The compound described in Implementation Scheme 68, wherein R 3For H.

[0290] Implementation Scheme 70: A compound of Formula 1 or any one of Implementation Schemes 1 to 69, wherein each R 3a All are independent (i.e., not related to R). 3b (combined together), then each R 3a Independently, it is H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxy, C2-C4 alkoxyalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylthioalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C4-C6 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl, or C3-C5 dialkylaminocarbonyl.

[0291] Implementation Scheme 71: The compound described in Implementation Scheme 70, wherein each R 3a Independently, it is H, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxyalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylthioalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C4-C6 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl;

[0292] Implementation Scheme 72: The compound described in Implementation Scheme 71, wherein each R 3a It can be independently H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxyalkyl, C1-C3 alkylsulfonyl, C2-C4 alkylthioalkyl, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminocarbonyl or C3-C4 dialkylaminocarbonyl.

[0293] Implementation Scheme 73: The compound of Formula 1 or any one of Implementation Schemes 1 to 69, wherein each R 3a It is independent (i.e., not related to R) 3b (combined together), then each R 3a Independently, it is H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C5 alkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C4-C6 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, or C3-C5 alkoxycarbonylalkyl.

[0294] Implementation Scheme 74: The compound described in Implementation Scheme 73, wherein each R 3a It can be independently H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl or C3-C5 alkoxycarbonylalkyl.

[0295] Implementation Scheme 74a: The compound described in Implementation Scheme 74, wherein each R 3a It can be independently H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl or C3-C5 alkoxycarbonylalkyl.

[0296] Implementation Scheme 75: The compound described in Implementation Scheme 74, wherein each R 3a It can be independently H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxyalkyl, or C3-C5 alkoxycarbonylalkyl.

[0297] Implementation Scheme 76: The compound of Formula 1 or any one of Implementation Schemes 1 to 75, wherein each R 3b It is independent (i.e., not related to R) 3a (combined together), then each R 3b Independently, it is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylaminoalkyl or C3-C8 dialkylaminoalkyl.

[0298] Implementation Scheme 77: The compound described in Implementation Scheme 76, wherein each R 3b Independently, it is H, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl, C2-C4 alkylaminoalkyl, or C3-C6 dialkylaminoalkyl. Example 78: The compound described in Example 77, wherein each R... 3b It can be independently H, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkylthioalkyl.

[0299] Implementation Scheme 79: A compound of Formula 1 or any one of Implementation Schemes 1 to 75, wherein when each R 3b Independent (i.e., not with R) 3a When combined, each R3b Independently, H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 ynyl, C2-C6 haloynyl, C1-C6 hydroxyalkyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C4-C 10 Alkyl cycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 Halogenated cycloalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C4-C 10 The cycloalkoxyalkyl group is optionally substituted with at most one substituent selected from cyano, hydroxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C4 alkylcarbonyl, C4-C4 alkylcarbonyl, C5-C6 alkylcarbonyl, C6-C6 alkylcarbonyl, C7-C6 alkylcarbonyl, C8-C6 alkylcarbonyl, C9-C9 ... 15 Trialkylsilyl and C3-C 15 Halogenated trialkylsilyl groups.

[0300] Implementation Scheme 80: The compound described in Implementation Scheme 79, wherein each R 3b Independently, it is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 ynyl, C2-C6 haloynyl, C3-C8 halocycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 The alkyl halocycloalkyl, C2-C6 alkoxyalkyl, or C2-C6 haloalkoxyalkyl group is optionally substituted with at most one substituent selected from cyano, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, and C3-C6 alkylcarbonyl. 15 Trialkylsilyl.

[0301] Implementation Scheme 81: The compound described in Implementation Scheme 80, wherein each R 3b Independently, it is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 ynyl, C2-C6 haloynyl, C4-C 10 cycloalkylalkyl, C4-C 10 The alkyl halocycloalkyl, C2-C6 alkoxyalkyl, or C2-C6 haloalkoxyalkyl group is optionally substituted with at most one substituent selected from C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl.

[0302] Implementation Scheme 82: The compound described in Implementation Scheme 81, wherein each R 3b It is independently H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl or C2-C6 haloalkenyl C, each optionally substituted by at most one substituent selected from C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl.

[0303] Implementation Scheme 83: The compound described in Implementation Scheme 82, wherein each R 3b It is independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl or C2-C4 haloalkenyl C, each optionally substituted by at most one substituent selected from C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl.

[0304] Implementation Scheme 84: The compound described in Implementation Scheme 83, wherein each R 3b It can be independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl or C2-C4 haloalkenyl.

[0305] Implementation Scheme 85: The compound of Formula 1 or any one of Implementation Schemes 1 to 84, wherein when a pair of R atoms attached to the same nitrogen atom 3a and R 3b When the substituents are combined to form a fully saturated heterocycle of 5 to 6 members, the ring comprises ring members selected from carbon atoms and at most one heteroatom, in addition to the connecting nitrogen atom, the heteroatom being selected from at most one O atom, at most one S atom and at most one N atom, each ring optionally being substituted by at most two methyl groups.

[0306] Implementation Scheme 86: The compound described in Implementation Scheme 85, wherein a pair of R atoms attached to the same nitrogen atom 3a and R 3b Substituents are combined to form an aza-butyl ring, a morpholinyl ring, a pyrrolidinyl ring, a piperidinyl ring, a piperazinyl ring, or a thiomorpholinyl ring, each ring optionally being substituted with up to two methyl groups.

[0307] Implementation Scheme 87: The compound of Formula 1 or any one of Implementation Schemes 1 to 86, wherein when each R 4a and R 4b When they are independent (i.e., not grouped together), then each R 4a and R 4b It can be H, halogen, cyano, hydroxyl, methyl or methoxy.

[0308] Implementation Scheme 88: The compound described in Implementation Scheme 87, wherein each R 4a and R 4b It can be H, halogen, hydroxyl, methyl or methoxy.

[0309] Implementation Scheme 89: The compound described in Implementation Scheme 88, wherein each R 4a and R 4b It can be H or methyl on its own.

[0310] Implementation Scheme 90: The compound described in Implementation Scheme 89, wherein each R 4a and R 4b For H.

[0311] Implementation Scheme 91: The compound of Formula 1 or any one of Implementation Schemes 1 to 90, wherein each R 4a and R 4b It exists independently.

[0312] Scheme 92: A compound of Formula 1 or any one of Schemes 1 to 91, wherein a pair of R atoms attached to the same carbon atom 4a and R 4b Substituents are combined to form a ring, which is a cyclopropyl ring optionally substituted with up to two substituents, the substituents being independently selected from halogens, methyl, methoxy, and methylthio.

[0313] Implementation Scheme 93: The compound described in Implementation Scheme 92, wherein a pair of R atoms attached to the same carbon atom 4a and R 4b The substituents are combined to form a cyclopropyl ring.

[0314] Implementation Scheme 94: The compound of Formula 1 or any one of Implementation Schemes 1 to 93, wherein each R 5 It is independently a cyano, halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy.

[0315] Implementation Scheme 95: The compound described in Implementation Scheme 94, wherein each R 5 It is independently a cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy.

[0316] Implementation Scheme 96: The compound described in Implementation Scheme 95, wherein each R 5 It can be cyano, halogen, methyl, or methoxy on its own.

[0317] Implementation Scheme 97: The compound described in Implementation Scheme 96, wherein each R 5 It can be methyl or methoxy on its own.

[0318] Implementation Scheme 98: The compound of Formula 1 or any one of Implementation Schemes 1 to 97, wherein each R 6 It can be H, cyano, halogen, methyl, or methoxy.

[0319] Implementation Scheme 99: The compound described in Implementation Scheme 98, wherein each R 6 It can be H, Cl, or methyl independently.

[0320] Implementation Scheme 100: The compound described in Implementation Scheme 99, wherein each R6 It can be H or methyl on its own.

[0321] Implementation Scheme 101: The compound of Implementation Scheme 100, wherein each R 6 For H.

[0322] Implementation Scheme 102: The compound of Formula 1 or any one of Implementation Schemes 1 to 101, wherein each R 7 Independently hydroxyl, NR 11a R 11b C1-C4 alkoxy, C2-C4 olefin, C2-C4 alkyl carbonyloxy, or C2-C4 alkoxycarbonyloxy.

[0323] Implementation Scheme 103: The compound described in Implementation Scheme 102, wherein each R 7 Independently hydroxyl, NR 11a R 11b Or C1-C2 alkoxy group.

[0324] Implementation Scheme 104: The compound described in Implementation Scheme 103, wherein each R 7 Independently hydroxyl, NR 11a R 11b Or methoxy.

[0325] Implementation Scheme 105: The compound described in Implementation Scheme 104, wherein each R 7 It is a hydroxyl group.

[0326] Implementation Scheme 106: The compound of Formula 1 or any one of Implementation Schemes 1 to 101, wherein each R 7 Independently hydroxyl or NR 11a R 11b ; or C1-C4 alkoxy, C2-C4 alkenoxy, C2-C4 alkynoxy or C2-C4 alkyl carbonyloxy, each optionally substituted with at most one substituent selected from cyano, hydroxy and -C(=O)OH.

[0327] Implementation Scheme 107: The compound described in Implementation Scheme 106, wherein each R 7 It is independently a C1-C4 alkoxy, C2-C4 alkenoxy, or C2-C4 alkynoxy, each optionally substituted by at most one substituent selected from cyano, hydroxy, and -C(=O)OH.

[0328] Implementation Scheme 108: The compound described in Implementation Scheme 107, wherein each R 7 It is independently C1-C4 alkoxy, C2-C4 alkenoxy, or C2-C4 alkynoxy.

[0329] Implementation Scheme 109: The compound of Formula 1 or any one of Implementation Schemes 1 to 108, wherein each R 8 It can be H, methyl, or methoxy on its own.

[0330] Implementation Scheme 110: The compound described in Implementation Scheme 109, wherein each R 8 It can be H or methyl on its own.

[0331] Implementation Scheme 111: The compound described in Implementation Scheme 110, wherein each R 8 For H.

[0332] Implementation Scheme 112: The compound of Formula 1 or any one of Implementation Schemes 1 to 111, wherein when each R 9a and R 9b When they are independent (i.e., not grouped together), then each R 9a and R 9b It can be H, methyl, or ethyl independently.

[0333] Implementation Scheme 113: The compound described in Implementation Scheme 112, wherein each R 9a and R 9b It can be H or methyl on its own.

[0334] Scheme 114: The compound of Formula 1 or any one of Schemes 1 to 113, wherein a pair of R 9a and R 9b When substituents are combined with the nitrogen atom to which they are attached to form a fully saturated heterocycle of 5 to 6 members, the ring contains ring members selected from carbon atoms and at most one heteroatom, in addition to the connecting nitrogen atom, the ring members being selected from at most one O atom, at most one S atom and at most one N atom, each ring optionally being substituted by at most two methyl groups.

[0335] Implementation Scheme 115: The compound described in Implementation Scheme 114, wherein a pair of R 9a and R 9b Substituents combine with the nitrogen atom to which they are attached to form a nitrogen heterocyclic butyl ring, morpholinyl ring, pyrrolidinyl ring, piperidinyl ring, piperazinyl ring, or thiomorpholinyl ring, each ring optionally being substituted with up to two methyl groups.

[0336] Implementation Scheme 116: The compound of Formula 1 or any one of Implementation Schemes 1 to 115, wherein each R 10It can be independently a halogen, cyano, hydroxyl, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl.

[0337] Implementation Scheme 117: The compound described in Implementation Scheme 116, wherein each R 10 It can be independently a halogen, cyano, hydroxyl, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkoxyalkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 haloalkylsulfonyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminocarbonyl, or C3-C5 dialkylaminocarbonyl.

[0338] Implementation Scheme 118: The compound described in Implementation Scheme 117, wherein each R 10 It can be independently a halogen, hydroxyl, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminocarbonyl, or C3-C5 dialkylaminocarbonyl.

[0339] Implementation Scheme 119: The compound of Formula 1 or any one of Implementation Schemes 1 to 115, wherein each R 10 Independently, it is halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C 15 Trialkylsilyl or -C(R) 13 ) = NOR 14 .

[0340] Implementation Scheme 120: The compound described in Implementation Scheme 119, wherein each R 10 Independently, it is a halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, or -C(R) 13 ) = NOR 14 .

[0341] Implementation Scheme 121: The compound described in Implementation Scheme 120, wherein each R 10 Independently, it is a halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl, C2-C5 alkoxy carbonyl, or -C(R) 13 ) = NOR 14 .

[0342] Implementation Scheme 122: The compound described in Implementation Scheme 121, wherein each R 10 It is independently a halogen, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl, C2-C5 alkoxy carbonyl or -C(R 13 ) = NOR 14 .

[0343] Implementation Scheme 123: The compound described in Implementation Scheme 122, wherein each R 10 It is independently a halogen, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl or C2-C5 alkoxy carbonyl.

[0344] Scheme 124: A compound of Formula 1 or any one of Schemes 1 to 123, wherein each U is independently a direct bond, C(=O)O, or C(=O)NR. 17 .

[0345] Implementation Scheme 125: The compound described in Implementation Scheme 124, wherein each U is a direct bond.

[0346] Implementation Scheme 126: The compound described in Implementation Scheme 125, wherein each U is independently C(=O)O or C(=O)NR. 17 .

[0347] Scheme 127: A compound of Formula 1 or any one of Schemes 1 to 126, wherein each V is independently a direct bond; or a C1-C6 alkylene, C2-C6 alkenylene, or C3-C6 alkynylene, each optionally substituted by up to two substituents independently selected from halogens, cyano, nitro, hydroxyl, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy.

[0348] Implementation Scheme 128: The compound of Implementation Scheme 127, wherein each V is independently a direct bond; or a C1-C3 alkylene, C2-C4 alkenylene, or C3-C4 alkyneene, each optionally substituted by up to two substituents independently selected from halogens, hydroxyl groups, C1-C2 alkyl groups, C1-C2 alkoxy groups, and C1-C2 haloalkoxy groups.

[0349] Implementation Scheme 129: The compound described in Implementation Scheme 128, wherein each V is independently a direct bond, a C1-C3 alkylene group, a C2-C4 alkenyl group, or a C3-C4 alkynyl group.

[0350] Implementation Scheme 130: The compound described in Implementation Scheme 129, wherein each V is independently a direct bond, a C1-C3 alkylene group, or a C2-C4 alkenyl group.

[0351] Implementation Scheme 131: The compound described in Implementation Scheme 130, wherein each V is a direct bond.

[0352] Implementation Scheme 132: The compound described in Implementation Scheme 130, wherein each V is independently a C1-C3 alkylene group.

[0353] Scheme 133: A compound of Formula 1 or any one of Schemes 1 to 132, wherein each Q is independently phenyl and is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 Or a 5- or 6-membered heteroaromatic ring, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R 12 Or a 3- to 7-membered non-aromatic heterocycle, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R 12 .

[0354] Implementation Scheme 134: The compound of Implementation Scheme 133, wherein each Q is independently phenyl and is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ; or pyridyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl, thiophene, isoxazolinyl, piperidinyl, morpholinyl, or piperazine, each ring optionally substituted with up to two substituents, said substituents being independently selected from R 12 .

[0355] Embodiment 135: The compound of Embodiment 134, wherein each Q is independently phenyl and is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ; or pyridyl, pyrazolyl, imidazole, triazolyl, thiazolyl, or oxazolyl, each ring optionally substituted by up to two substituents, said substituents being independently selected from R 12 .

[0356] Implementation Scheme 136: The compound of Implementation Scheme 135, wherein each Q is independently phenyl and is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ; or pyridyl or pyrazolyl, each ring optionally substituted with up to two substituents, said substituents being independently selected from R 12 .

[0357] Implementation Scheme 137: The compound of Formula 1 or any one of Implementation Schemes 1 to 136, wherein each R 11a It is independent (i.e., not related to R) 11b (combined together), then each R 11a It is independently H, C1-C2 alkyl or C2-C3 alkyl carbonyl.

[0358] Implementation Scheme 138: The compound described in Implementation Scheme 137, wherein each R 11a It can be H, methyl, or methyl carbonyl.

[0359] Implementation Scheme 139: The compound of Formula 1 or any one of Implementation Schemes 1 to 138, wherein each R 11b It is independent (i.e., not related to R) 11a (combined together), then each R 11b It can be independently H, cyano, C1-C2 alkyl, C2-C4 alkyl carbonyl, C2-C4 alkoxy carbonyl, C3-C5 alkoxy carbonyl alkyl, C2-C5 alkylamino carbonyl or C3-C5 dialkylamino carbonyl.

[0360] Implementation Scheme 140: The compound described in Implementation Scheme 139, wherein each R 11bIt can be independently H, cyano, methyl, methyl carbonyl, methoxy carbonyl, methoxy carbonylmethyl, methylamino carbonyl, or dimethylamino carbonyl.

[0361] Implementation Scheme 141: The compound described in Implementation Scheme 140, wherein each R 11b It can be H, methyl, methyl carbonyl or methoxy carbonyl independently.

[0362] Scheme 142: The compound of Formula 1 or any one of Schemes 1 to 141, wherein a pair of R 11a and R 11b When substituents are combined with the nitrogen atom to which they are attached to form a fully saturated heterocycle of 5 to 6 members, the ring contains ring members selected from carbon atoms and at most one heteroatom, in addition to the connecting nitrogen atom, the ring members being selected from at most one O atom, at most one S atom and at most one N atom, each ring optionally being substituted by at most two methyl groups.

[0363] Implementation Scheme 143: The compound described in Implementation Scheme 142, wherein a pair of R 11a and R 11b Substituents combine with the nitrogen atom to which they are attached to form a nitrogen heterocyclic butyl ring, morpholinyl ring, pyrrolidinyl ring, piperidinyl ring, piperazinyl ring, or thiomorpholinyl ring, each ring optionally being substituted with up to two methyl groups.

[0364] Implementation Scheme 144: The compound of Formula 1 or any one of Implementation Schemes 1 to 143, wherein each R 12 It is independently a halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy.

[0365] Implementation Scheme 145: The compound described in Implementation Scheme 144, wherein each R 12 It is independently a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy.

[0366] Implementation Scheme 146: The compound described in Implementation Scheme 145, wherein each R 12 It is independently a halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl or C1-C2 alkoxy.

[0367] Implementation Scheme 147: The compound described in Implementation Scheme 146, wherein each R 12 It can be halogen, methyl, or methoxy on its own.

[0368] Implementation Scheme 148: The compound of Formula 1 or any one of Implementation Schemes 1 to 147, wherein each R 13 and R 15It can be independently H, cyano, halogen, methyl, halomethyl or methoxy.

[0369] Implementation Scheme 149: The compound described in Implementation Scheme 148, wherein each R 13 and R 15 It can be H, halogen, methyl or methoxy independently.

[0370] Implementation Scheme 150: The compound described in Implementation Scheme 149, wherein each R 13 and R 15 For H. Embodiment 151: The compound of formula 1 or any one of embodiments 1 to 150, wherein each R 14 It can be H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkyl carbonyl or C2-C5 alkoxy carbonyl.

[0371] Implementation Scheme 152: The compound described in Implementation Scheme 151, wherein each R 14 It can be independently H, C1-C2 alkyl, C1-C2 haloalkyl, C2-C4 alkenyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

[0372] Implementation Scheme 153: The compound described in Implementation Scheme 152, wherein each R 14 It can be independently H, methyl, halomethyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

[0373] Implementation Scheme 154: The compound of Formula 1 or any one of Implementation Schemes 1 to 153, wherein each R 16 It can be independently H, cyano, methyl, halomethyl, methoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

[0374] Implementation Scheme 155: The compound described in Implementation Scheme 154, wherein each R 16 It can be H, cyano, methyl, halomethyl or methoxy.

[0375] Implementation Scheme 156: The compound described in Implementation Scheme 155, wherein each R 16 It can be H or methyl on its own.

[0376] Implementation Scheme 157: The compound described in Implementation Scheme 156, wherein each R 16 For H.

[0377] Implementation Scheme 158: The compound of Formula 1 or any one of Implementation Schemes 1 to 157, wherein each R 17 and R 18 It can be H, cyano, methyl, or halomethyl independently.

[0378] Embodiments of the present invention, including embodiments 1-158 described above and any other embodiments described herein, can be combined in any manner, and the description of variables in the embodiments relates not only to compounds of formula 1, but also to starting compounds and intermediate compounds that can be used to prepare compounds of formula 1. Furthermore, embodiments of the present invention, including embodiments 1-158 described above and any other embodiments described herein, and any combination thereof, relate to the compositions and methods of the present invention.

[0379] Combinations of implementation schemes 1-158 can be shown as follows:

[0380] Implementation Scheme A: The compound of Formula 1, wherein

[0381] R 1 Selected from U-1 to U-118

[0382]

[0383]

[0384]

[0385]

[0386]

[0387] The floating bond therein is connected to L in Formula 1 via any available carbon or nitrogen atom in the ring or ring system shown;

[0388] x is 0, 1, or 2;

[0389] L is O, (CR) 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O or CH2OCH2, each carbon atom is optionally substituted by up to 2 substituents, said substituents being independently selected from halogen, cyano, hydroxyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy;

[0390] J is selected from J-1 to J-93.

[0391]

[0392]

[0393]

[0394]

[0395] The bonds extending to the left are bonded to L, and the bonds extending to the right are bonded to the oxadiazole ring in Formula 1.

[0396] Each R 5a Independently for H or R 5 The prerequisite is that there are at most two R's. 5a The substituent is not H;

[0397] Each R 2 Independently halogen, cyano, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy, or C2-C6 alkylcarbonylamino, each optionally substituted with up to 3 substituents, said substituents being independently selected from R 10 ;

[0398] Each R 3a Independently, it can be H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C5 alkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C4-C6 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, or C3-C5 alkoxycarbonylalkyl;

[0399] Each R 3b Independently, H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 ynyl, C2-C6 haloynyl, C1-C6 hydroxyalkyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C4-C 10 Alkyl cycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 Halogenated cycloalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C4-C 10 The cycloalkoxyalkyl group is optionally substituted with at most one substituent selected from cyano, hydroxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C4 alkylcarbonyl, C4-C4 alkylcarbonyl, C5-C6 alkylcarbonyl, C6-C6 alkylcarbonyl, C7-C6 alkylcarbonyl, C8-C6 alkylcarbonyl, C9-C9 ... 15 Trialkylsilyl and C3-C 15Halogenated trialkylsilyl; or

[0400] A pair of R atoms attached to the same nitrogen atom 3a and R 3b Substituents are combined to form an aza-butyl ring, a morpholinyl ring, a pyrrolidinyl ring, a piperidinyl ring, a piperazinyl ring, or a thiomorpholinyl ring, each ring optionally being substituted with up to two methyl groups;

[0401] Each R 4a and R 4b Independently, it is H, halogen, cyano, hydroxyl, methyl, or methoxy; or

[0402] A pair of R atoms attached to the same carbon atom 4a and R 4b The substituents are combined to form a cyclopropyl ring, which is optionally substituted by up to two substituents, said substituents being independently selected from halogen, methyl, methoxy or methylthio;

[0403] Each R 5 It is independently a cyano, halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy;

[0404] Each R 6 Independently, it can be H, cyano, halogen, methyl, or methoxy.

[0405] Each R 7 Independently hydroxyl or NR 11a R 11b ; or C1-C4 alkoxy, C2-C4 alkenoxy, C2-C4 alkynoxy or C2-C4 alkyl carbonyloxy, each optionally substituted by at most one substituent selected from cyano, hydroxy and -C(=O)OH;

[0406] Each R 10 Independently, it is halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C 15 Trialkylsilyl or -C(R) 13 ) = NOR 14 ;

[0407] Each U is independently a direct bond, C(=O)O, or C(=O)NR. 17 ;

[0408] Each V is independently a direct bond; or a C1-C6 alkylene, C2-C6 alkenylene, or C3-C6 ynylene, each optionally substituted by up to two substituents independently selected from halogens, cyano, nitro, hydroxyl, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy.

[0409] Each Q is independently phenyl, and each is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ; or pyridyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl, thiophene, isoxazolinyl, piperidinyl, morpholinyl, or piperazine, each ring optionally substituted with up to two substituents, said substituents being independently selected from R 12 ;

[0410] Each R 11a It is independently H, C1-C2 alkyl, or C2-C3 alkyl carbonyl;

[0411] Each R 11b Independently, it is H, cyano, C1-C2 alkyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl, or C3-C5 dialkylaminocarbonyl; or

[0412] A pair of R 11a and R 11b Substituents combine with the nitrogen atom to which they are attached to form a nitrogen heterocyclic butyl ring, morpholinyl ring, pyrrolidinyl ring, piperidinyl ring, piperazinyl ring, or thiomorpholinyl ring, each ring optionally being substituted with up to two methyl groups;

[0413] Each R 12 It is independently a halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy;

[0414] Each R 13 Independently, it can be H, cyano, halogen, methyl, halomethyl, or methoxy.

[0415] Each R 14 It is H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 alkylcarbonyl, or C2-C5 alkoxycarbonyl; and

[0416] Each R 17 It can be H, cyano, methyl, or halomethyl independently.

[0417] Implementation Scheme B: The compound of Implementation Scheme A, wherein

[0418] R 1is U-1, U-2, U-4, U-5, U-8, U-12, U-29, U-58, U-69, U-79, U-80, U-104, U-115, U-116, U-117 or U-118;

[0419] L is (CR) 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O or CH2OCH2;

[0420] J is J-4, J-18, J-27, J-40, J-41, J-63, J-73 or J-93;

[0421] Each R 2 Independently halogen, cyano, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy, or C2-C6 alkylcarbonylamino, each optionally substituted with up to two substituents, said substituents being independently selected from R 10 ;

[0422] Each R 3a Independently, it is H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl or C3-C5 alkoxycarbonylalkyl;

[0423] Each R 3b Independently, it is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 ynyl, C2-C6 haloynyl, C3-C8 halocycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 The alkyl halocycloalkyl, C2-C6 alkoxyalkyl, or C2-C6 haloalkoxyalkyl group is optionally substituted with at most one substituent selected from cyano, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, and C3-C6 alkylcarbonyl. 15 Trialkylsilyl;

[0424] Each R 4a and R 4b Independently, it can be H, halogen, hydroxyl, methyl, or methoxy.

[0425] Each R 5 It can be methyl or methoxy independently;

[0426] Each R 6 Independently, it is either H or methyl;

[0427] Each R 7 It is independently a C1-C4 alkoxy, C2-C4 alkenoxy, or C2-C4 alkynoxy, each optionally substituted by at most one substituent selected from cyano, hydroxy, and -C(=O)OH;

[0428] Each R 10 Independently, it is a halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, or -C(R) 13 ) = NOR 14 ;

[0429] Each V is independently a direct bond, a C1-C3 alkylene group, a C2-C4 alkenyl group, or a C3-C4 ynylene group;

[0430] Each R 12 It is independently a halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl or C1-C2 alkoxy;

[0431] Each R 13 Independently H, halogen, methyl, or methoxy; and

[0432] Each R 14 It can be independently H, C1-C2 alkyl, C1-C2 haloalkyl, C2-C4 alkenyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

[0433] Implementation Scheme C: The compound described in Implementation Scheme B, wherein

[0434] R 1 Is U-1, U-2, U-12, or U-29;

[0435] L is (CR) 4a R 4b ) n ;

[0436] J can be J-27, J-40, or J-63;

[0437] Each R 2 Independently -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C2-C6 alkoxycarbonyl, C3-C6 alkenoxycarbonyl, or C3-C6 alkynoxycarbonyl, each optionally substituted with at most one substituent selected from R 10 ;

[0438] Each R 3a Independently, it is H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl or C3-C5 alkoxycarbonylalkyl;

[0439] Each R 3b Independently, it is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 ynyl, C2-C6 haloynyl, C4-C 10 cycloalkylalkyl, C4-C 10 The halocycloalkylalkyl, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl groups are each optionally substituted with at most one substituent selected from C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl groups;

[0440] Each R 4a and R 4b Independently, it is either H or methyl;

[0441] Each R 6 H is independent;

[0442] Each R 7 It is independently C1-C4 alkoxy, C2-C4 alkenoxy, or C2-C4 alkynoxy;

[0443] Each R 10 Independently, it is a halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl, C2-C5 alkoxy carbonyl, or -C(R) 13 ) = NOR 14 ;

[0444] Each V is independently a direct bond, a C1-C3 alkylene group, or a C2-C4 alkenyl group;

[0445] Each Q is independently phenyl, and each is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ; or pyridyl, pyrazolyl, imidazole, triazolyl, thiazolyl, or oxazolyl, each ring optionally substituted with up to two substituents, said substituents being independently selected from R 12 ;

[0446] Each R 12 Independently halogenated, methyl, or methoxy; and

[0447] Each R 14 It can be independently H, methyl, halomethyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

[0448] Implementation Scheme D: The compound described in Implementation Scheme C, wherein

[0449] R 1 It is either U-2 or U-12;

[0450] J is either J-40 or J-63;

[0451] R 5a For H;

[0452] Each R 2 Independently -C(=O)NR 3a R 3b ; or a C2-C6 alkoxycarbonyl group, optionally substituted with at most one substituent selected from R 10 ;

[0453] Each R 3a Independently, it is H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxyalkyl, or C3-C5 alkoxycarbonylalkyl;

[0454] Each R 3b Independently, it is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, or C2-C6 haloalkenyl, each optionally substituted by at most one substituent selected from C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl; and

[0455] Each R 10 It is independently a halogen, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl or C2-C5 alkoxy carbonyl.

[0456] Implementation Scheme E: The compound described in Implementation Scheme D, wherein

[0457] R 1 To connect U-2 to L at its 2nd position; or

[0458] R 1 U-12 is connected to L at its 1st position;

[0459] Each R 2 Independently -C(=O)NR 3a R 3b Or C2-C6 alkoxycarbonyl; and

[0460] n is 1.

[0461] Implementation scheme F: a compound of formula 1, wherein

[0462] R 1 A benzene ring optionally substituted with up to 3 substituents, said substituents being independently selected from R 2 ;or

[0463] R 1 It is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 3 substituents, wherein the substituents are independently selected from R 2 The prerequisite is R. 1 Linked to L via a carbon atom ring member;

[0464] J is

[0465]

[0466] The bonds extending to the left are bonded to L, and the bonds extending to the right are bonded to the oxadiazole ring in Formula 1.

[0467] Each R 5a Independently for H or R 5 The prerequisite is that there are at most two R's. 5a The substituent is not H; and

[0468] n is 3.

[0469] Implementation scheme G: a compound of formula 1, wherein

[0470] R 1 A benzene ring optionally substituted with up to 3 substituents, said substituents being independently selected from R 2 ;or

[0471] R 1It is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 3 substituents, wherein the substituents are independently selected from R 2 ;and

[0472] Each R 2 Independently, it is a C5-C6 alkyl, C5-C6 alkenyl, C5-C6 alkoxy, C5-C6 alkenyloxy, or C5-C6 alkoxy, each optionally substituted with up to three substituents, said substituents being independently selected from R. 10 .

[0473] This invention provides antifungal compositions comprising a compound of formula 1 (including all its stereoisomers, N-oxides, hydrates, and salts) and at least one other antifungal agent. As embodiments of such compositions, compositions comprising compounds corresponding to any of the above-described compound embodiments are noteworthy.

[0474] This invention provides an antifungal composition comprising a compound of Formula 1 (including all its stereoisomers, N-oxides, hydrates, and salts) (i.e., in an effective antifungal amount) and at least one additional component selected from: surfactants, solid diluents, and liquid diluents. As embodiments of such compositions, compositions comprising compounds corresponding to any of the above-described compound embodiments are noteworthy.

[0475] This invention provides a method for controlling plant diseases caused by fungal plant pathogens, the method comprising applying to a plant or parts thereof, or to plant seeds, a fungicide-effective amount of a compound of formula 1 (including all its stereoisomers, N-oxides, hydrates, and salts). As an embodiment of such a method, it is noteworthy that it includes methods comprising applying a fungicide-effective amount of a compound corresponding to any of the above-described compound embodiments. Particularly noteworthy are embodiments in which the compound is applied as a composition of this invention.

[0476] It is noteworthy that compounds of Formula 1, which are compounds of Formula 1G (including all geometric and stereoisomers), N-oxides, hydrates, and salts, as well as agricultural compositions containing them and their use as fungicides, are included.

[0477]

[0478] in

[0479] R 1A benzene ring optionally substituted with up to 3 substituents, said substituents being independently selected from R 2 ;or

[0480] R 1 It is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 3 substituents, wherein the substituents are independently selected from R 2 ;or

[0481] R 1 It is a 3- to 7-membered non-aromatic ring or an 8- to 11-membered bicyclic ring system, each ring or ring system comprising a ring member selected from carbon atoms and optionally up to 4 heteroatoms, wherein the heteroatoms are independently selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms, wherein the up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, and each ring or ring system is optionally substituted by up to 3 substituents, wherein the substituents are independently selected from R2;

[0482] L represents O, NR 3 NR 3 CH2, CH2NR 3 NR 3 CH2CH2, CH2CH2NR 3 、(CR 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O, or CH2OCH2, where the atom on the left is attached to R. 1 And the atom on the right is attached to J, and each carbon atom is optionally substituted by up to 2 substituents, which are independently selected from halogen, cyano, hydroxy, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

[0483] J is

[0484] or

[0485] The bonds extending to the left are bonded to L, and the bonds extending to the right are bonded to the oxadiazole ring in Formula 1.

[0486] Each R 5a Independently for H or R 5 ;

[0487] Each R 2Independently, it can be halogen, cyano, hydroxyl, nitro, thioyl, -SF5, -CH(=O), -C(=O)OH, or -NR. 3a R 3b -C(=O)NR 3a R 3b -C(=O)C(=O)NR 3a R 3b -C(=S)NR 3a R 3b -C(R) 6 ) = NR 7 -N=CR 8 NR 9a R 9b Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminosulfinyl, C2-C6 dialkylaminosulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl The group consists of a C4-C7 cycloalkoxycarbonyl group, a C3-C6 alkoxycarbonylcarbonyl group, a C2-C6 alkylcarbonyloxy group, a C4-C7 cycloalkylcarbonyloxy group, a C2-C6 alkoxycarbonyloxy group, a C4-C7 cycloalkoxycarbonyloxy group, a C2-C6 alkylaminocarbonyloxy group, a C4-C7 cycloalkylaminocarbonyloxy group, a C2-C6 alkylcarbonylamino group, a C4-C7 cycloalkylcarbonylamino group, a C2-C6 alkoxycarbonylamino group, a C4-C7 cycloalkoxycarbonylamino group, a C2-C6 alkylaminocarbonylamino group, a C4-C7 cycloalkylaminocarbonylamino group, or a C2-C6 diekoxyphosphonoyl group, each optionally substituted with up to three substituents, said substituents being independently selected from R. 10 ;

[0488] Each R 3 and R 3aIndependently, it can be H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C5 alkoxy, C2-C4 alkoxyalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylthioalkyl, 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 dialkylaminocarbonyl;

[0489] Each R 3b Independently, it can be H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C4-C 10 Alkyl cycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 Halogenated cycloalkyl alkyl, C6-C 14 cycloalkyl, C5-C 10 Alkylcycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C4-C 10 Cycloalkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfinylalkyl, C2-C6 alkylsulfonylalkyl, C2-C6 alkylaminoalkyl, C2-C6 haloalkylaminoalkyl, C3-C8 dialkylaminoalkyl or C4-C 10 Cycloalkylaminoalkyl groups, each optionally substituted with at most one substituent selected from cyano, hydroxy, nitro, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C4 alkylcarbonyl, C4-C4 alkylcarbonyl, C5-C6 alkylcarbonyl, C6-C6 alkylcarbonyl, C7-C6 alkylcarbonyl, C8-C6 alkylcarbonyl, C9-C9 alkylcarbonyl, C9-C 15 Trialkylsilyl and C3-C 15 Halogenated trialkylsilyl; or

[0490] A pair of R 3a and R 3b Substituents are combined with the nitrogen atom to which they are attached to form a 4- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to two heteroatoms in addition to the connecting nitrogen atom. The heteroatoms are independently selected from up to two O atoms, up to two S atoms, and up to two N atoms. Each ring is optionally substituted by up to three substituents, which are independently selected from halogens and C1-C3 alkyl groups.

[0491] Each R 4a and R 4b Independently, it is H, halogen, cyano, hydroxyl, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy; or

[0492] A pair of R atoms attached to the same carbon atom 4a and R 4b The substituents are combined to form a C3-C5 cycloalkyl ring, which is optionally substituted by up to two substituents, said substituents being independently selected from halogen, methyl, methoxy and methylthio;

[0493] Each R 5 It can be independently hydroxyl, cyano, nitro, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl or C1-C4 alkoxy;

[0494] Each R 6 It can be independently H, cyano, halogen, methyl, methoxy, methylthio, or methoxycarbonyl;

[0495] Each R 7 Independently hydroxyl or NR 11a R 11b ; or C1-C4 alkoxy, C2-C4 alkenoxy, C2-C4 alkynoxy, C2-C4 alkyl carbonyloxy, C2-C5 alkoxy carbonyloxy, C2-C5 alkylamino carbonyloxy or C3-C5 dialkylamino carbonyloxy, each optionally substituted with at most one substituent selected from halogen, cyano, hydroxyl and -C(=O)OH;

[0496] Each R 8 It can be independently H, methyl, methoxy, or methylthio;

[0497] Each R 9a and R 9b Independently H or C1-C4 alkyl; or

[0498] A pair of R 9a and R 9b Substituents are combined with the nitrogen atom to which they are attached to form a 5- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms in addition to the connecting nitrogen atom, the ring member being independently selected from up to 2 O atoms, up to 2 S atoms and up to 2 N atoms, each ring optionally being substituted by up to 2 methyl groups;

[0499] Each R 10Independently, it is a halogen, amino, cyano, hydroxyl, nitro, thioyl, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C1-C6 alkylamino, C2-C6 dialkylamino, C2-C5 alkylaminocarbonyl, C3-C5 dialkylaminocarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C 15 Trialkylsilyl, C3-C 15 Halogenated trialkylsilyl, -C(R) 13 ) = NOR 14 or -C(R) 15 ) = NR 16 ;

[0500] Each U is independently a direct bond, C(=O)O, C(=O)NR. 17 Or C(=S)NR 18 The atom on the left is connected to R. 1 And the atom on the right is connected to V;

[0501] Each V is independently a direct bond; or a C1-C6 alkylene, C2-C6 alkenylene, C3-C6 ynylene, C3-C6 cycloalkylene, or C3-C6 cycloalkenylene, each optionally substituted by up to three substituents independently selected from halogens, cyano, nitro, hydroxyl, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy.

[0502] Each Q is independently phenyl or phenoxy, and each is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ;or

[0503] Each Q is independently a 5- to 6-membered heteroaromatic ring, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R. 12 ;or

[0504] Each Q is independently a 3- to 7-membered non-aromatic heterocycle, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R. 12 ;

[0505] Each R 11a Independently, it is H, C1-C4 alkyl, or C2-C4 alkyl carbonyl;

[0506] Each R 11b Independently, it is H, cyano, C1-C5 alkyl, C2-C5 alkylcarbonyl, C2-C5 haloalkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl, or C3-C5 dialkylaminocarbonyl; or

[0507] A pair of R 11a and R 11b Substituents are combined with the nitrogen atom to which they are attached to form a 5- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms in addition to the connecting nitrogen atom, the ring member being independently selected from up to 2 O atoms, up to 2 S atoms and up to 2 N atoms, each ring optionally being substituted by up to 2 methyl groups;

[0508] Each R 12 It can be independently a halogen, cyano, hydroxyl, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl or C2-C4 alkoxy carbonyl;

[0509] Each R 13 and R 15 The benzene ring is independently H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl or C1-C3 alkoxy; or optionally substituted with up to 2 substituents, said substituents being independently selected from halogen and C1-C3 alkyl;

[0510] Each R 14 Independently, it is H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 ynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C5 alkylcarbonyl, or C2-C5 alkoxycarbonyl; or

[0511] Each R 14The benzene ring is optionally substituted with up to two substituents, the substituents being independently selected from halogens and C1-C3 alkyl groups; or a 5- to 6-membered fully saturated heterocycle, each ring comprising a ring member selected from carbon atoms and up to two heteroatoms, the heteroatoms being independently selected from up to two O atoms, up to two S atoms and up to two N atoms, each ring optionally substituted with up to two substituents, the substituents being independently selected from halogens and C1-C3 alkyl groups;

[0512] Each R 16 It can be independently H, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C4 alkoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;

[0513] Each R 17 and R 18 Independently, it is H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C4 alkoxycarbonyl, or C2-C4 haloalkoxycarbonyl; and

[0514] n is 1, 2, or 3;

[0515] Therefore, it is noteworthy that compounds selected from Formula 1G as defined above (including all geometric and stereoisomers), its N-oxides, hydrates, and salts are included. Also noteworthy are the corresponding embodiments of embodiments 1 to 158 and embodiments A to F, wherein in these corresponding embodiments, “Formula 1” is replaced by “Formula 1G”, and the scope of these corresponding embodiments does not exceed the scope defined above for Formula 1G. Examples of combinations of embodiments 1 to 158 applicable to Formula 1G, and any other embodiments described herein, are embodiments AG and BG below.

[0516] Implementation scheme AG: a compound of formula 1G, wherein

[0517] R 1 is U-1, U-2, U-4, U-5, U-8, U-12, U-29, U-58, U-69, U-79, U-104, U-115, U-116, U-117 or U-118;

[0518] The floating bond therein is connected to L in Formula 1 via any available carbon or nitrogen atom in the ring or ring system shown;

[0519] x is 0, 1, or 2;

[0520] L is (CR) 4a R 4b ) n ;

[0521] J is J-40;

[0522] R 5a For H;

[0523] Each R 2 Independently halogen, cyano, -CH(=O), -C(=O)OH, -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl or C4-C7 cycloalkoxycarbonyl, each optionally substituted with at most one substituent, said substituent being independently selected from R 10 ;

[0524] Each R 3a Independently, it is H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C5 alkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl or C3-C5 alkoxycarbonylalkyl;

[0525] Each R 3b Independently, it is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 ynyl, C2-C6 haloynyl, C3-C8 halocycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 The alkyl halocycloalkyl, C2-C6 alkoxyalkyl, and C2-C6 haloalkoxyalkyl groups are each optionally substituted with at most one substituent selected from cyano, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, and C3-C6 alkylcarbonyl groups. 15 Trialkylsilyl;

[0526] Each R 6 H is independent;

[0527] Each R 7 It is independently C1-C4 alkoxy, C2-C4 alkenoxy, or C2-C4 alkynoxy;

[0528] Each R 10 Independently, it is a halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl, C2-C5 alkoxy carbonyl, or -C(R) 13 ) = NOR 14 ;

[0529] Each U is independently a direct bond, C(=O)O, or C(=O)NR. 17 ;

[0530] Each V is independently a C1-C3 alkylene group;

[0531] Each Q is independently phenyl, and each is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ; or pyridyl, pyrazolyl, imidazole, triazolyl, thiazolyl, or oxazolyl, each ring optionally substituted with up to two substituents, said substituents being independently selected from R 12 ;

[0532] Each R 12 It is independently a halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl or C1-C2 alkoxy;

[0533] Each R 13 Independently H, halogen, methyl or methoxy;

[0534] Each R 14 It is H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 alkylcarbonyl, or C2-C5 alkoxycarbonyl; and

[0535] Each R 17 It can be H, cyano, methyl, or halomethyl independently.

[0536] Implementation Scheme BG: The compound described in Implementation Scheme AG, wherein

[0537] R 1 It is either U-2 or U-12;

[0538] Each R 2 Independently -C(=O)NR 3a R 3b ; or a C2-C6 alkoxycarbonyl group, optionally substituted with at most one substituent selected from R 10 ;

[0539] Each R 3a Independently, it is H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxyalkyl, or C3-C5 alkoxycarbonylalkyl;

[0540] Each R 3b It can be independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl or C2-C4 haloalkenyl;

[0541] Each R 10Independently, it is a halogen, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl, or C2-C5 alkoxy carbonyl; and

[0542] n is 1.

[0543] Also noteworthy are the fungicidal compositions comprising a fungicide-effective amount of a compound of formula 1G (including all its geometric and stereoisomers, N-oxides, and salts) or as any of the corresponding embodiments of embodiments 1 to 158 and embodiments A to F (e.g., embodiments AG and BG), and at least one additional component selected from: surfactants, solid diluents, and liquid diluents. Also noteworthy are methods for controlling plant diseases caused by fungal plant pathogens, comprising applying to a plant or parts thereof, or to plant seeds, a fungicide-effective amount of a compound of formula 1G (including all its geometric and stereoisomers, N-oxides, and salts) or any of the corresponding embodiments. Particularly noteworthy are embodiments in which a compound of formula 1G is applied as a composition of the present invention.

[0544] Also noteworthy are compounds of Formula 1, which are compounds of Formula 1P (including all geometric and stereoisomers), N-oxides, hydrates, and salts, as well as agricultural compositions containing them and their use as fungicides:

[0545]

[0546] in

[0547] R 1 A benzene ring optionally substituted with up to 3 substituents, said substituents being independently selected from R 2 ;or

[0548] R 1 It is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 3 substituents, wherein the substituents are independently selected from R 2 ; or ; the prerequisite is R 1 Linked to L via a carbon atom ring member;

[0549] L represents O, NR 3 NR 3 CH2, CH2NR 3 NR 3 CH2CH2, CH2CH2NR3 、(CR 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O, or CH2OCH2, where the atom on the left is attached to R. 1 And the atom on the right is attached to J, and each carbon atom is optionally substituted by up to 2 substituents, which are independently selected from halogen, cyano, hydroxy, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

[0550] J is

[0551]

[0552] The bonds extending to the left are bonded to L, and the bonds extending to the right are bonded to the oxadiazole ring in Formula 1.

[0553] Each R 5a Independently for H or R 5 The prerequisite is that there are at most two R's. 5a The substituent is not H;

[0554] Each R 2 Independently for -NR 3a R 3b -C(=O)NR 3a R 3b -C(R) 6 ) = NR 7 Or -UVQ; or C3-C6 olefinic carbonyl or C3-C6 alkynyl carbonyl, each optionally substituted with up to 3 substituents, said substituents being independently selected from R 10 .

[0555] Each R 3 and R 3a It is independently C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C5 alkoxy, C2-C4 alkoxyalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylthioalkyl, 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 dialkylaminocarbonyl;

[0556] Each R 3bIndependently, it is C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C4-C 10 Alkyl cycloalkyl, C4-C 10 cycloalkylalkyl, C4-C 10 Halogenated cycloalkyl, C6-C 14 cycloalkyl, C5-C 10 Alkylcycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C4-C 10 Cycloalkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfinylalkyl, C2-C6 alkylsulfonylalkyl, C2-C6 alkylaminoalkyl, C2-C6 haloalkylaminoalkyl, C3-C8 dialkylaminoalkyl or C4-C 10 Cycloalkylaminoalkyl groups, each optionally substituted with at most one substituent selected from cyano, hydroxy, nitro, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C4 alkylcarbonyl, C4-C4 alkylcarbonyl, C5-C4 alkylcarbonyl, C6-C4 alkylcarbonyl, C7-C8 alkylcarbonyl, C9-C ... 15 Trialkylsilyl and C3-C 15 Halogenated trialkylsilyl; or

[0557] A pair of R 3a and R 3b Substituents are combined with the nitrogen atom to which they are attached to form a 4- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to two heteroatoms in addition to the connecting nitrogen atom. The heteroatoms are independently selected from up to two O atoms, up to two S atoms, and up to two N atoms. Each ring is optionally substituted by up to three substituents, which are independently selected from halogens and C1-C3 alkyl groups.

[0558] Each R 4a and R 4b Independently, it is H, halogen, cyano, hydroxyl, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy, or C1-C2 haloalkoxy; or

[0559] A pair of R atoms attached to the same carbon atom 4a and R 4b The substituents are combined to form a C3-C5 cycloalkyl ring, which is optionally substituted by up to two substituents, said substituents being independently selected from halogens, methyl, methoxy and methylthio;

[0560] Each R 5It can be independently hydroxyl, cyano, nitro, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl or C1-C4 alkoxy;

[0561] Each R 6 It can be independently H, cyano, halogen, methyl, methoxy, methylthio, or methoxycarbonyl;

[0562] Each R 7 Independently hydroxyl or NR 11a R 11b ; or C1-C4 alkoxy, C2-C4 alkenoxy, C2-C4 alkynoxy, C2-C4 alkyl carbonyloxy, C2-C5 alkoxy carbonyloxy, C2-C5 alkylamino carbonyloxy or C3-C5 dialkylamino carbonyloxy, each optionally substituted with at most one substituent selected from halogen, cyano, hydroxyl and -C(=O)OH;

[0563] Each R 10 Independently, it is a halogen, amino, cyano, hydroxyl, nitro, thioyl, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C1-C6 alkylamino, C2-C6 dialkylamino, C2-C5 alkylaminocarbonyl, C3-C5 dialkylaminocarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C 15 Trialkylsilyl, C3-C 15 Halogenated trialkylsilyl, -C(R) 13 ) = NOR 14 or -C(R) 15 ) = NR 16 ;

[0564] Each U is independently a direct bond, C(=O)O, C(=O)NR. 17 Or C(=S)NR 18 The atom on the left is connected to R. 1 And the atom on the right is connected to V;

[0565] Each V is independently a direct bond; or a C1-C6 alkylene, C2-C6 alkenylene, C3-C6 ynylene, C3-C6 cycloalkylene, or C3-C6 cycloalkenylene, each optionally substituted by up to three substituents independently selected from halogens, cyano, nitro, hydroxyl, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy.

[0566] Each Q is independently phenyl or phenoxy, and each is optionally substituted by up to two substituents, said substituents being independently selected from R. 12 ;or

[0567] Each Q is independently a 5- to 6-membered heteroaromatic ring, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R. 12 ;or

[0568] Each Q is independently a 3- to 7-membered non-aromatic heterocycle, each ring comprising a ring member selected from carbon atoms and 1 to 4 heteroatoms, wherein the heteroatoms are independently selected from at most 2 O atoms, at most 2 S atoms, and at most 4 N atoms, wherein the at most 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, and each ring is optionally substituted by at most 2 substituents, wherein the substituents are independently selected from R. 12 ;

[0569] Each R 11a Independently, it is H, C1-C4 alkyl, or C2-C4 alkyl carbonyl;

[0570] Each R 11b Independently, it is H, cyano, C1-C5 alkyl, C2-C5 alkylcarbonyl, C2-C5 haloalkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl, or C3-C5 dialkylaminocarbonyl; or

[0571] A pair of R 11a and R 11b Substituents are combined with the nitrogen atom to which they are attached to form a 5- to 6-membered fully saturated heterocycle, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms in addition to the connecting nitrogen atom, the ring member being independently selected from up to 2 O atoms, up to 2 S atoms and up to 2 N atoms, each ring optionally being substituted by up to 2 methyl groups;

[0572] Each R 12 It can be independently a halogen, cyano, hydroxyl, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl or C2-C4 alkoxy carbonyl;

[0573] Each R 13 and R15 The benzene ring is independently H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl or C1-C3 alkoxy; or optionally substituted with up to 2 substituents, said substituents being independently selected from halogen and C1-C3 alkyl;

[0574] Each R 14 Independently, it is H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 ynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C5 alkylcarbonyl, or C2-C5 alkoxycarbonyl; or

[0575] Each R 14 The benzene ring is optionally substituted with up to two substituents, the substituents being independently selected from halogens and C1-C3 alkyl groups; or a 5- to 6-membered fully saturated heterocycle, each ring comprising a ring member selected from carbon atoms and up to two heteroatoms, the heteroatoms being independently selected from up to two O atoms, up to two S atoms and up to two N atoms, each ring optionally substituted with up to two substituents, the substituents being independently selected from halogens and C1-C3 alkyl groups;

[0576] Each R 16 It can be independently H, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C4 alkoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;

[0577] Each R 17 and R 18 Independently, it is H, cyano, hydroxyl, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C4 alkoxycarbonyl, or C2-C4 haloalkoxycarbonyl; and

[0578] n is 1, 2, or 3;

[0579] Therefore, it is noteworthy that compounds selected from Formula 1P as defined above (including all geometric and stereoisomers), its N-oxides, hydrates, and salts are included. Also noteworthy are the corresponding embodiments of embodiments 1 to 158 and embodiments A to F, wherein in these corresponding embodiments, “Formula 1” is replaced by “Formula 1P”, and the scope of these corresponding embodiments does not exceed the scope defined above for Formula 1P. Examples of combinations of embodiments 1 to 158 applicable to Formula 1P, and any other embodiments described herein, are embodiments AP and BP.

[0580] Implementation scheme AP: a compound of formula 1P, wherein

[0581] R 1 for

[0582]

[0583] The floating bond is connected to L in Formula 1 via any available carbon atom in the ring or ring system shown;

[0584] x is 0, 1, or 2;

[0585] L is (CR) 4a R 4b ) n OCH2, CH2O, OCH2CH2, CH2CH2O, or CH2OCH2, where the atom on the left is attached to R. 1 And the atom on the right is connected to J, and each carbon atom is optionally substituted by up to 2 substituents, which are independently selected from halogen, cyano, hydroxyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy;

[0586] R 5a For H; and

[0587] Each R 2 Independently -C(=O)NR 3a R 3b ; or C3-C6 olefinic carbonyl or C3-C6 alkynyl carbonyl, each optionally substituted by up to 3 substituents, said substituents being independently selected from R 10 .

[0588] Implementation Plan BP: The compound described in Implementation Plan AP, wherein...

[0589] R 1 It is either U-2 or U-12;

[0590] L is (CR) 4a R 4b ) n ;

[0591] Each R 2 Independently -C(=O)NR 3a R 3b ; or a C2-C6 alkoxycarbonyl group, optionally substituted with at most one substituent selected from R 10 ;

[0592] Each R 3a It is independently a C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkoxyalkyl, or C3-C5 alkoxycarbonylalkyl;

[0593] Each R 3b It is independently a C1-C3 haloalkyl, C2-C4 alkenyl or C2-C4 haloalkenyl;

[0594] Each R 10 Independently, it is a halogen, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl, or C2-C5 alkoxy carbonyl; and

[0595] n is 1.

[0596] Also noteworthy are the fungicidal compositions comprising a fungicide-effective amount of a compound of formula 1P (including all its geometric and stereoisomers, N-oxides, and salts) or as any of the corresponding embodiments of embodiments 1 to 158 and embodiments A to E (e.g., embodiments AP and BP), and at least one additional component selected from: surfactants, solid diluents, and liquid diluents. Also noteworthy are methods for controlling plant diseases caused by fungal plant pathogens, comprising applying to a plant or parts thereof, or to plant seeds, a fungicide-effective amount of a compound of formula 1P (including all its geometric and stereoisomers, N-oxides, and salts) or any of the corresponding embodiments. Particularly noteworthy are embodiments in which a compound of formula 1P is applied as a composition of the present invention.

[0597] One or more of the methods and variations described in Schemes 1-13 below can be used to prepare compounds of Formula 1. Unless otherwise stated, R in compounds of Formulas 1-21 below 1 R 2 The definitions of L and J are as defined in the invention description above. The compounds of formulas 1a, 1b, 1c, 3a, 6a and 6b are various subsets of formula 1, and all substituents of formulas 1a, 1b, 1c, 3a, 6a and 6b are as defined above for formula 1.

[0598] As shown in Scheme 1, the compound of Formula 1 can be prepared by reacting the amide oxime of Formula 2 with trifluoroacetic anhydride (TFAA) or an equivalent. In addition to the compound of Formula 2 and TFAA, the reaction can be carried out in a solvent-free environment. Typically, the reaction is carried out in a liquid phase with a solvent such as tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or toluene at a temperature between about 0 and 100 °C, optionally in the presence of a base such as pyridine or trimethylamine. The preparation of oxadiazole rings by this and other methods is known in the art; see, for example, Comprehensive Heterocyclic Chemistry, Vol. 6, Part 4B, pp. 365-391, edited by Kevin T. Potts, Pergamon Press, New York, 1984. The method of Scheme 1 is also shown in step C of Example 10 of the present invention.

[0599] Option 1

[0600]

[0601] As shown in Scheme 2, the oxime of Formula 2 can be prepared from the corresponding nitrile or hydroxylamine of Formula 3 and a hydroxylamine salt (e.g., hydroxylamine hydrochloride) in a solvent such as ethanol, methanol, or N,N-dimethylformamide at a temperature generally in the range of about 0 to 80°C. Hydroxylamine can be used in aqueous solution form; alternatively, hydroxylamine can be generated in situ by treating the acid salt of hydroxylamine with a base such as an alkali metal hydroxide or carbonate, preferably sodium hydroxide or sodium carbonate. Hydroxylamine salts include salts formed by hydroxylamine with inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, or with organic acids such as formic acid, acetic acid, propionic acid, and sulfonic acid. For reaction conditions, see Example 10 of the present invention, step B.

[0602] Option 2

[0603]

[0604] Compound of Formula 1 (where L is (CR) 4a R 4b ) n And R 1 For heterocyclic or cyclic systems, such as pyrazoles, indazoles, imidazoles, pyrroles, and triazoles, linked via a nitrogen atom to L), the appropriate leaving group X of the compound of formula 4 can be replaced with a nitrogen-containing heterocycle of formula 5 in the presence of a base. 1 The preparation is carried out as described in Scheme 3. Suitable bases include inorganic bases such as alkali metal or alkaline earth metal (e.g., lithium, sodium, potassium, and cesium) hydrides, alkoxides, carbonates, phosphates, and hydroxides. A variety of solvents are suitable for the reaction, including, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, and acetone. Particularly usable reaction conditions include using cesium carbonate or potassium carbonate and N,N-dimethylformamide or acetonitrile as solvents at temperatures ranging from about 0°C to 80°C. Suitable leaving groups in the compounds of Formula 4 include bromide ions, chloride ions, iodide ions, methanesulfonate groups (OS(O)₂CH₃), trifluoromethanesulfonate groups (OS(O)₂CF₃), etc. The method of Scheme 3 is shown in Example 1, step C; Examples 2-9; and Example 11, step C of the present invention.

[0605] Option 3

[0606]

[0607] Compounds of Formula 4 can be obtained by converting the corresponding alcohol of Formula 6 into a suitable leaving group (i.e., X). 1Alcohols of formula 6 can be prepared as shown in Scheme 4. For example, alcohols of formula 6 can be converted to alkyl chlorides of formula 4 by treatment with thionyl chloride, oxalyl chloride, or phosphorus trichloride (see Example 1, step B for conditions). Alkyl bromides can be prepared using phosphorus tribromide or phosphorus tribromide oxychloride in a similar reaction. Sulfonates can be prepared by reacting formula 6 with a sulfonating agent such as methanesulfonyl chloride, typically in the presence of a base, under conditions well known to those skilled in the art of organic synthesis.

[0608] Option 4

[0609]

[0610] Alternatively, compounds of formula 1 (where R) 1 The N-linked heterocycle can be prepared by reacting the primary or secondary alcohol of Formula 6 with the nitrogen-containing heterocycle of Formula 5 using Mitsunobu coupling reaction conditions, as shown in Scheme 5. The photo-coiling reaction is typically carried out at room temperature in tetrahydrofuran with triphenylphosphine and diisopropyl azodicarboxylate (DIAD) or diethyl azodicarboxylate (DEAD). Polymer-supported triphenylphosphine can be used to facilitate purification. For a review of the photo-coiling reaction, see Mitsunobu, O. Comprehensive Organic Synthesis; Trost, BM, Fleming, I. (eds.); Pergamon: Oxford, 1991; Vol. 6, pp. 65-101. Additionally, step C of Example 12 illustrates the preparation of the compound of Formula 1 using photo-coiling conditions.

[0611] Option 5

[0612]

[0613] Compounds of Formula 6 can be prepared by treating the corresponding nitriles with hydroxylamine or hydroxylamine salts, followed by TFAA treatment similar to that described in Schemes 1 and 2, and as shown in step A of Example 1 of the present invention. Alternatively, secondary alcohols of Formula 6 can be prepared by oxidizing the corresponding alcohol to an aldehyde, and then reacting the aldehyde with a Grignard reagent. The oxidation reaction can be carried out by various methods, such as treating the alcohol of Formula 6 with manganese dioxide, Dess-Martin periodinane, pyridinium chlorochromate, or pyridinium dichromate. For example, as shown in Scheme 6, compounds of Formula 6b (i.e., Formula 6 in the form of CHMe) can be synthesized by converting Formula 6a (Formula 6 in which L is CH2) to an aldehyde of Formula 7, and then treating with methylmagnesium bromide. The method of Scheme 6 is shown in Example 12, steps AB.

[0614] Option 6

[0615]

[0616] The compound of Formula 1 can also be prepared by reacting a suitably functionalized compound of Formula 8 with a suitably functionalized compound of Formula 9, as shown in Scheme 7. Functional group Y 1 and Y 2 Selected from, but not limited to, the following groups, such as aldehydes, ketones, esters, acids, amides, thioamides, nitriles, amines, alcohols, thiols, hydrazines, oximes, amidines, amide oximes, alkenes, acetylenes, halides, haloalkanes, methanesulfonates, trifluoromethanesulfonates (trifluoromethanesulfonate group), boric acids, borates, etc., under appropriate reaction conditions, will allow the construction of various R groups. 1 Rings. For example, compounds of formula 8 (where Y... 1 (the chlorooxime moiety) and the compound of formula 9 (where Y is the chlorooxime moiety) 2 The reaction of a vinyl or ethynyl group in the presence of a base will yield a compound of formula 1, wherein R 1 They are isoxazoline or isoxazole, respectively. Example 3 of the present invention, step C, shows that R... 1 Preparation of compounds of formula 1 for isoxazolines. Synthetic literature describes numerous general methods for forming heterocyclic and cyclic systems (e.g., U-1 to U-114); see, for example, *Comprehensive Heterocyclic Chemistry*, Volumes 4–6, edited by A.R. Katritzky and C.W. Rees, Pergamon Press, Oxford, 1984; *Comprehensive Heterocyclic Chemistry II*, Volumes 2–4, edited by A.R. Katritzky, C.W. Rees and E.F. V. Criven, Pergamon Press, Oxford, 1996; and the series *The Chemistry of Heterocyclic Compounds*, edited by E.T. A. C. Rees, Wiley, New York. Those skilled in the art know how to select appropriate functional groups to construct the desired ring R. 1 The compounds of Formula 8 are known or can be prepared by general methods known in the art. The compounds of Formula 9 can be prepared by treating the corresponding nitriles with hydroxylamine or hydroxylamine salts, followed by TFAA reactions similar to those described in Schemes 1 and 2 and as shown in steps AB of Example 12 of the present invention.

[0617] Option 7

[0618]

[0619] Compounds of formula 1a (i.e., where R) 1The oxazoline of formula 1) can also be prepared as outlined in scheme 8. In this method, the amine of formula 11 is reacted with the compound of formula 10 to provide the amide of formula 12 at a temperature of 0°C to 100°C in the presence of O-(7-azabenzotriazol-1-yl)-N,N,N',N'-t-tetramethylureonium hexafluorophosphate (HATU) or 2-chloro-1-methylpyridinium iodide and a base such as triethylamine, N,N-diisopropylethylamine or 4-methylmorpholine. In a subsequent step, the amide of formula 12 is dehydrated in a suitable solvent using a dehydrating agent such as diethylaminosulfur trifluoride (DAST). The reaction is typically carried out by adding 0.9 to 2 equivalents, preferably 1.5 equivalents, of diethylaminosulfur trifluoride to a mixture of the compound of formula 12 in a solvent such as dichloromethane at a temperature of –78°C to 0°C. The method of scheme 8 is illustrated by step BC of example 15. The compounds of Formula 11 are commercially available or their preparation is known in the art. The compounds of Formula 10 can be prepared by treating the corresponding nitriles with hydroxylamine or hydroxylamine salts, followed by a reaction similar to that described in Schemes 1 and 2 (Example 15, step A) to carry out TFAA.

[0620] Option 8

[0621]

[0622] As shown in Scheme 9, the compound of Formula 1b (i.e., Formula 1 where L is an amino nitrile) can be prepared by means of the Strecker reaction from an amine of Formula 14, an aldehyde of Formula 13, and a cyanide source. A variety of solvents and cyanide sources can be used in the method of Scheme 9. The presence of Lewis acids such as titanium isopropoxide (IV) can be advantageous. For the conditions and variations of this reaction, see the following references and the references cited therein: DTMowry, Chemical Reviews 1948, 42, 236; H. Groeger, Chemical Reviews 2003, 103, 2795-2827; and M. North in Comprehensive Organic Functional Group Transformations, edited by ARKatritsky, O. Meth-Cohn, and CWRees, Vol. 3, pp. 615-617; Pergamon, Oxford, 1995. The method of Scheme 9 is also shown in step E of Example 14. For less reactive amines of formula 14, such as arylamines containing an ortho electron-withdrawing group, the use of trimethylsilyl cyanide with a catalyst such as guanidine hydrochloride may be advantageous. For reference, see, for example, Heydari et al., Journal of Molecular Catalysis A: Chemical 2007, 271(1-2), 142-144.

[0623] Option 9

[0624]

[0625] As shown in Scheme 2 above, the nitrile of Formula 3 is a useful intermediate for the preparation of the compound of Formula 2, which can react with TFAA to provide the compound of Formula 1. The compound of Formula 3 can be prepared from the compounds of Formulas 15 and 16 as shown in Scheme 10 below, wherein Y 3 and Y 4 Suitable functional groups are those that, under appropriate reaction conditions, will allow the construction of various L groups. Suitable functional groups include, but are not limited to, ionizable hydrogen (e.g., hydrogen attached to a nitrogen atom in a heterocycle or hydrogen attached to a carbon atom adjacent to a C(=O) moiety), carbonyl, aldehyde, ketone, ester, acid, acyl chloride, amine, alcohol, thiol, hydrazine, oxime, alkene, acetylene, halide, haloalkane, boric acid, borate ester, etc. For example, a compound of formula 3 (where L is CH2) can be constructed by making Y... 3 For hydrogen (i.e., attached to R) 1 Compounds of formula 15 (containing ionizable hydrogen atoms of the nitrogen atom ring member) react with bases such as potassium carbonate or sodium hydride, followed by the reaction of Y... 4Prepared by treatment of a 16-form compound of halomethane (e.g., BrCH2-); and using Y in which 4 Treatment of a compound of formula 16, where L is CH(=O)-, yields a compound of formula 3, where L is CH(OH). Compounds of formula 3, where L is O, can be obtained by treating a compound where Y is in the presence of a base such as sodium hydride. 3 Compounds of formula 15 containing Br and Y 4 The compound of formula 16, where L is CH2O, is prepared by reacting it with the OH group. The compound of formula 3, where L is CH2O, can be prepared by reacting Y in the presence of a base. 3 Compounds of formula 15 containing BrCH2- and Y 4 The compound of formula 16, where L is OCH2CH2, is prepared by reacting it with the compound containing Y in the presence of a base. 3 Compound of formula 15 with OH and Y 4 The reaction is carried out to prepare compounds of formula 16 for haloethanes (e.g., ICH2CH2-). Synthetic literature describes numerous general methods for forming saturated chains containing 1 to 3 atoms, such as the L-group of the present invention; see, for example, *Comprehensive Organic Functional Group Transformations*, Volumes 1, 2, 3, and 5, edited by A.R. Katritzky, Pergamon Press, New York, 1995; *Vogel's Textbook of Practical Organic Chemistry*, 5th edition, pp. 470–823, Longman Group, London, 1989; and *Advanced Organic Chemistry*, 4th edition, Jerry March, Wiley, New York, 1992. Those skilled in the art can readily determine how to select appropriate compounds of formulas 15 and 16 to construct the desired L-group.

[0626] Option 10

[0627]

[0628] Scheme 11 illustrates the preparation of compounds of formula 3a (i.e., where R...). 1A specific example of the general method of Scheme 10 (where L is CH2, of Formula 3) is a pyrazole. In this method, the pyrazole of Formula 17 is reacted with bromohexane of Formula 18 in the presence of a base such as sodium hydroxide or potassium hydroxide, sodium hydride or potassium carbonate, in a solvent such as tetrahydrofuran, N,N-dimethylformamide, ethanol or acetonitrile, typically at a temperature between about 0°C and 80°C. Example 10 of the present invention, step A illustrates the method of Scheme 11.

[0629] Option 11

[0630]

[0631] Those skilled in the art will recognize that the method of Scheme 10 can also be carried out when the substituent –C≡N in Formula 16 is replaced by 5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl (i.e., Formula 19), thereby providing a compound of Formula 1 as shown in Scheme 12 below.

[0632] Option 12

[0633]

[0634] Scheme 13 illustrates the preparation of compounds of formula 1c (i.e., where R...). 1 A specific example of the general method of Scheme 12 (of formula 1, where L is CH2O) is an oxazole. In this method, the chloromethane of formula 20 is reacted with the alcohol of formula 21 in the presence of a base such as sodium hydroxide or potassium hydroxide, sodium hydride or potassium carbonate, in a solvent such as tetrahydrofuran, N,N-dimethylformamide, ethanol or acetonitrile, typically at a temperature between about 0°C and 80°C. Examples 17 and 18 of the present invention illustrate the method of Scheme 19.

[0635] Option 13

[0636]

[0637] It should be recognized that some of the reagents and reaction conditions described above for the preparation of compounds of Formula 1 may be incompatible with certain functional groups present in the intermediates. In these cases, incorporating protecting / deprotecting sequences or interconversions of functional groups into the synthesis will facilitate obtaining the desired product. The use and selection of protecting groups will be readily apparent to those skilled in the art of chemical synthesis (see, for example, T.W. Greene and P.G. M. Uts., Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). Those skilled in the art will recognize that in some cases, after the introduction of a given reagent as described in any individual scheme, additional conventional synthetic steps, not described in detail, may be required to complete the synthesis of compounds of Formula 1. Those skilled in the art will also recognize that combinations of the steps shown in the above schemes may need to be performed in a sequence other than that implied by the specific sequences presented to prepare compounds of Formula 1.

[0638] Those skilled in the art will also recognize that the compounds of Formula 1 and the intermediates described herein can undergo a variety of electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0639] Without further detailed explanation, it is believed that those skilled in the art will be able to fully utilize the invention using the foregoing description. Therefore, the following examples are to be interpreted merely as illustrative and, in any way, not as limiting the scope of this disclosure. The steps in the following examples illustrate the process of each step in the overall synthetic transformation, and the starting material for each step may not necessarily be prepared by the specific preparation process described in other examples or steps. Percentages are by weight, except for chromatographic solvent mixtures or otherwise specified. Unless otherwise specified, the parts and percentages of chromatographic solvent mixtures are by volume. 1 1H NMR spectra are recorded in low-field ppm from tetramethylsilane; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dt" means doublet of doublet, "br s" means broad singlet, and "br d" means broad doublet. 19 F NMR uses trichlorofluoromethane as a reference and records data in ppm.

[0640] Example 1

[0641] Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrazolo[3,4-b] Pyridine (compound 147)

[0642] Step A: Preparation of 4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl alcohol

[0643] A mixture of 4-(hydroxymethyl)benzonitrile (52.8 g, 397 mmol), hydroxylamine hydrochloride (33.1 g, 476 mmol), N,N-diisopropylethylamine (107 mL, 595 mmol), and 8-hydroxyquinoline (0.3 g) in ethanol (400 mL) was heated under reflux for 5 hours. The reaction mixture was concentrated under reduced pressure to give the intermediate compound N-hydroxy-4-(hydroxymethyl)benzoamide.

[0644] At room temperature, pyridine (70 mL, 873 mmol) and trifluoroacetic anhydride (121 mL, 873 mmol) were added dropwise to a mixture of N-hydroxy-4-(hydroxymethyl)benzamidinium in acetonitrile and tetrahydrofuran (1:1, 400 mL). The reaction mixture was refluxed and heated for 15 hours, then cooled to room temperature, followed by the slow addition of 300 mL of saturated aqueous sodium bicarbonate solution, ethyl acetate (400 mL), and water. The resulting mixture was separated, and the organic layer was washed with 100 mL of saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the title compound.

[0645] 1 H NMR (CDCl3): δ4.77(s,2H),7.50(d,2H),8.08(d,2H).

[0646] 19 F NMR (CDCl3): δ–65.47.

[0647] Step B: Preparation of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0648] At 5 °C, thionyl chloride (57 mL) was added to a mixture of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl alcohol (i.e., the product of step A) (98.0 g, 397 mmol) and N,N-dimethylformamide (4 drops) in dichloromethane (500 mL). The reaction mixture was heated at about 42 °C for 30 minutes and then concentrated under reduced pressure to remove the dichloromethane. The resulting mixture was diluted with acetonitrile (80 mL) and poured into ice water (700 mL). The resulting solid precipitate was collected by filtration, washed with water, and dried in a vacuum oven under nitrogen to give the title compound as a solid (55 g).

[0649] 1 H NMR (CDCl3): δ4.64(s,2H),7.54-7.55(d,2H),8.10-8.12(d,2H).

[0650] 19 F NMR (CDCl3): δ–65.45.

[0651] Step C: Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrazol [3,4-b]pyridine

[0652] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B) (0.3 g, 1.1 mmol), 1H-pyrazolo[3,4-b]pyridine (0.136 g, 1.1 mmol), and cesium carbonate (0.38 g, 1.1 mmol) in N,N-dimethylformamide (2.5 mL) was stirred at room temperature for 12 hours. The reaction mixture was partitioned between ethyl acetate (25 mL) and water (5 mL). The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a solid (0.090 g).

[0653] 1 H NMR (CDCl3): δ5.80(s,2H),7.13-7.21(m,1H),7.42-7.51(m,2H),8.01-8.13(m,4H),8.58(dd,1H).

[0654] 19 F NMR (CDCl3): δ–65.43.

[0655] Example 2

[0656] Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrazole-4-carboxynitrile (Compound 95)

[0657] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (3.60 g, 13.7 mmol), 1H-pyrazole-4 (1.91 g, 20.6 mmol), potassium carbonate (3.41 g, 24.7 mmol), and sodium bromide (1.62 g, 15.8 mmol) in acetonitrile (100 mL) was heated under reflux for 18 hours. The reaction mixture was cooled to room temperature, filtered, and the filtrate was concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexane) to give a white solid (4.38 g). The solid was crystallized from ethanol to provide the title compound, which is the compound of the present invention, a white solid (3.29 g) that melts at 106–108 °C.

[0658] 1H NMR (CDCl3): δ5.42(s,2H),7.38-7.39(d,2H),7.86-7.87(m,2H),8.13-8.15(d,2H).

[0659] 19 F NMR (CDCl3): δ–65.33

[0660] Example 3

[0661] Preparation of 6-chloro-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3(2H)-pyridazinone (Compound 4)

[0662] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (0.2 g, 0.76 mmol), 6-chloro-3(2H)-pyridazinone (0.099 g, 0.76 mmol), and potassium carbonate (0.21 g, 1.52 mmol) in N,N-dimethylformamide (5 mL) was stirred overnight at room temperature. The reaction mixture was diluted with water and extracted with diethyl ether (2x). The combined extracts were washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a 1:1 hexane solution of ethyl acetate) to give the title compound, which is the compound of the present invention, as a white solid (0.18 g).

[0663] 1 H NMR (CDCl3): δ8.10(d,2H),7.58(d,2H),7.19(d,1H),6.95(d,1H),5.32(s,2H).

[0664] Example 4

[0665] Preparation of 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-2H-indazole-4-carboxylic acid Ester (compound 36) and

[0666] 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-indazole-4-carboxylic acid methyl ester (Compound 49)

[0667] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (0.3 g, 1.1 mmol), methyl 1H-indazole-4-carboxylate (0.2 g, 1.1 mmol), and cesium carbonate (0.56 g, 1.7 mmol) in N,N-dimethylformamide (2.5 ml) was stirred at room temperature for 12 hours. The reaction mixture was partitioned between ethyl acetate (25 ml) and water (5 ml). The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting in a gradient of 5% to 50% ethyl acetate in hexane) to give title compound 49 (faster elution product) as a solid (0.11 g). Title compound 36 (slower elution product) was also obtained as a solid (0.04 g).

[0668] 1 ¹H NMR (CDCl₃): δ 3.97 (s, 3H), 5.73 (s, 2H), 7.33–7.42 (m, 1H), 7.42–7.49 (m, 2H), 7.90–8.02 (m, 2H), 8.07–8.16 (m, 2H), 8.53 (s, 1H) (Compound 36).

[0669] 19 F NMR (CDCl3): δ–65.39 (compound 36).

[0670] 1 ¹H NMR (CDCl₃): δ 3.98–4.08 (m, 3H), 5.67–5.76 (m, 2H), 7.28–7.35 (m, 2H), 7.37–7.48 (m, 1H), 7.50–7.59 (m, 1H), 7.89–7.98 (m, 1H), 8.01–8.10 (m, 2H), 8.59 (s, 1H) (Compound 49).

[0671] 19 F NMR (CDCl3): δ–65.42 (compound 49).

[0672] Example 5

[0673] Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrrolo[3,2-b] Pyridine (compound 136)

[0674] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (0.3 g, 1.1 mmol), 1H-pyrrolo[3,2-b]pyridine (0.14 g, 1.1 mmol), and cesium carbonate (0.56 g, 1.7 mmol) in N,N-dimethylformamide (2.5 mL) was stirred at room temperature for 12 hours. The reaction mixture was partitioned between ethyl acetate (25 mL) and water (5 mL). The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a solid (0.045 g).

[0675] 1 H NMR (CDCl3): δ5.42(m,2H),6.79-6.88(m,1H),7.06-7.15(m,1H),7.23(m,2H),7.41(d,1H),7.54(d,1H),8.07(d,2H),8.49(br d,1H).

[0676] 19 F NMR (CDCl3): δ–65.40.

[0677] Example 6

[0678] Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-2(1H)-quinoxaline (chemical) Compound 158)

[0679] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (0.3 g, 1.1 mmol), 2(1H)-quinoxaloline (0.17 g, 1.1 mmol), and cesium carbonate (0.56 g, 1.7 mmol) in N,N-dimethylformamide (2.5 mL) was stirred at room temperature for 12 hours. The reaction mixture was partitioned between ethyl acetate (25 mL) and water (5 mL). The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a solid (0.08 g).

[0680] 1H NMR (CDCl3): δ5.57(s,2H),7.19-7.24(m,1H),7.32-7.38(m,1H),7.40(d,2H),7.45-7.53(m,1H),7.90-7.97(m,1H),8.08(d,2H),8.44(s,1H).

[0681] 19 F NMR (CDCl3): δ–65.40.

[0682] Example 7

[0683] Preparation of 1,3-dihydro-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]- 2H-benzimidazol-2-one (compound 159)

[0684] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (0.3 g, 1.1 mmol), 1,3-dihydro-1-methyl-2H-benzimidazole-2-one (0.17 g, 1.1 mmol), and cesium carbonate (0.56 g, 1.7 mmol) in N,N-dimethylformamide (2.5 ml) was stirred at room temperature for 12 hours. The reaction mixture was partitioned between ethyl acetate (25 ml) and water (5 ml). The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 0 to 50% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a solid (0.095 g).

[0685] 1 H NMR (CDCl3): δ3.49(s,3H),5.16(s,2H),6.81-6.90(m,1H),6.97-7.06(m,2H),7.06-7.18(m,1H),7.47(d,2H),8.07(d,2H).

[0686] Example 8

[0687] Preparation of 1,2-dihydro-2-oxo-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]- 4-Pyridinecarboxylic acid methyl ester (compound 24)

[0688] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (1.0 g, 3.8 mmol), methyl 1,2-dihydro-2-oxo-4-pyridinecarboxylate (0.59 g, 3.81 mmol), and cesium carbonate (1.90 g, 5.72 mmol) in N,N-dimethylformamide (5 ml) was stirred at room temperature for 12 hours. The reaction mixture was partitioned between ethyl acetate (25 ml) and water (5 ml). The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a solid (0.35 g).

[0689] 1 H NMR (CDCl3): δ3.92(s,3H),5.23(s,2H),6.64-6.73(m,1H),7.27(d,1H),7.33-7.40(m,1H),7.40-7.49(m,2H),8.04-8.17(m,2H).

[0690] 19 F NMR (CDCl3): δ–65.39.

[0691] Example 9

[0692] Preparation of 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-isoindole-1,3 (2H)-Diketone (Compound 90)

[0693] A mixture of 3-[4-(chloromethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B in Example 1) (0.25 g, 0.85 mmol) and potassium phthalimide (0.17 g, 0.95 mmol) in N,N-dimethylformamide (2.5 mL) was stirred at room temperature for 12 hours. The reaction mixture was partitioned between ethyl acetate (25 mL) and water (5 mL). The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a solid (0.21 g).

[0694] 1 H NMR (CDCl3): δ4.92(s,2H),7.50-7.63(m,2H),7.68-7.79(m,2H),7.82-7.93(m,2H),8.01-8.13(m,2H).

[0695] 19 F NMR (CDCl3): δ–65.39.

[0696] Example 10

[0697] Preparation of ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrazole-4-carboxylic acid Ester (Compound 83)

[0698] Step A: Preparation of ethyl 1-[(4-cyanophenyl)methyl]-1H-pyrazole-4-carboxylate

[0699] A mixture of ethyl 1H-pyrazole-4-carboxylate (4.96 g, 35.4 mmol), 4-(bromomethyl)benzonitrile (6.92 g, 35.3 mmol), and potassium carbonate (6.0 g, 43.5 mmol) in acetonitrile (100 mL) was heated at 60 °C for 6 hours and then stirred overnight at room temperature. The reaction mixture was diluted with water, and the resulting solid precipitate was filtered, washed with water, and air-dried to give the title compound as a white solid (8.65 g).

[0700] 1 H NMR (CDCl3): δ1.34(t,3H),4.30(q,2H),5.37(s,2H),7.29-7.31(m,2H),7.65-7.66(m,2H),7.93(s,1H),7.96(s,1H).

[0701] Step B: Preparation of ethyl 1-[[4-[(hydroxyamino)iminomethyl]phenyl]methyl]-1H-pyrazole-4-carboxylate

[0702] Ethyl 1-[(4-cyanophenyl)methyl]-1H-pyrazole-4-carboxylate (i.e., the product of step A) (29.1 g, 114 mmol) and hydroxylamine (50% aqueous solution, 12 mL, 194 mmol) in N,N-dimethylformamide (200 mL) were stirred at room temperature for 3 days. The reaction mixture was poured into ice water, and the resulting solid precipitate was filtered and washed with water. The wet solid was mixed with acetonitrile (500 mL) and concentrated under reduced pressure to give the title compound as a white solid (31.32 g).

[0703] 1 H NMR(DMSO-d6): δ1.26(t,3H),4.21(q,2H),5.38(s,2H),5.79(s,2H),7.2 5-7.27(m,2H),7.63-7.65(m,2H),7.87(s,1H),8.47(s,1H),9.63(s,1H).

[0704] Step C: Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrazole-4- Ethyl carboxylate

[0705] Over 20 minutes, trifluoroacetic anhydride (19 mL, 140 mmol) was added dropwise to a mixture of ethyl 1-[[4-[(hydroxyamino)iminomethyl]phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e., the product of step B) (33.65 g, 117 mmol) and pyridine (13 mL, 160 mmol) in N,N-dimethylformamide (100 mL) at 0 °C. The reaction mixture was heated at 70 °C for 2 hours, cooled, and stirred overnight at room temperature. The reaction mixture was poured into ice water, and the resulting solid precipitate was filtered and washed with water. The solid was crystallized from ethanol (250 mL) to give the title compound, which is the compound of the present invention, as a molten solid needle-like substance (35.1 g) at 127-129 °C.

[0706] 1 H NMR (CDCl3): δ1.34(t,3H),4.30(q,2H),5.39(s,2H),7.37-7.39(m,2H),7.93(s,1H),7.97(s,1H),8.11-8.13(m,2H).

[0707] 19 F NMR (CDCl3): δ–65.34.

[0708] Example 11

[0709] Preparation of 3-[5-[(4-bromo-1H-pyrazol-1-yl)methyl]-2-thienyl]-5-(trifluoromethyl)-1,2,4-oxa diazole (compound 71)

[0710] Step A: Preparation of 3-(5-methyl-2-thienyl)-5-(trifluoromethyl)-1,2,4-oxadiazole

[0711] A mixture of 5-methyl-2-thiophenecarboxynitrile (4.0 g, 32 mmol), hydroxylamine hydrochloride (3.3 g, 48 mmol), diisopropylethylamine (10 mL, 56 mmol), and 8-hydroxyquinoline (0.074 g) in ethanol (65 mL) was refluxed for 5 hours. The reaction mixture was concentrated under reduced pressure to give the intermediate compound N-hydroxy-5-methyl-2-thiophenecarboximide amide.

[0712] A solution of N-hydroxy-5-methyl-2-thiophenecarboximide amide in tetrahydrofuran (65 mL) was added dropwise to a mixture of trifluoroacetic anhydride (13 mL, 96 mmol), diisopropylethylamine (20 mL, 112 mmol), and 4-dimethylaminopyridine (1.0 g, 8 mmol). The reaction mixture was stirred at room temperature for 15 hours and then diluted with a saturated aqueous sodium bicarbonate solution (30 mL). The aqueous mixture was extracted with ethyl acetate (80 mL), and the organic layer was washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a 1:10 ethyl acetate solution in hexane) to give the title compound as a solid (3.2 g).

[0713] 1 H NMR (CDCl3): δ2.57(s,3H),6.85(d,1H),7.68(d,1H).

[0714] 19 F NMR (CDCl3): δ–65.46.

[0715] Step B: Preparation of 3-[5-(bromomethyl)-2-thienyl]-5-(trifluoromethyl)-1,2,4-oxadiazole N-bromosuccinimide (2.6 g, 14.8 mmol) and 2,2'-azobisisobutyronitrile (0.2 g, 1.3 mmol) were added to a mixture of 3-(5-methyl-2-thienyl)-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step A) (3.1 g, 13.2 mmol) in dichloromethane (30 mL). The reaction mixture was refluxed and heated for 6 hours, cooled to room temperature, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a 1:10 ethyl acetate solution in hexane) to give the title compound as a white solid (2.8 g).

[0716] 1 H NMR (CDCl3): δ4.73(s,2H),7.18(m,1H),7.73(m,1H).

[0717] 19 F NMR (CDCl3): δ–65.40.

[0718] Step C: Preparation of 3-[5-[(4-bromo-1H-pyrazol-1-yl)methyl]-2-thienyl]-5-(trifluoromethyl)-1, 2,4-oxadiazole

[0719] A mixture of 3-[5-(bromomethyl)-2-thienyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B) (0.16 g, 0.5 mmol), 4-bromo-1H-pyrazole (0.080 g, 0.55 mmol), and potassium carbonate (0.152 g, 1.1 mmol) in acetonitrile (4 mL) was heated under reflux for 2 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with ethyl acetate in a 3:1 hexane solution) to give the title compound as an oil (0.088 g).

[0720] 1 H NMR (CDCl3): δ5.47(s,2H),7.09(m,1H),7.48(s,1H),7.50(s,1H),7.74(m,1H).

[0721] 19 F NMR (CDCl3): δ–65.41.

[0722] Example 12

[0723] Preparation of 1-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]-1H-pyrazole-4-carboxylic acid Ethyl ester (compound 2)

[0724] Step A: Preparation of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzaldehyde

[0725] At room temperature, 1,1,1-tris(acetoxy)-1,1-dihydro-1,2-benzodiazepine-3-yl]benzyl alcohol (2.00 g, 8.19 mmol) (Martin's reagent) (3.47 g, 8.19 mmol) was added dropwise to a mixture of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl alcohol (20 mL) and Martin's reagent. After stirring for 3 minutes, the reaction mixture was diluted with dichloromethane and saturated aqueous sodium bicarbonate solution. The organic layer was separated and washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound as an oil (1.53 g).

[0726] 1 H NMR (CDCl3): δ8.05(d,2H),8.32(d,2H),10.12(s,1H).

[0727] 19 F NMR (CDCl3): δ–65.32.

[0728] Step B: Preparation of α-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl alcohol

[0729] A solution of methyl magnesium bromide (3M in diethyl ether; 2.1 mL, 6.3 mmol) was added dropwise to a mixture of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzaldehyde (i.e., the product of step A) (1.53 g, 6.3 mmol) in tetrahydrofuran (20 mL) at -12 °C. The reaction mixture was stirred at -12 °C for 2 hours and then quenched with an aqueous solution containing ammonium chloride. The resulting mixture was poured into water and extracted with ethyl acetate. The combined organic extracts were washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting in a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound as a solid (1.63 g).

[0730] 1 H NMR (CDCl3): δ1.40-1.61(m,3H), 4.84-5.06(m,1H), 7.50(d,2H), 8.06(d,2H).

[0731] 19 F NMR (CDCl3): δ–65.49.

[0732] Step C: Preparation of 1-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]-1H-pyrazole- 4-Carboxylic acid ethyl ester

[0733] At room temperature, a mixture of α-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl alcohol (i.e., the product of step B) (0.372 g, 0.95 mmol), ethyl 1H-pyrazole-4-carboxylate (0.202 g, 0.95 mmol), and triphenylphosphine (0.377 g, 0.95 mmol) in tetrahydrofuran (10 mL) was stirred for 10 minutes, and then 1,2-bis(1-methylethyl)1,2-diazeline dicarboxylate (DIAD) (0.285 mL, 0.95 mmol) was added. After 12 hours, the reaction mixture was concentrated under reduced pressure. The resulting substance was purified by silica gel rapid chromatography (eluting with a gradient of 5% to 50% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a solid (0.11 g).

[0734] 1 H NMR (CDCl3): δ1.25-1.38(m,3H),1.88-2.00(m,3H),4.28(q,2H),5.49-5.67(m,1H),7.29-7.41(m,2H),7.89-8.02(m,2H),8.03-8.16(m,2H).

[0735] 19F NMR (CDCl3): δ–65.44.

[0736] Example 13

[0737] Preparation of 4,5-dihydro-N,N-dimethyl-5-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl [3-Isoxazole carboxamide (compound 12)]

[0738] Step A: Preparation of N-hydroxy-4-(2-propen-1-yl)benzamidin

[0739] A mixture of 4-(2-propen-1-yl)benzonitrile (5.0 g, 35 mmol) and hydroxylamine (50% aqueous solution, 4.5 mL, 73 mmol) in anhydrous ethanol (50 mL) was stirred at room temperature for 16 hours. The reaction mixture was concentrated under reduced pressure, diluted with acetonitrile (50 mL), concentrated under reduced pressure, and diluted again with acetonitrile (50 mL) and concentrated under reduced pressure to give the title compound as a colorless oil that crystallized upon standing (6.1 g).

[0740] 1 H NMR (CDCl3): δ3.39-3.41(m,2H),4.90(br s,2H),5.07-5.10(m,2H),5.90-6.00(m,1H),7.20-7.22(m,2H),7.54-7.56(m,2H),8.5-9.5(br s,1H).

[0741] Step B: Preparation of 3-[4-(2-propen-1-yl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0742] Trifluoroacetic anhydride (5.5 mL, 40 mmol) was added dropwise to a mixture of N-hydroxy-4-(2-propen-1-yl)benzamidin (the product of step A) (6.0 g, 34 mmol) and pyridine (3.5 mL, 43 mmol) in acetonitrile (25 mL) over 20 minutes at 0 °C. The reaction mixture was heated at 60 °C for 4 hours, cooled, and then poured into ice water and extracted with diethyl ether (3 × 100 mL). The combined organic extracts were washed with aqueous hydrochloric acid (1 N), saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the title compound as a pale yellow oil (8.0 g).

[0743] 1 H NMR (CDCl3): δ3.46-3.48(m,2H), 5.10-5.15(m,2H), 5.90-6.05(m,1H), 7.34-7.36(m,2H), 8.03-8.05(m,2H).

[0744] 19 F NMR (CDCl3): δ–65.40.

[0745] Step C: Preparation of 4,5-dihydro-N,N-dimethyl-5-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl] [Phenylene]methyl]-3-isoxazolecarboxamide

[0746] A mixture of 3-[4-(2-propen-1-yl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step B) (0.254 g, 1.0 mmol), 2-(dimethylamino)-N-hydroxy-2-oxo-iminoacetyl chloride (0.152 g, 1.0 mmol), and sodium bicarbonate (0.3 g, 3.5 mmol) in ethyl acetate (20 mL) was stirred for 24 hours at room temperature. The reaction mixture was filtered, washed with a small amount of ethyl acetate, and the filtrate was concentrated under reduced pressure. The resulting substance was purified by silica gel rapid chromatography (eluting with a gradient of 0-100% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, as a white solid (0.27 g).

[0747] 1 H NMR (CDCl3): δ3.00-3.15(m,2H),3.03(s,3H),3.17(s,3H),3.33-3.40(m,1H),4.92-5.00(m,1H),7.40-7.44(m,2H),8.06-8.10(m,2H).

[0748] 19 F NMR (CDCl3): δ–65.36.

[0749] Example 14

[0750] Preparation of α-(phenylamino)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenylacetonitrile (Compound 13)

[0751] Step A: Preparation of 4-(1,3-dioxolane-2-yl)benzonitrile

[0752] Ethylene glycol (35.73 g, 576 mmol) and p-toluenesulfonic acid monohydrate (2.92 g, 15.3 mmol) were added to a mixture of 25.16 g (191.9 mmol) and toluene (250 mL). The reaction mixture was heated under reflux for 18 hours using a Dean-Stark water separator to remove water via azeotropic extraction. After cooling to room temperature, the reaction mixture was washed with saturated aqueous solutions of sodium bicarbonate and sodium chloride, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the title compound as a white solid (33.6 g).

[0753] 1 H NMR (CDCl3): δ4.04-4.13(m,4H),5.85(s,1H),7.57-7.62(m,2H),7.66-7.70(m,2H).

[0754] Step B: Preparation of 4-(1,3-dioxolane-2-yl)-N-hydroxybenzamide

[0755] A mixture of 33.6 g (192 mmol) of 4-(1,3-dioxolane-2-yl)benzonitrile (i.e., the product of step A) and hydroxylamine (50% aqueous solution, 14 mL, 228 mmol) in ethanol (200 mL) was heated at 70 °C for 1 hour. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The resulting product was diluted with acetonitrile and concentrated under reduced pressure to give the title compound as a white solid (40.2 g).

[0756] 1 H NMR (DMSO-d6): δ3.91-4.09(m,4H),5.74(s,1H),5.77-5.88(m,2H),7.42-7.44(m,2H),7.68-7.71(m,2H),9.67(s,1H).

[0757] Step C: Preparation of 3-[4-(1,3-dioxolane-2-yl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0758] Over 10 minutes, trifluoroacetic anhydride (28.8 mL, 207 mmol) was added dropwise to a mixture of 4-(1,3-dioxolane-2-yl)-N-hydroxybenzamidinium (i.e., the product of step B) (40.2 g, 192 mmol) and pyridine (18.3 mL, 226 mmol) in acetonitrile (350 mL) at 0 °C. The reaction mixture was heated to room temperature and stirred overnight. The reaction mixture was concentrated under reduced pressure, and the resulting substance was partitioned between dichloromethane and water. The organic layer was separated and washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting substance was purified by silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexane) to give the title compound as a white solid that melts at 53–55 °C.

[0759] 1 H NMR (CDCl3): δ4.05-4.23(m,4H),5.88(s,1H),7.65(d,2H),8.14(d,2H).

[0760] 19 F NMR (CDCl3): δ–65.36.

[0761] Step D: Preparation of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)]benzaldehyde

[0762] At room temperature, a mixture of 3-[4-(1,3-dioxolane-2-yl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (i.e., the product of step C) (2.48 g 8.67 mmol), tetrahydrofuran (25 mL), water (25 mL), and concentrated hydrochloric acid (25 mL) was stirred for 30 minutes. The reaction mixture was diluted with ethyl acetate (100 mL) and separated into layers. The organic layer was washed with water and a saturated aqueous solution of sodium chloride, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the title compound as a white solid (2.09 g) that melts at 50–52 °C.

[0763] 1 H NMR (CDCl3): δ8.04-8.06(m,2H)8.31-8.33(m,2H)10.12(s,1H).

[0764] Step E: Preparation of α-(phenylamino)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenylacetonitrile

[0765] At room temperature, a mixture of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzaldehyde (i.e., the product of step D) (2.59 g, 10.7 mmol), aniline (95 μL, 1.0 mmol), and titanium isopropoxide (IV) (500 μL, 170 mmol) in tetrahydrofuran (5 mL) was stirred for 2 hours, followed by the addition of trimethylsilane cyanide (500 μL, 3.9 mol). The reaction mixture was stirred overnight at room temperature, and then added to a mixture of ice and ethyl acetate under vigorous stirring. After 1 hour, the mixture was filtered, and the filtrate was washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give a yellow solid. The solid was crystallized from diethyl ether (4 mL) and hexane (10 mL) to give the title compound, which is the compound of the present invention, as a colorless solid (163 mg).

[0766] 1 H NMR (CDCl3): δ4.12(d,1H),5.55(d,1H),6.80(m,2H),6.95(m,1H),7.27-7.32(m,2H),7.79-7.81(m,2H),8.20-8.24(m,2H).

[0767] 19 F NMR (CDCl3): δ–65.31.

[0768] Example 15

[0769] Preparation of 4,5-dihydro-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazole Methyl carboxylate (compound 74)

[0770] Step A: Preparation of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenylacetic acid

[0771] A mixture of 4-cyanophenylacetic acid (25.0 g, 155 mmol) and hydroxylamine (50% aqueous solution, 23.8 mL, 780 mmol) in ethanol (500 mL) was heated under reflux overnight. The reaction mixture was concentrated under reduced pressure and the resulting solid was dried in a vacuum oven overnight. The solid (i.e., the intermediate compound 4-[(hydroxyamino)iminomethyl]phenylacetic acid) was suspended in tetrahydrofuran (500 mL) and cooled to 0 °C, and then trifluoroacetic anhydride (48 mL, 340 mmol) and triethylamine (47 mL, 340 mmol) were added. The reaction mixture was stirred overnight at room temperature and then concentrated under reduced pressure. The resulting substance was partitioned between water and dichloromethane. The organic layer was separated, dried on sodium sulfate, filtered, and concentrated to [a specific concentration]. Top (diatomaceous earth filter aid). The mixture was purified by medium-pressure silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexane) to give the title compound as a white solid (17.8 g).

[0772] 1 H NMR (CDCl3): δ8.10(d,2H),7.46(d,2H),3.76(s,2H).

[0773] 19 F NMR (CDCl3): δ–65.35.

[0774] Step B: Preparation of N-[2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]serine methyl ester

[0775] To a solution of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenylacetic acid (i.e., the product of step A) (17.8 g, 65.3 mmol) in N,N-dimethylformamide (220 mL), DL-serine methyl hydrochloride (1:1) (12.2 g, 78.4 mmol), 1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxyhexafluorophosphate (HATU) (29.8 g, 78.4 mmol), and 4-methylmorpholine (14.4 mL, 131 mmol) were added. The reaction was stirred overnight at room temperature, then diluted with water and extracted with ethyl acetate (3x). The combined organic layers were washed with water and a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated to […]. (Diatomaceous earth filter aid) on top. The mixture was purified by medium-pressure silica gel chromatography (eluting with a gradient of hexane solution from 0% to 100% ethyl acetate) to give the title compound.

[0776] 1 H NMR (CDCl3): δ8.12(d,2H),7.48(d,2H),6.47,(br s,1H),4.68(dt,1H),4.00(dd,1H),3.92(m,1H),3.78(s,3H),3.72(s,2H).

[0777] 19 F NMR (CDCl3): δ–65.34.

[0778] Step C: Preparation of 4,5-dihydro-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]- 4-Oxazolylcarboxylate

[0779] At –78 °C, diethylaminosulfur trifluoride (DAST) (13 mL, 98 mmol) was added to a solution of N-[2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetyl]serine methyl ester (i.e., the product of step B) (65.3 mmol) in dichloromethane (650 mL). The reaction was stirred at –78 °C for 1.5 h, and then quenched with a saturated aqueous sodium bicarbonate solution and separated into layers. The aqueous layer was further extracted with dichloromethane and the combined organic layers were washed with a saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate, filtered, and concentrated to […]. (Diatomaceous earth filter aid) on top. The mixture was purified by medium-pressure silica gel rapid chromatography (eluting with a gradient of 0% to 100% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, in solid form (8.17 g).

[0780] 1 H NMR (CDCl3): δ8.08(d,2H),7.48(d,2H),4.78(m,1H),4.53(m,1H),4.43(m,1H),3.80(s,3H),3.76(m,2H).

[0781] 19 F NMR (CDCl3): δ–65.33.

[0782] Example 16

[0783] Preparation of 4,5-dihydro-N,N-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl [4-oxazolamide (compound 178)]

[0784] To a mixture of methyl 4,5-dihydro-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolylcarboxylate (i.e., the product of step C in Example 15) (0.25 g, 0.7 mmol) in methanol (7 mL), N,N-dimethylamine (5.6N ethanol solution, 0.63 mL) was added. The reaction mixture was stirred overnight at 65 °C and then cooled to room temperature and concentrated to... (Diatomaceous earth filter aid) on top. The mixture was purified by medium-pressure silica gel rapid chromatography (eluting with a gradient of 0% to 100% ethyl acetate in hexane) to give the title compound, which is the compound of the present invention, in solid form (0.009 g).

[0785] 1 H NMR (CDCl3): δ 8.06 (d, 2H), 7.46 (d, 2H), 4.95 (m, 2H), 4.29 (dd, 1H), 3.71 (m, 2H), 3.26 (s, 3H), 3.00 (s, 3H).

[0786] 19 F NMR (CDCl3): δ–65.36.

[0787] Example 17

[0788] Preparation of 4,5-dihydro-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazole Formamide (Compound 75)

[0789] A mixture of methyl 4,5-dihydro-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolylcarboxylate (i.e., the product of step C in Example 15) (0.5 g, 1.4 mmol) and ammonia (7 N methanol solution, 14 mL) was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to give the title compound, which is the compound of the present invention, as a solid (0.134 g).

[0790] 1 H NMR (CDCl3): δ8.10(d,2H),7.46(d,2H),4.68(m,2H),4.52,m,2H),3.73(m,2H).

[0791] 19 F NMR (CDCl3): δ–65.32.

[0792] Example 18

[0793] Preparation of 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-phenoxy]-methyl]oxazol-4-carboxylic acid Ester (compound 403)

[0794] Step A: Preparation of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenol

[0795] Hydroxylamine (50% aqueous solution, 13.4 mL, 440 mmol) was added to a mixture of 4-hydroxybenzonitrile (20 g, 168 mmol) and ethanol (177 mL). The reaction mixture was stirred for 18 hours and then concentrated under reduced pressure. The solid (i.e., the intermediate compound N,4-dihydroxybenzoamide) was dissolved in dichloromethane (336 mL) and trifluoroacetic anhydride (47 mL, 336 mmol) was added. The reaction mixture was heated to reflux for 18 hours and then cooled to room temperature and quenched with water. The layers were separated, and the aqueous layer was further extracted twice with dichloromethane. The combined organic matter was washed with saturated aqueous solutions of sodium bicarbonate and sodium chloride, dried over magnesium sulfate, filtered, and concentrated to [a specific concentration]. (Diatomaceous earth filter aid) on top. The mixture was purified by medium-pressure silica gel chromatography (using a hexane solution of 0% to 100% ethyl acetate as eluent) to give the title compound (16.3 g).

[0796] 1 H NMR (CDCl3): δ8.10(d,2H), 6.96(d,2H).

[0797] 19 F NMR (CDCl3): δ–65.45.

[0798] Step B: Preparation of 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-phenoxy]-methyl]oxazol-4- Methyl carboxylate

[0799] To a solution of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenol (i.e., the product of step A) (1.13 g, 5 mmol) in acetonitrile (50 mL), methyl 2-(chloromethyl)oxazol-4-carboxylate (0.95 g, 5.4 mmol), potassium carbonate (1.52 g, 11 mmol), and tetrabutylammonium iodide (0.18 g, 0.5 mmol) were added. The reaction mixture was heated to 80 °C for 18 hours, then cooled to room temperature and concentrated to […]. (Diatomaceous earth filter aid) on top. The mixture was purified by medium-pressure liquid chromatography (using a hexane solution of 0% to 100% ethyl acetate as eluent) to give the title compound, which is the compound of the present invention, in solid form (1.14 g).

[0800] 1 H NMR (CDCl3): δ8.29(s,1H),8.07(d,2H),7.13(d,2H),5.27(s,2H),3.94(s,3H).

[0801] 19 F NMR (CDCl3): δ–65.38.

[0802] The following compounds in Tables 1, 1A-92A, 2, and 1B-92B can be prepared by the methods described herein in conjunction with methods known in the art. The following abbreviations are used in the tables: t for tert-, s for sec-, n for n-, i for iso-, c for cyclo-, Me for methyl, Et for ethyl, Pr for propyl, i-Pr for isopropyl, c-Pr for cyclopropyl, Bu for butyl, i-Bu for isobutyl, t-Bu for tert-butyl, and Ph for phenyl.

[0803] Table 1

[0804]

[0805] R in Table 1 1 The definitions of R and J are as defined in examples A and B of the above implementation schemes. In column R... 1 In the diagram, the number in parentheses following the U-ring number indicates the connection point between the ring and L. (R) 2 ) x A column refers to one or more substituents attached to the U-ring, as shown in Example A above. (R) 2 ) x The dash "—" in the text means that R does not exist. 2 The substituents are present and the remaining valence is occupied by hydrogen atoms.

[0806]

[0807]

[0808]

[0809]

[0810]

[0811]

[0812] This disclosure also includes Tables 1A to 47A, each of which is constructed to be identical to Table 1 above, except that the header row in Table 1 (i.e., “L is CH2 and J is J-40”) is replaced by the corresponding header row shown below.

[0813]

[0814]

[0815] Table 2 discloses specific compounds of formula 3 that can be used as intermediates for the preparation of compounds of formula 1, as described in schemes 2 and 10 above.

[0816] Table 2

[0817]

[0818] R in Table 2 1 The definitions of R and J are as defined in examples A and B of the above implementation schemes. In column R... 1 In the diagram, the number in parentheses following the U-ring indicates the connection point between the ring and the L-ring. (R) 2 ) x A column refers to one or more substituents attached to the U-ring, as shown in Example A above. (R) 2 ) x The dash "—" in the text means that R does not exist. 2 The substituents are present and the remaining valence is occupied by hydrogen atoms.

[0819]

[0820]

[0821]

[0822]

[0823]

[0824]

[0825] This disclosure also includes Tables 1B to 47B, each of which is constructed to be identical to Table 2 above, except that the header row in Table 2 (i.e., “L is CH2 and J is J-40”) is replaced by the corresponding header row shown below.

[0826]

[0827]

[0828] Formulation / Practicality

[0829] The compounds of Formula 1 of the present invention (including their N-oxides and salts) are generally used as the fungicidal active ingredient in compositions, i.e., formulations, having at least one additional component selected from the following: surfactants, solid diluents, and liquid diluents, which serve as a carrier. The formulation or composition components are selected to be consistent with the physical properties of the active ingredient, the application method, and environmental factors such as soil type, moisture, and temperature.

[0830] Available 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 suspensions), which may optionally thicken into a gel. Common types of aqueous liquid compositions include soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspension emulsions. Common types of non-aqueous liquid compositions include emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0831] Solid compositions are generally available in the form of powders, granules, pellets, microspheres, lozenges, tablets, and filler films (including seed coatings), and 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 ingredients can be (micro)encapsulated and further formed into suspensions or solid formulations; alternatively, the entire formulation of the active ingredient can be encapsulated (or “coated”). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of emulsifiable concentrate formulations and dry granule formulations. High-concentration compositions are primarily used as intermediates for further formulation.

[0832] Before spraying, sprayable formulations are typically extended in a suitable medium. These liquid and solid formulations are formulated to be easily diluted in the spraying medium (usually water), but occasionally in another suitable medium such as aromatic hydrocarbons, paraffinic hydrocarbons, or vegetable oils. Spray volumes can range from approximately one thousand liters to several thousand liters per hectare, but more typically from approximately ten liters to several hundred liters per hectare. Sprayable formulations can be mixed with water or another suitable medium for foliar application via air or ground application, or for application to plant growth media. Liquid and dry formulations can be metered directly into drip irrigation systems or into furrows during planting. Liquid and solid formulations can be applied as seed treatments to the seeds of crops and other desired vegetation prior to planting to protect developing roots and other underground plant parts and / or leaves through systemic absorption.

[0833] The formulation will typically contain effective amounts of the active ingredient, diluent, and surfactant, which, in approximate ranges, total up to 100% by weight.

[0834]

[0835] Solid diluents include, for example, clays such as bentonite, montmorillonite, palygorskite, 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 sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd ed., Dorland Books, Caldwell, New Jersey.

[0836] Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), alkyl phosphate esters (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene glycol carbonate, butanediol carbonate, alkanes (e.g., white mineral oil, n-alkanes, isoalkanes), alkylbenzenes, alkylnaphthalenes, glycerol, triacetylglycerol, sorbitol, aromatic hydrocarbons, and dearomatized aliphatic hydrocarbons. Alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptanyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, other esters such as alkyl lactates, diesters, alkyl benzoates and aryl benzoates, and γ-butyrolactone, and alcohols that can be straight-chain, branched, saturated, or unsaturated, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isoctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol, and benzyl alcohol. Liquid diluents also include glycerides of saturated and unsaturated fatty acids (typically C6–C). 22 Oils containing plant seeds and fruits (e.g., olive oil, castor oil, flaxseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm oil), animal fats (e.g., beef 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 can be obtained by hydrolysis of glycerides from plant and animal sources and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950.

[0837] The solid and liquid compositions of this invention typically contain one or more surfactants. When added to a liquid, the surfactant (also known as a "surfactant") generally changes, most typically reducing the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant can be used as a wetting agent, dispersant, emulsifier, or defoamer.

[0838] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants that can be used in the compositions of this invention 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 alcohols and ethylene oxide, propylene oxide, butane oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and trans-block polymers wherein the terminal blocks are prepared from propylene oxide; ethyl... Oxylated fatty acids; ethoxylated fatty acid esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters such as polyethoxylated sorbitol fatty acid esters, polyethoxylated sorbitan fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitol derivatives such as sorbitol esters; polymer surfactants such as random copolymers, block copolymers, alkyd resins, PEG (polyethylene glycol) resins, grafted or comb-type polymers, and star-shaped polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; siloxane-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0839] Available anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; 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 N,N-alkyl taurine; sulfonates of benzene, isopropylbenzene, toluene, xylene and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; sulfonates of fractionated petroleum; sulfosuccinates; and sulfosuccinates and their derivatives, such as dialkylsulfosuccinates.

[0840] Available cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines, such as N-alkylpropylenediamine, tripropylenetriamine and dipropylenetetraamine, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butyl oxide or mixtures thereof); amine salts such as amine acetate and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides, such as alkyl dimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0841] Also usable in the compositions of the present invention are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic surfactants, anionic surfactants, and cationic surfactants, and their recommended uses, are disclosed in a number of published references, including McCutcheon's *Emulsifiers and Detergents*, North American and International Yearbooks published by McCutcheon, The Manufacturing Confectioner Publishing Co.; Sisley and Wood, *Encyclopedia of Surface Active Agents*, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, *Synthetic Detergents*, 7th edition, John Wiley and Sons, New York, 1987.

[0842] The compositions of the present invention may also contain formulation adjuvants and additives known to those skilled in the art as formulation auxiliaries (some of which may also be considered as solid diluents, liquid diluents, or surfactants). Such formulation adjuvants and additives can control: pH (buffers), foaming during processing (defoamers such as polysiloxanes), precipitation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth within the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), rinsing (film-forming agents or adhesives), evaporation (anti-evaporation agents), and other formulation properties. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation adjuvants and additives include those listed in: McCutcheon Volume 2: Functional Materials, North American and International Yearbooks published by McCutcheon, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03 / 024222.

[0843] Compounds of Formula 1 and any other active ingredients are typically incorporated into the compositions of the present invention 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 the liquid composition intended to be used as an emulsifiable concentrate is immiscible with water, an emulsifier is typically added during dilution with water to emulsify the solvent containing the active substance. Active ingredient slurries with particle sizes up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average diameter of less than 3 μm. Aqueous slurries can be prepared as finished suspension concentrates (see, for example, US 3,060,084) or further processed by spray drying to form water-dispersible particles. Dry formulations typically require a dry milling process, which produces an average particle size in the range of 2 μm to 10 μm. Powders and pellets can be prepared by blending and typically by milling (such as with a hammer mill or kinetic mill). Granules and pellets can be prepared by spraying the active material onto a pre-formed granular carrier or by agglomeration techniques. See Browning, “Agglomeration,” Chemical Engineering, December 4, 1967, pp. 147-48; Perry’s Chemical Engineer’s Handbook, 4th edition, McGraw-Hill, New York, 1963, pp. 8-57 and follow-up; and WO 91 / 13546. Pills may be prepared as described in US 4,172,714. Water-dispersible and water-soluble granules may be prepared as taught in US 4,144,050, US 3,920,442, and DE 3,246,493. Tablets may be prepared as taught in US 5,180,587, US 5,232,701, and US 5,208,030. Films may be prepared as taught in GB 2,095,558 and US 3,299,566.

[0844] One embodiment of the present invention relates to a method for controlling fungal pathogens, the method comprising diluting the fungicidal composition of the present invention (a compound of formula 1 formulated together with a surfactant, a solid diluent and a liquid diluent, or a 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 the diluted composition.

[0845] While spray compositions formed by diluting a sufficient concentration of the fungicidal composition of the present invention with water can provide sufficient efficacy for controlling fungal pathogens, separately formulated adjuvant products can also be added to the spray can mixture. These adjuvants are generally referred to as “spray adjuvants” or “can mixture adjuvants” and include any substance mixed in the spray can to improve the performance of the insecticide or alter the physical properties of the spray mixture. Adjuvants can be anionic or nonionic surfactants, emulsifiers, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners, or defoamers. Adjuvants are used to enhance efficacy (e.g., bioavailability, adhesion, penetration, uniform coverage, and protective durability) or to minimize or eliminate spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization, and degradation. To obtain optimal performance, adjuvants are selected based on the characteristics of the active ingredient, formulation, and target (e.g., crop, pest).

[0846] The amount of adjuvants added to the spray mixture is typically in the range of about 2.5% by volume to 0.1% by volume. The application rate of adjuvants added to the spray mixture is typically between about 1 L and 5 L per hectare. Representative examples of spray adjuvants include: (Syngenta), a liquid hydrocarbon solution of 47% methylated rapeseed oil. (Helena Chemical Company), polyepoxide-modified heptamethyltrisiloxane, and (BASF) 17% surfactant blend in 83% paraffin-based mineral oil.

[0847] One method of seed treatment is to spray or dust the seeds with the compounds of the present invention (i.e., in the form of a formulated composition) before sowing. Compositions formulated for seed treatment generally contain a film-forming agent or binder. Therefore, the seed coating compositions of the present invention typically contain a biologically effective amount of the compound of formula 1 and a film-forming agent or binder. Seed coating can be achieved by spraying a flowable suspension concentrate directly onto a tumble bed of seeds and then drying the seeds. Alternatively, other formulation types such as wet powders, solutions, suspensions, emulsions, and aqueous emulsions can be sprayed onto the seeds. This method is particularly suitable for applying film coatings to seeds. Various coating machines and methods are available to those skilled in the art. Suitable methods include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57, and the references listed therein.

[0848] For further information on formulation, see T.S. Woods, “The Formulator’s Toolbox – Product Forms for Modern Agriculture,” Pesticide Chemistry and Bioscience, The Food – Environment Challenge, edited by T. Brooks and TR. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120–133. See also US 3,235,361, column 6, lines 16-7, line 19, and Examples 10-41; US ​​3,309,192, column 5, lines 43-7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138–140, 162–164, 166, 167, and 169–182; US 2,891,855, column 3, lines 66-5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th edition, Blackwell Scientific, Oxford, 1989; and Developments in Formulation Technology, PJB Publishing, Richmond, UK, 2000.

[0849] In the following examples, all percentages are by weight, and all formulations were prepared in a conventional manner. Compound numbers refer to compounds in Index Table A. Without further detailed description, it is believed that those skilled in the art will be able to utilize the invention to the fullest extent using the foregoing description. Therefore, the following examples are to be interpreted as merely illustrative and, in any way, not as limiting the scope of this disclosure.

[0850] Example A

[0851] High-strength concentrate

[0852] Compound 21 98.5%

[0853] 0.5% silica aerogel

[0854] Synthetic amorphous fine silica 1.0%

[0855] Example B

[0856] Wetting powder

[0857]

[0858] Example C

[0859] Granules

[0860] Compound 316 10.0%

[0861] Green slope palygorskite particles (low volatile matter, 90.0%)

[0862] 0.71 / 0.30mm; USS25-50 sieve)

[0863] Example D

[0864] Extruded pills

[0865]

[0866] Example E

[0867] Emulsifiable concentrate

[0868] Compound 56 10.0%

[0869] Polyoxyethylene sorbitan hexaoleate 20.0%

[0870] C6-C 10 Fatty acid methyl esters 70.0%

[0871] Example F

[0872] microemulsion

[0873]

[0874] Example G

[0875] Seed treatment

[0876]

[0877] Example H

[0878] Fertilizer sticks

[0879]

[0880] Example I

[0881] Suspended concentrate

[0882]

[0883] Example J

[0884] water emulsion

[0885]

[0886] Example K

[0887] oil dispersion

[0888]

[0889] Example L

[0890] suspension emulsion

[0891]

[0892] Typically, water-soluble and water-dispersible formulations are diluted with water between applications to form an aqueous composition. Aqueous compositions intended for direct application to plants or parts thereof (e.g., spray can compositions) typically contain at least about 1 ppm or more (e.g., 1 ppm to 100 ppm) of one or more of the compounds of the present invention.

[0893] Seeds are typically treated at a rate of about 0.001 g (more typically about 0.1 g) to about 10 g / kg of seeds (i.e., about 0.0001% to 1% by weight of seeds before treatment). The flowable suspensions formulated for seed treatment typically contain about 0.5% to about 70% of the active ingredient, about 0.5% to about 30% of the film-forming binder, about 0.5% to about 20% of the dispersant, 0 to about 5% of the thickener, 0 to 5% of the pigment and / or dye, 0 to about 2% of the defoamer, 0 to about 1% of the preservative, and 0 to about 75% of the volatile liquid diluent.

[0894] The compounds of this invention can be used as plant disease control agents. Therefore, this invention also includes a method for controlling plant diseases caused by fungal plant pathogens, the method comprising applying an effective amount of the compound of this invention or a fungicidal composition containing said compound to the plant to be protected or to the seeds of the plant to be protected. The compounds and / or compositions of this invention provide control against diseases caused by broad-spectrum fungal plant pathogens of the Ascomycota, Basidiomycota, Zygomycota, and fungi-like Oomycetes. They are effective against a broad spectrum of plant diseases, specifically leaf pathogens of ornamental plants, turf, vegetables, field crops, cereal crops, and fruit crops. These pathogens include, but are not limited to, those listed in Table 1-1. For Ascomycota and Basidiomycota, the names for the sexual / sexual / complete stage and the names for the asexual / asexual / incomplete stage (in parentheses) are listed where known. Synonyms for pathogens are indicated by an equal sign. For example, the name for the sexual / sexual / complete stage of wheat glume blight (Phaeosphaeria nodorum) is followed by the corresponding name for the asexual / asexual / incomplete stage, Sta gnospora nodorum, and the synonymous old name Septoria nodorum.

[0895] Table 1-1

[0896]

[0897]

[0898] In addition to their antifungal activity, the compositions or combinations also exhibit activity against bacteria such as *Erwinia amylovora*, *Xanthomonas campestris*, *Pseudomonas syringae*, and other related species. By controlling harmful microorganisms, the compounds of the present invention can be used to improve (i.e., increase) the ratio of beneficial to harmful microorganisms in contact with crops or their propagations (e.g., seeds, bulbs, tubers, cuttings), or in agricultural environments of crops or their propagations.

[0899] The compounds of this invention can be used to treat all plants, plant parts, and seeds. Plant and seed varieties and cultivars can be obtained through conventional propagation and breeding methods or through genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgenic) has been stably integrated into the genome of the plant or seed. A transgenic event is defined by its specific location in the plant genome as a transformation or transgenic event.

[0900] Genetically modified plant cultivars that can be treated according to the present invention include those resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinity, etc.) or containing other desired characteristics. Plants can be genetically modified to exhibit characteristics such as herbicide tolerance, insect resistance, improved oil distribution, or drought tolerance.

[0901] Treatment of genetically modified plants and seeds with the compounds of this invention can lead to superadditional or synergistic effects. For example, reduced application rates, broadened activity profiles, increased tolerance to biotic / abiotic stresses, or enhanced storage stability can be greater than the simple additive effects expected from the application of the compounds of this invention to genetically modified plants and seeds.

[0902] The compounds of this invention can be used in seed treatment to protect seeds from plant diseases. In the context of this disclosure and claims, seed treatment means contacting seeds with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of this invention. This seed treatment protects seeds from soil-borne pathogens and generally also protects roots and other plant parts in contact with the soil of seedlings developing from germinating seeds. Seed treatment can also provide protection to leaves by translocation of the compound of this invention or a second active ingredient in the developing plant. Seed treatment is applicable to all types of seeds, including those genetically transformed to express a specific trait that the plant will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin, or those expressing herbicide resistance, such as glyphosate acetyltransferase, which provides resistance to glyphosate. Seed treatment with the compounds of this invention can also increase the vigor of plants grown from seeds.

[0903] The compounds and compositions thereof of the present invention, alone and in combination with other fungicides, nematicides and insecticides, are particularly useful for seed treatment of crops including, but not limited to, maize or corn, soybeans, cotton, cereals (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and rapeseed.

[0904] Furthermore, the compounds of the present invention can be used to treat postharvest diseases of fruits and vegetables caused by fungi and bacteria. These infections can occur before, during, and after harvesting. For example, an infection can occur before harvesting and then remain dormant until some point during maturity (e.g., the host begins tissue changes in a way that allows the infection to progress); infections can also be caused by surface wounds resulting from mechanical or insect damage. In this respect, the compounds of the present invention can reduce losses (i.e., losses in quantity and quality) due to postharvest diseases that can occur at any time from harvest to consumption. Treatment of postharvest diseases with the compounds of the present invention can increase the period during which perishable edible plant parts (e.g., fruits, seeds, leaves, stems, bulbs, tubers) can be refrigerated or not after harvesting and remain edible without significant or harmful degradation or contamination by fungi or other microorganisms. Treatment of edible plant parts before or after harvesting with the compounds of the present invention can also reduce the formation of toxic metabolites of fungi or other microorganisms, such as mycotoxins like aflatoxin.

[0905] Plant disease control is typically achieved by applying an effective amount of the compound of the present invention to the plant parts to be protected, such as roots, stems, leaves, fruits, seeds, tubers, or bulbs, before or after infection, or by applying it to the growing medium (soil or sand) of the plant to be protected. The compound can also be applied to seeds to protect seeds and seedlings developing from seeds. The compound can also be applied to treat plants via irrigation water. Control of postharvest pathogens infecting products is typically achieved by applying the compound of the present invention in the field before harvest, and in the event of postharvest infection, the compound can be applied to postharvest crops in the form of dips, sprays, fumigants, treated wrapping materials, and box liners.

[0906] The application rate of these compounds (i.e., the effective fungicide dose) can be affected by factors such as the plant disease to be controlled, the plant species to be protected, and ambient humidity and temperature, and should be determined under actual application conditions. Those skilled in the art can readily determine the effective fungicide dose necessary for the desired level of plant disease control through simple experiments. Leaves are generally protected when treated at a rate of less than about 1 g / ha to about 5,000 g / ha of active ingredient. Seeds and seedlings are generally protected when treated at a rate of about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seeds.

[0907] The compounds of the present invention can also be mixed with one or more other biologically active compounds or reagents, including fungicides, insecticides, nematicides, bactericides, acaricides, herbicides, herbicides safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemical sterilizers, chemical pheromones, insect repellents, inducers, pheromones, feeding stimulants, and phytonutrients, to form multi-component insecticides, thereby providing broader agricultural protection from other biologically active compounds or insect pathogens, viruses, or fungi. Therefore, the present invention also relates to compositions comprising a compound of formula 1 (in a fungicide effective amount) and at least one additional biologically active compound or reagent (in a biologically effective amount), and may further comprise at least one of a surfactant, a solid diluent, or a liquid diluent. Other biologically active compounds or reagents may be formulated in compositions comprising at least one of a surfactant, a solid diluent, or a liquid diluent. For the mixtures of the present invention, one or more other biologically active compounds or reagents may be formulated together with the compounds of Formula 1 to form a premix, or one or more other biologically active compounds or reagents may be formulated separately from the compounds of Formula 1 and the formulations are mixed together prior to application (e.g., in a spray can), or alternatively, applied continuously.

[0908] As described in the invention summary, one aspect of the invention is a fungicidal composition (i.e., a mixture or combination of the following substances) comprising a compound of Formula 1, its N-oxide or a salt thereof (i.e., component a), and at least one other fungicide (i.e., component b). It is noteworthy that such combinations contain other fungicide active ingredients having different sites of action than the compound of Formula 1. In some cases, combinations with at least one other fungicide active ingredient having a similar range of action but a different site of action will be particularly advantageous for resistance management. Therefore, the compositions of the invention may also contain a fungicide-effective amount of at least one additional fungicide active ingredient having a similar range of action but a different site of action.

[0909] It is noteworthy that, in addition to the compound of Formula 1 in component (a), the composition also includes at least one fungicidal compound as component (b), said at least one fungicidal compound being selected from the following FRAC-defined modes of action (MOA) types: (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (G) sterol biosynthesis in the membrane, (H) cell wall biosynthesis in the membrane, (I) melanin synthesis in the cell wall, (P) host plant defense induction, multi-site contact activity, and unknown modes of action.

[0910] The target sites identified or proposed by FRACs, which are connected to the target sites of FRACs belonging to the above-mentioned MOA class, are encoded as follows: (A1) RNA polymerase I, (A2) adenosine deaminase, (A3) DNA / RNA synthesis (proposed), (A4) RNA topoisomerase, (B1-B3) β-microtubule assembly in mitosis, (B4) cell division (proposed), (B5) delocalization of spectroscopy-like proteins, (C1) INADH racemic-reductase complex, (C2) succinate dehydrogenase complex II, (C3) cytochrome bc1 (ubiquinone reductase) at the Qo site of the complex, (C4) cytochrome bc1 (ubiquinone reductase) at the Qi site of the complex, (C5) oxidative phosphorylation uncoupling agent, (C6) inhibitor of oxidative phosphorylation, ATP synthase, (C7) ATP production (proposed), (C8) cytochrome bc1 (ubiquinone reductase) at the Qx (unknown) site of the complex. (Original enzyme), (D1) Methionine biosynthesis (proposed), (D2-D5) Protein synthesis, (E1) Signal transduction (mechanism unknown), (E2-E3) MAP / histamine kinase in osmotic signal transduction, (F2) Phospholipid biosynthesis, methyltransferase, (F3) Lipid peroxidation (proposed), (F4) Cell membrane permeability, fatty acids (proposed), (F6) Microbial disruption of pathogen cell membranes, (F7) Cell membrane disruption (proposed), (G 1) C14-demethylase in sterol biosynthesis, (G2) Δ14-reductase and Δ8→Δ7-isomerase in sterol biosynthesis, (G3) 3-ketoreductase, C4-demethylation, (G4) squalene epoxidase in sterol biosynthesis, (H3) trehalase and inositol biosynthesis, (H4) chitin synthase, (H5) cellulase, (I1) reductase in melanin biosynthesis, and (I2) dehydrogenase in melanin biosynthesis.

[0911] Of particular note is the composition comprising, in addition to the compound of formula 1 in component (a), at least one fungicidal compound as component (b), wherein the at least one fungicidal compound is of the following type: (b1) methyl benzimidazole carbamate (MBC) fungicide; (b2) dicarboximide fungicide; (b3) demethylation inhibitor (DMI) fungicide; (b4) phenylamide fungicide; (b5) amine / morpholine fungicide; (b6) phospholipid biosynthesis inhibitor fungicide; (b7) succinate dehydrogenase inhibitor fungicide; b8) Hydroxy(2-amino-)pyrimidine fungicides; (b9) Aniline pyrimidine fungicides; (b10) N-phenylcarbamate fungicides; (b11) Quinone external inhibitors (QoI) fungicides; (b12) Phenylpyrrole fungicides; (b13) Azanaphthalene fungicides; (b14) Lipid peroxidation inhibitor fungicides; (b15) Melanin biosynthesis inhibitor reductase (MBI-R) fungicides; (b16) Melanin biosynthesis inhibitor dehydratase (MBI-D) fungicides; (b17) Sterol biosynthesis inhibitors ( SBI): Class III fungicides; (b18) Squalene-cyclooxygenase inhibitor fungicides; (b19) Polyoxin fungicides; (b20) Phenylephrine fungicides; (b21) Quinone internal inhibitor (QiI) fungicides; (b22) Benzamide and thiazole fungicides; (b23) Enolpyranose antibiotic fungicides; (b24) Hexopyranose antibiotic fungicides; (b25) Gluopyranose antibiotics: protein synthesis fungicides; (b26) Gluopyranose antibiotics: trehalase and inositol biosynthesis (b27) Cyanoacetamide oxime fungicide; (b28) Carbamate fungicide; (b29) Oxidative phosphorylation uncoupling fungicide; (b30) Organotin fungicide; (b31) Carboxylic acid fungicide; (b32) Heteroaromatic fungicide; (b33) Phosphate fungicide; (b34) o-Carbamoylbenzoic acid fungicide; (b35) Benzotriazine fungicide; (b36) Benzenesulfonamide fungicide; (b37) Pyridazinone fungicide; (b38) Thiophene-formamide fungicide; (b39) Complex I NADH oxidoreductase inhibitors (fungicides); (b40) Carboxylamide (CAA) fungicides; (b41) Tetracycline antibiotics (fungicides); (b42) Thiocarbamate fungicides; (b43) Benzamide fungicides; (b44) Microbial fungicides; (b45) Q x I. Fungicides; (b46) Plant extract fungicides; (b47) Host plant defense-inducing fungicides; (b48) Multi-site contact active fungicides; (b49) Fungicides that are not fungicides of categories (b1) to (b48); and salts of compounds of categories (b1) to (b48).

[0912] Further description of these classes of antifungal compounds is provided below.

[0913] (b1) "Benzimazole methyl carbamate (MBC) fungicides" (FRAC code 1) inhibit mitosis by binding to β-microtubules during microtubule assembly. Inhibition of microtubule assembly disrupts cell division, intracellular transport, and cell structure. Benzimazole methyl carbamate fungicides include benzimidazole and thiophanate-methyl fungicides. Benzimidazole includes benomyl, carbendazim, thiamethoxam, and thiamethoxam. Thiophanate-methyl includes thiophanate-methyl and methyl thiophanate-methyl.

[0914] (b2) "Dicarboximide fungicides" (FRAC No. 2) inhibit MAP / histamine kinase in osmotic signal transduction. Examples include tebufenozide, iprodione, procymidone, and vinclozolin.

[0915] (b3) "Demethylation Inhibitor (DMI) Fungicides" (FRAC code 3) (Sterol Biosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylases that play a role in sterol production. Sterols, such as ergosterol, are required for membrane structure and function, making them crucial for the development of functional cell walls. Therefore, exposure to these fungicides leads to abnormal growth and eventual death of susceptible fungi. DMI fungicides are classified into several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines, pyridines, and triazolinethions. Triazoles include tebuconazole, bifenthrin, bromoxynil, cyproconazole, oxadiazon, tebuconazole (including tebuconazole-M), flutriafol, eticonazole, fenoxam, fluquinazole, flusilazole, fenbuconazole, hexaconazole, imidacloprid, tebuconazole, tebuconazole, propiconazole, quinconazole, silfluzazole, tebuconazole, tetrafluoroether, triadimefon, triadimefon, tebuconazole, uniconazole, uniconazole-P, α-(1-chloropropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, rel-1-[[(2R,3S)-3-( [2-Chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole. Imidazoles include econazole, imazalil, oxadiazine, imazalil, isoprothiolane, and fluopyram. Pyrimidines include chloropyrimidinol, flupyrimidinol, and pyraclostrobin. Piperazines include pyrazinazole. Pyridines include bis(2-methyl)pyridine, pyridoxime, pyridodioxazole (a mixture of 3-[(3R)-5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolinyl]-pyridine, 3R,5R-isomers, and 3R,5S-isomers), and (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol. Triazolinethions include prothioconazole and 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazol-3-thione.Biochemical studies have shown that all the fungicides mentioned above are DMI fungicides, as described by KHKuck et al. in Modern Selective Fungicides-Properties, Applications and Mechanisms of Action, H. Lyr (ed.), Gustav Fischer Verlag: New York, 1995, 205–258.

[0916] (b4) "Phenylamides" (FRAC code 4) are specific inhibitors of RNA polymerase in oomycete fungi. Susceptible fungi exposed to these fungicides exhibit a reduced ability to bind uridine to rRNA. Exposure to these fungicides can prevent the growth and development of susceptible fungi. Phenylamides include acylalanine, oxazolidinone, and butyrolactone fungicides. Acylalanine fungicides include benzalkonium chloride, benzalkonium chloride-M (also known as methylbenzalkonium chloride), furazolidone, metalaxyl, and metalaxyl-M (also known as methylmetalaxyl). Oxazolidinone fungicides include oxazolidinium. Butyrolactone fungicides include meflurane.

[0917] (b5) "Amine / morpholine fungicides" (FRAC code 5) (SBI: Class II) inhibit two target sites in the sterol biosynthesis pathway, Δ 8 →Δ 7 Isomerase and Δ 14 Reductases. Sterols, such as ergosterol, are required for membrane structure and function, making them crucial for the development of functional cell walls. Therefore, exposure to these fungicides leads to abnormal growth and eventual death of susceptible fungi. Amine / morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholines, piperidines, and spiroketone acetals. Morpholines include aldimorph, dodecylmorpholine, butylmorpholine, tridecamorpholine, and cyclomethonamide. Piperidines include benzyl benzoate and spiroketone acetals. Spiroketone acetals include spirocylamide.

[0918] (b6) "Phospholipid biosynthesis inhibitors fungicides" (FRAC code 6) inhibit fungal growth by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include thiophosphates and dithiopentyl fungicides. Thiophosphates include dichlorvos, isoprothiolane, and dimethomorph. Dithiopentyl fungicides include isoprothiolane.

[0919] (b7) "Succinate dehydrogenase inhibitors (SDHI) fungicides" (FRAC code 7) inhibit the respiration of Complex II fungi by disrupting a key enzyme in the Krebs cycle (TCA cycle) called succinate dehydrogenase. Inhibition of respiration prevents fungal ATP production, thereby inhibiting growth and reproduction. SDHI fungicides include phenylbenzamide, furfural, oxothiazines, thiazole, pyrazole-4-carboxamide, pyridinecarboxamide, phenyloxoethylthiophenamide, and pyridineethylbenzamide. Benzamides include carboxin, fluoxetine, and thiocarboxamide. Furanamides include thifluzamide. Oxothiazines include carboxin and oxothiazines. Thiazolecarboxamides include thifluzamide. Pyrazole-4-carboxamides include benzo[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-bridged methylenenaphthyl-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, bifenthiophanate-methyl, fluopyram, and fluopyram (3-(difluoromethyl)-1-methyl-N-(3',4',5'-trifluoro[1,1'-biphenyl]-2-yl). -1H-pyrazole-4-carboxamide), Forabi, pyrazolenaphthylamine (3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanenaphth-5-yl]-1H-pyrazole-4-carboxamide), fluopyram aniline (N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide), pyrimethanil Amines, fluoxastrobin (N-[2-[1,1'-dicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide), N-[2-(1S,2R)-[1,1'-dicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl) Pyridine carboxamides include pyridoxin (N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyridoxin-4-carboxamide, and N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methylethyl)]phenyl]methyl]-1H-pyridoxin-4-carboxamide. Pyridine carboxamides include boscalidamide. Phenyroxoethylthiophenamides include isopropylthiophenamide (N-[1,1-dimethyl-2-[2-methyl-4-(1-methylethoxy)phenyl]-2-oxoethyl]-3-methyl-2-thiophene carboxamide). Pyridylethylbenzamides include fluopyram.

[0920] (b8) "Hydroxy(2-amino-)pyrimidine fungicides" (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include ethirimol sulfonate, methylphenidate, and ethirimol.

[0921] (b9) "Phenylemine fungicides (FRAC code 9) are designed to inhibit the biosynthesis of the amino acid methionine and disrupt the secretion of hydrolytic enzymes that dissolve plant cells during infection. Examples include pyrimethanil, azoxystrobin, and pyrimethanil."

[0922] (b10) "N-Phenylecarbamate fungicides" (FRAC code 10) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly disrupts cell division, intracellular transport, and cell structure. Examples include acetamiprid.

[0923] (b11) The "quinone external inhibitor (QoI) fungicide" (FRAC code 11) inhibits mitochondrial respiration of Complex III in fungi by affecting ubiquitin oxidase. The oxidation of ubiquitin occurs at the "quinone external" (QoI) site of the cytochrome bc1 complex located in the inner mitochondrial membrane of the fungus. oBlocking at the site. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone external inhibitors of fungicides include methoxyacrylates, methoxycarbamates, oxime acetates, oxime acetamides, and dihydrodioxazine fungicides (also collectively referred to as methoxyacrylate fungicides), oxazolidinones, imidazolinones, and benzylcarbamate fungicides. Methoxyacrylates include azoxystrobin, eugenol ((αE)-2-[[(3-butyl-4-methyl-2-oxo-2H-1-benzopyran-7-yl)oxy]methyl]-α-(methoxymethylene)phenylacetic acid methyl ester), and oxadiazon ((αE)-2-[[[(E)-[(2E)-3-(4-chlorophenyl)-1-methyl-2-propen-1-yl]amino]oxy]methyl]-α-( Methyl methoxymethylene phenylacetate (also known as tebufenozide), flufenoxuron ((αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)phenylacetate), pyraclostrobin, and azoxystrobin ((αE)-2-[[[3-(4-chlorophenyl)-1-methyl-1H-pyrazol-5-yl]oxy]methyl]-α-(methoxymethylene)phenylacetate). Methoxycarbamates include azoxystrobin, methyl azoxystrobin (N-[2-[[(1,4-dimethyl-3-phenyl-1H-pyrazol-5-yl)oxy]methyl]phenyl]-N-methoxycarbamate, and chlorpyrifos (N-methoxy-N-[2-[[(3,5,6-trichloro-2-pyridyl)oxy]methyl]phenyl]carbamate). Oxime acetates include cymoxanil and oximetrifos. Oxime acetamides include fenvalerate and tebufenozide ((αE)-2-[[[(E)-[(2E)-3-(2,6-dichlorophenyl)-1-methyl-2-propane)). [[[(2,5-dimethylphenoxy]methyl]-α-(methoxyimino)-N-methylphenylacetamide], phenoxyacetamide, oxime ether amine, and α-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]phenylacetamide. Dihydrodioxazins include flupyraclostrobin. Oxazolidinones include oxazolidinone. Imidazolinones include imidacloprid. Benzylcarbamates include pyraclostrobin. Class (b11) also includes m-mansterin (2-[(2,5-dimethylphenoxy)methyl]-α-methoxy-N-phenylacetamide).

[0924] (b12) "Phenylopyrrole fungicides" (FRAC code 12) inhibit MAP / histidine kinases associated with osmotic signal transduction in fungi. Seed dressings and fludioxons are examples of this class of fungicides.

[0925] (b13) "Azanaphthyl fungicides" (FRAC code 13) are designed to inhibit signal transduction through mechanisms previously unknown. They have been shown to interfere with germination and / or appressorium formation in fungi that cause powdery mildew. Azanaphthyl fungicides include aryloxyquinolines and quinazolinones. Aaryloxyquinolines include fenofibrate. Quinazolinones include propoxyquinoline.

[0926] (b14) "Lipid peroxidation inhibitor fungicides" (FRAC code 14) are designed to inhibit lipid peroxidation that affects membrane synthesis in fungi. Members of this class, such as tebuconazole, can also affect other biological processes, such as respiration and melanin biosynthesis. Lipid peroxidation fungicides include aromatic hydrocarbon and 1,2,4-thiadiazole fungicides. Aromatic hydrocarbon fungicides include biphenyl, dimethoate, chloronitrobenzene, pentachloronitrobenzene, tetrachloronitrobenzene, and methyl thiophanate. 1,2,4-thiadiazoles include tebuconazole.

[0927] (b15) "Melanin Biosynthesis Inhibitor Reductase (MBI-R) Fungicides" (FRAC code 16.1) inhibit the naphthalyl reduction step in melanin biosynthesis. Melanin is required for host plants to be infected by certain fungi. Melanin biosynthesis inhibitor reductase fungicides include isobenzofuranones, pyrroloquinolones, and triazolobenzothiazole fungicides. Isobenzofuranones include tetrachlorophthalide. Pyrroloquinolones include pyrroloquinones. Triazolobenzothiazoles include tricyclazoles.

[0928] (b16) "Melanin Biosynthesis Inhibitor Dehydrating Enzyme (MBI-D) Fungicide" (FRAC code 16.2) inhibits the microsporidium dehydrating enzyme in melanin biosynthesis. Melanin is required for host plants to be infected by some fungi. Melanin biosynthesis inhibitor dehydrating enzyme fungicides include cyclopropaneformamide, formamide, and propionamide fungicides. Cyclopropaneformamide includes cyclopropionamide. Formamide includes cyhalofop-p-ethyl. Propionamide includes cyhalofop-p-ethyl.

[0929] (b17) "Sterol Biosynthesis Inhibitors (SBI): Class III Fungicides" (FRAC code 17) inhibit 3-keto reductase during C4-demethylation in sterol production. SBI: Class III inhibitors include hydroxyaniline fungicides and aminopyrazolone fungicides. Hydroxyanilines include cyclopyrazol. Aminopyrazolones include pyrazo ...

[0930] (b18) "Squalene-Cyclooxygenase Inhibitors" (FRAC code 18) (SBI: Class IV) inhibit squalene-cyclooxygenase in the sterol biosynthesis pathway. Sterols, such as ergosterol, are required for membrane structure and function, making them crucial for the development of functional cell walls. Therefore, exposure to these fungicides leads to abnormal growth and eventual death of susceptible fungi. Squalene-cyclooxygenase inhibitors include thiocarbamates and allylamines. Thiocarbamates include barnyardgrass. Allylamines include netitin and terbinafine.

[0931] (b19) "Polyoxin fungicide" (FRAC code 19) inhibits chitin synthase. Examples include polyoxin.

[0932] (b20) "Phenylephrine fungicides" (FRAC code 20) are designed to affect cell division. Examples include pendimethalin.

[0933] (b21) The "quinone interior inhibitor (QiI) fungicide" (FRAC code 21) inhibits mitochondrial respiration of Complex III in fungi by affecting ubiquinone reductase. The reduction of ubiquinone in the "quinone interior" (QiI) of the cytochrome bc1 complex located in the inner mitochondrial membrane of fungi... i Blocking at the ) site. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Internal quinone inhibitors of fungicides include cyanimidazole and ammoniasulfonyltriazole fungicides. Cyanoimidazole includes cyproconazole. Ammoniasulfonyltriazole includes indoxofensulfonamide.

[0934] (b22) "Benzamide and thiazocarboxamide fungicides" (FRAC code 22) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly disrupts cell division, intracellular transport, and cell structure. Benzamides include oxalamide. Thiazolecarboxamides include thiazocarboxamide.

[0935] (b23) "Enolpyranouronic acid antibiotic fungicides" (FRAC code 23) inhibit fungal growth by affecting protein biosynthesis. Examples include blastomycin-S.

[0936] (b24) "Hexylpyranosyl antibiotics (FRAC code 24) inhibit fungal growth by affecting protein biosynthesis. Examples include kasugamycin."

[0937] (b25) "Glucanopyranosyl antibiotics: protein synthesis fungicides" (FRAC code 25) inhibit fungal growth by affecting protein biosynthesis. Examples include streptomycin.

[0938] (b26) "Gluranyl-based antibiotics: fungicides that inhibit the biosynthesis of trehalase and inositol" (FRAC code 26) inhibit the biosynthesis of trehalase and inositol. Examples include jinggangmycin.

[0939] (b27) "Cyanoacetamide oxime fungicides" (FRAC code 27) include cymoxanil.

[0940] (b28) "Carbamate fungicides" (FRAC code 28) are considered multisite inhibitors of fungal growth. They are designed to interfere with the synthesis of fatty acids in the cell membrane, which in turn disrupts cell membrane permeability. Propamocarb, iodopropynyl butylcarbamate, and thiocarb are examples of this type of fungicide.

[0941] (b29) "Oxidative phosphorylation uncoupling fungicides" (FRAC code 29) inhibit fungal respiration through uncoupling oxidative phosphorylation. Inhibition of respiration prevents normal fungal growth and development. This type includes 2,6-dinitroanilines such as fluazinam, and crotonic acid dinitrophenyl esters such as abamectin, fenvalerate, and chlorfenapyr.

[0942] (b30) "Organotin fungicides" (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in the oxidative phosphorylation pathway. Examples include triphenyltin acetate, triphenylene chloride, and triphenyltin hydroxide.

[0943] (b31) "Carboxylic acid fungicides" (FRAC code 31) inhibit fungal growth by affecting type II deoxyribonucleic acid (DNA) topoisomerase (gyrase). Examples include oxaquinic acid.

[0944] (b32) "Hybrid aromatic fungicides" (FRAC No. 32) are designed to affect DNA / ribonucleic acid (RNA) synthesis. Hybrid aromatic fungicides include isoxazoles and isothiazolones. Isoxazoles include hymexazol, and isothiazolones include octahidone.

[0945] (b33) "Phosphoester fungicides" (FRAC code 33) include phosphorous acid and its various salts, including aluminum tris(ethylphosphonate).

[0946] (b34) "o-carbamoylbenzoic acid bactericides" (FRAC code 34) include chlorothalonil.

[0947] (b35) "Benzotriazine fungicides" (FRAC code 35) include imidazosin.

[0948] (b36) "Benzylsulfonamide fungicides" (FRAC code 36) include sulfonamides.

[0949] (b37) “Pyridazinone fungicides” (FRAC code 37) include pyridaben.

[0950] (b38) "Thiophene-formamide fungicides" (FRAC code 38) are designed to affect ATP production. Examples include silthiamethoxam.

[0951] (b39) "Complex I NADH oxidoreductase inhibitor fungicides" (FRAC code 39) inhibit electron transport in mitochondria and include pyrimidine amides such as diflubenzuron and pyrazole-5-carboxamides such as acetamiprid.

[0952] (b40) "Carboxylic amide (CAA) fungicides" (FRAC code 40) inhibit cellulase, which prevents growth and leads to the death of the target fungus. Carboxylic amide fungicides include cinnamic acid amide, valine amide and other carbamates, as well as mandelic acid amide fungicides. Cinnamic acid amides include dimethomorpholine, flumorpholine, and pyrmorpholine (3-(2-chloro-4-pyridyl)-3-[4-(1,1-dimethylethyl)phenyl]-1-(4-morpholinyl)-2-propen-1-one). Valamide and other carbamates include benzimidazole, benzimidazole-isopropyl, propineb, tolprocarb (N-[(1S)-2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate 2,2,2-trifluoroethyl ester), and valamide (N-[(1-methylethoxy)carbonyl]-L-valyl-3-(4-chlorophenyl)-β-alanine methyl ester) (also known as cymoxanil). Mandelic acid amides include diacetyl amide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethanesulfonyl)amino]butamide, and N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethanesulfonyl)amino]butamide.

[0953] (b41) "Tetracycline antibiotics (FRAC code 41) inhibit fungal growth by affecting protein synthesis. Examples include oxytetracycline."

[0954] (b42) "Thiocarbamate fungicides" (FRAC code 42) include sulfadiazine.

[0955] (b43) "Benzamide fungicides" (FRAC code 43) inhibit fungal growth by delocalizing spectroscopy. Examples include pyridylmethylbenzamide fungicides, such as fluopyram (now FRAC code 7, pyridylethylbenzamide).

[0956] (b44) "Microbial fungicides" (FRAC code 44) disrupt the cell membranes of fungal pathogens. Microbial fungicides include species of the genus Bacillus, such as Bacillus amyloliquefaciens strains QST 713, FZB24, MB1600, D747, and the fungicidal lipopeptides they produce.

[0957] (b45) "Q" x I fungicides (FRAC No. 45) work by affecting an unknown (Q) cytochrome bc1 complex. x Ubiquinone reductase at the site of [Q] inhibits mitochondrial respiration of Complex III in fungi. Inhibition of mitochondrial respiration prevents normal fungal growth and development. x I. Fungicides include triazolopyrimidine amines, such as azithromycin (5-ethyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidine-7-amine).

[0958] (b46) "Plant extract fungicides" are designed to work by disrupting cell membranes. Plant extract fungicides include terpenes and terpene alcohols, such as extracts from Melaleuca alternifolia (tea tree).

[0959] (b47) “Host-plant defense-inducing fungicides” (FRAC code P) induce host plant defense mechanisms. Host-plant defense-inducing fungicides include benzothiadiazole, benzisothiazazole, and thiadiazole-formamide fungicides. Benzothiadiazole includes aramid-type benzyl-S-methyl. Benzisothiazazole includes allylisothiazazole. Thiadiazole-formamide includes thiamethoxam and isothiazine.

[0960] (b48) "Multi-site contact active fungicides" inhibit fungal growth through multiple sites of action and have contact / preventive activity. Such fungicides include: (b48.1) "Copper fungicide" (FRAC code M1), (b48.2) "Sulfur fungicide" (FRAC code M2), (b48.3) "Dithiocarbamate fungicide" (FRAC code M3), (b48.4) "Phenylimide fungicide" (FRAC code M4), (b48.5) "Chlorocyanide fungicide" (FRAC code M5), (b48.6) "Sulfonamide fungicide" (FRAC code M6), (b48.7) "Guidine fungicide" (FRAC code M7) with multiple contact sites, (b48.8) "Triazine fungicide" (FRAC code M8), (b48.9) "Quinone fungicide" (FRAC code M9), (b48.10) "Quinoxaline fungicide" (FRAC code M10), and (b48.11) "Maleimide fungicide" (FRAC code M11). "Copper fungicides" are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate, and copper hydroxide, including compositions such as Bordeaux mixtures (ternary copper sulfate). "Sulfur fungicides" are inorganic chemicals containing a ring or chain of sulfur atoms; examples include elemental sulfur. "Dithiocarbamate fungicides" contain a dithiocarbamate moiety; examples include mancozeb, methyl mancozeb, ferrous sulfate, mancozeb, thiram, zinc sulfate, and thiram. "Phyllium imide fungicides" contain a phthalimide moiety; examples include captan, thiophanate-methyl, and dichlorvos. "Chlorothalonil fungicides" contain an aromatic ring substituted with chlorine and cyanide; examples include chlorothalonil. "Sulfoamide fungicides" include sulfadiazine and toluenesulfonamide. Multi-site contact "guanidine fungicides" include chlorfenapyr, alkylbenzene sulfonate, and biguanide octylamine acetate. "Triazine fungicides" include difenoconazole. "Quinone fungicides" include dithionol. "Quinoxoline fungicides" include miticide (also known as acaricide). "Maleimide fungicides" include fluoroimide.

[0961] (b49) "Fungicides that are not in categories (b1) through (b48)" includes certain fungicides whose mode of action may be unknown. These include: (b49.1) "Phenylacetamide fungicides" (FRAC code U6), (b49.2) "Arylphenyl-ketone fungicides" (FRAC code U8), (b49.3) "Guanidin fungicides" (FRAC code U12), (b49.4) "Thiazolidinyl fungicides" (FRAC code U13), (b49.5) "Pyrimidinone-hydrazone fungicides" (FRAC code U14), and (b49.6) compounds that bind to oxysterone-binding proteins, such as those published in PCT Patent WO. As described in 2013 / 009971. Phenylacetamides include cyclofluoroacetamide and N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]phenylacetamide. Arylphenyl ketones include benzophenone, such as benzopyridine, and benzoylpyridine, such as flufenoxuron (5-chloro-2-methoxy-4-methyl-3-pyridyl)(2,3,4-trimethoxy-6-methylphenyl) ketone. Guanidines include dextrin. Thiazolidines include ((2Z)-2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinyl]acetonitrile. Pyrimidinone hydrazones include pyrimethanil. (b49.6) includes oxothiazolinone (1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl] ethyl ketone) and its R-enantiomer, which is 1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl] ethyl ketone (registration number 1003319-79-6).(b49) also includes bethoxazin, frometoquin (2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinyl methyl carbonate), fluoroimide, neoassurin (arsine ferric ammonium), picarbutrazox (N-[6-[[[[(Z)-1-methyl-1H-tetrazol-5-yl]phenylmethylene]amino]oxy]methyl]-2-pyridyl]carbamate 1,1-dimethyl ethyl ester), pyrrolidine group, miticide, tebufloquin ((6-(1,1-dimethylethyl)-8-fluoro-2,3-di... Methyl-4-quinolinyl acetate), mesotrione (N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide), 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-ylN-[6[[[[(1-methyl-1H-tetrazol-5-yl]phenylmethylene]amino]oxy]methyl]-2-pyridyl]carbamate, (N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide), N'-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethylene] Aminoamides, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]phenylacetamide, 2,6-dimethyl-1H,5H-[1,4]dithiacyclohexadiene[2,3-c:5,6-c']-dipyrrole-1,3,5,7(2H,6H)-tetraone, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine, and 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, N-[6-[[[[ [(1-Methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridyl]carbamate, N-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate, and N-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridyl]carbamate. In addition to the specific classes mentioned above (e.g., (b1), (b10), and (b22)), class (b46) also includes fungicides that inhibit mitosis and cell division.

[0962] The additional “fungicides that are not of class (1) to (46)” whose mode of action may be unknown or may not yet be classified include fungicides selected from components (b49.7) to (b49.12), as shown below.

[0963] Component (b49.7) relates to compounds of formula b49.7.

[0964]

[0965] Where R b1 for or

[0966] Examples of compounds of formula b49.7 include (b49.7a) (2-chloro-6-fluorophenyl)-methyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl]-4-piperidinyl]-4-thiazole-carboxylic acid methyl ester (registration number 1299409-40-7) and (b49.7b) (1R)-1,2,3,4-tetrahydro-1-naphthyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]acetyl]-4-piperidinyl]-4-thiazole-carboxylic acid ester (registration number 1299409-42-9). Methods for preparing compounds of formula b46.2 are described in PCT patent publications WO 2009 / 132785 and WO 2011 / 051243.

[0967] Component (b49.8) relates to compounds of formula b49.8.

[0968]

[0969] Where R b2 For CH3, CF3, or CHF2; R b3 For CH3, CF3, or CHF2; R b4 It is a halogen or cyano group; and n is 0, 1, 2 or 3.

[0970] Examples of compounds of formula b49.8 include (b49.8a)1-[4-[4-[5-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetone. Methods for preparing compounds of formula b49.8 are described in PCT patent application PCT / US11 / 64324.

[0971] Component (b4799) relates to compounds of formula b49.9.

[0972]

[0973] Where R b5 is -CH2OC(O)CH(CH3)2, -C(O)CH3, -CH2OC(O)CH3, -C(O)OCH2CH(CH3)2 or

[0974] Examples of compounds of formula b49.9 include (b49.9a)[[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxane-3-yl]amino]carbonyl]-3-pyridyl]oxy]methyl 2-methylpropionate (registration number 517875-34-2), (b49.9b)(3S,6S) (b49.9c)(3S,6S,7R,8R)-3-[[[3-(acetoxy)-4-methoxy-2-pyridyl]-carbonyl]-amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxane-7-yl-2-methacrylate (registration number 234112-93-7), (b49.9c)(3S,6S,7R,8R)-3-[[[3[(acetoxy)-methoxy]-4-methoxy-2-pyridyl]carbonyl]amino [[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxane-7-yl 2-methylpropionate (registration number 517875-31-9), (b49.9d)(3S,6S,7R,8R)-3[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxane- 7-yl-2-methylpropionate (registration number 328256-72-0) and (b49.9e)N-[[3-(1,3-benzodioxane-5-ylmethoxy)-4-methoxy-2-pyridyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxypropyl)-2-(phenyl-methyl)-L-arabinoyl]-L-serine,(1→4')-lactone (registration number 1285706-70-8). Methods for preparing compounds of formula b49.9 are described in PCT patent publications WO 99 / 40081, WO 2001 / 014339, WO 2003 / 035617 and WO 2011044213.

[0975] Component (b49.10) relates to compounds of formula b49.10.

[0976]

[0977] Where R b6 It is H or F, and R b7The form is -CF2CHFCF3 or -CF2CF2H. Examples of compounds of formula b49.10 are (b49.10a) 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoro-propoxy)]phenyl]-1-methyl-1H-pyrazole-4-carboxamide (registration number 1172611-40-3) and (b49.10b) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide (registration number 923953-98-4). Compounds of formula 49.10 can be prepared by the method described in PCT patent publication WO 2007 / 017450.

[0978] Component b49.11 relates to compounds of formula b49.11.

[0979]

[0980] in

[0981] R b8 It is a C1-C4 alkoxy or C2-C4 alkynyl group of halogen;

[0982] R b9 It is H, halogen, or C1-C4 alkyl;

[0983] R b10 For C1-C 12 Alkyl, C1-C 12 Haloalkyl, C1–C 12 Alkoxy, C2-C 12 Alkoxyalkyl, C2-C 12 alkenyl, C2-C 12 alkynyl group, C4-C 12 Alkoxyalkenyl, C4-C 12 Alkoxyalkynyl, C1-C 12 Alkyl thio or C2-C 12 Alkylthioalkyl;

[0984] R b11 Methyl or –Y b13 -R b12 ;

[0985] R b12 It is a C1-C2 alkyl group; and

[0986] Y b13 It can be CH2, O, or S.

[0987] Examples of compounds of formula b49.11 include (b49.11a) 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide, (b49.11b) 2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide, (b49.11c) N-(1, 1-Dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide, (b49.11d)2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propynyl)-1-yl)-2-(methylthio)acetamide, and (b49.11e)2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butyramide. Compounds of formula b49.11, their use as fungicides, and methods of preparation are generally known; see, for example, PCT patent publications WO 2004 / 047538, WO 2004 / 108663, WO 2006 / 058699, WO 2006 / 058700, WO 2008 / 110355, WO 2009 / 030469, WO 2009 / 049716 and WO 2009 / 087098.

[0988] Component 49.12 involves N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidin, which is believed to inhibit C24-methyltransferase involved in sterol biosynthesis.

[0989] Therefore, it is noteworthy that mixtures (i.e., compositions) comprising a compound of formula 1 and at least one fungicidal compound selected from categories (1) to (49) above are included. It is also noteworthy that compositions comprising the mixture (in an effective fungicidal amount) and further comprising at least one additional component selected from surfactants, solid diluents, and liquid diluents are included. Particularly noteworthy are mixtures (i.e., compositions) comprising a compound of formula 1 and at least one fungicidal compound selected from the specific compounds listed above relating to categories (1) to (49). Particularly noteworthy are compositions comprising the mixture (in an effective fungicidal amount) and further comprising at least one additional surfactant selected from surfactants, solid diluents, and liquid diluents are included.

[0990] Examples of fungicides in component (b) include aramid-type benzyl-S-methyl, azoxystrobin, pyraclostrobin, indoxam, tebuconazole, pyraclostrobin, benzalkonium chloride (including benzalkonium chloride-M), cymoxanil, benomyl, benomyl (including benzalkonium chloride-isopropyl), benzovindiflubenzuron, bethoxazin, chlorfenapyr, biphenyl, bispyrimethanil, bifenpyroxanil, cymoxanil, cymoxanil, pyrimethanil, furazolidone, pyrimethanil sulfonate, dicofol, captan, carbendazim, carbendazim, cymoxanil, cymoxanil, cymoxanil, chlorothalonil, ethoxysulfuron, clotrimazole, copper hydroxide, copper oxychloride, copper sulfate, buprofen, cyazofamid, cymoxanil, cymoxanil, pyrimethanil, cymoxanil, pyrimethanil, diclofenac, pyridaben, chlorpyrifos, ethoxysulfuron, oxadixyl. Azoxystrobin, diflubenzuron, dimethomorph, dimethomorph, tebuconazole, tebuconazole (including tebuconazole-M), difenoconazole, dianthraquinone, dithiazoline, dithiocarbamate, phosmet, spodoxystrobin, econazole, chlorpyrifos, tebuconazole (also known as tebuconazole), flutriafol, eticonazole, thiamethoxam, ethirimol, chlorpyrifos, oxadiazon, imidacloprid, chlorpyrifos, tebuconazole, cyproconazole, methamidophos, cyclopyrifos, fenonamide, seed dressing, benzyl benzoate, fipronil, fenproxetine, fenproxetine acetate, fenproxetine chloride, fenproxetine hydroxide, ferrous sulfate, pyraclostrobin, flumectin, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinamimide, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam Sulfovirdiamide, Flutinib, Tetrachlorophthalide, Wheat bran, Furazolidone, Furazolidone, Biguanide salts, Hexaconazole, Hymexazol, Imazalil, Imidazole, Biguanide trioctanebenzenesulfonate, Biguanide octamine acetate, Iodopropynyl butyl methylamine ester, Izoxystrobin, Isopyram, Propranolol, Isokonazole, Isopyram, Isopyram, Pyraclostrobin, Isopyram, Kasugamycin, Azoxystrobin, Mancozeb, Dimethomorph, Mandestrobin, Azoxystrobin, Cymoxanil, Metalaxyl, Metalaxyl-M / Methamphetamine, Ethiophanate-methyl, Sulfocarb, Mancozeb, Phenoxybenzonitrate, Benomyl, Miconazole, Cyproconazole, Naftifine, Ferrous ammonium sulfate, Flufenoxuron, Octethiazoline Furazolidone, oxathiapiprolin, oxadiazon, oxadiazon, oxadiazon, oxytetracycline, isoprothiolane, tebuconazole, fenpropathrin, fluopyram, pyraclostrobin, phosphorous acid (including its salts, such as aluminum tris(ethyl phosphonate)), pyrrolizazole, azoxystrobin, pyraclostrobin, polyoxin, thiamethoxam, prochloraz, iprodione, propiconazole, zinc methyl, propoxyquin, thiophanate-methyl, prothiophanate-methyl, azoxystrobin, azoxystrobin, azoxystrobin, azoxystrobin, difenoconazole, pyraclostrobin, barnyardgrass, pyridaben, pyrimethanil, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyridaben, pyraclostrobin, quinconazole, fenpropathrin, quinoxalic acid, pentachloronitrobenzene, fluopyram, thiophanate-methyl, siloxystrobin, spirocycline, streptomycin, sulfur, tebuconazole, pentofluquinazonLeaf blight, tetrachloronitrobenzene, terbinafine, tetraflufenicol, thiabendazole, thifluzamide, thiophanate-methyl, methyl thiophanate, thiamethoxam, methyl thiophanate, mesotrione, tolprocarb, toluenesulfonamide, triadimefon, triazole, pyraclostrobin, cymoxanil, imidacloprid, copper sulfate, tricyclazole, chlorpyrifos, tridemorph, azoxystrobin, fluopyram, cymoxanil, cymoxanil, uniconazole, uniconazole-P, jinggangmycin, valiphenal (also known as cymoxanil), vinclozolin, zineb, thiram, benzyl benzoate, (3S,6S,7R,8R)-3-[[[3[(acetoxy)methoxy]-4-methoxy-2-pyridyl]carbonyl]amino]-6-methyl-4,9 -dioxo-8-(phenylmethyl)-1,5-dioxane-7-yl 2-methylpropionate, (3S,6S,7R,8R)-3-[[[3-(acetoxy)-4-methoxy-2-pyridyl]carbonyl]-amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxane-7-yl 2-methylpropionate, N-[[3-(1,3-benzodioxane-5-ylmethoxy)-4-methoxy-2-pyridyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)-L-arabinoyl]-L-serine, (1→4')-lactone, N[2-(1S,2R )-[1,1'-dicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide, 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butamide, 2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyn-1-yl)-2-(methylthio)acetamide, 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-ylN-[6-[[[[(1-methyl-1H-tetrazole-5- [2-(2,2-dichlorocyclopropyl)ethyl]-2-pyridyl]carbamate, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazol-1-ethanol, 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazol-3-thione, (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isooxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-1H-1,2,4-triazole,rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-1,2-dihydro-3H-1,2,4-triazol-3-thione, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole, 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isooxazolyl]pyridine, (2-chloro-6-fluorophenyl)methyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazole-1-yl]ethyl] [Acyl]-4-piperidinyl]-4-thiazolium carboxylate, N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidinium, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methanesulfonyl)amino]butyramide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethanesulfonyl)amino]butyramide, N'-[4-[4-chloro-3- [(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methyl-methyleneimine, N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methylethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]phenylacetamide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-(3',4'-difluoro[1,1'-biphenyl]-2-yl)-3-(trifluoromethyl) 2-Pyrazinamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-1-methyl-1H-pyrazole-4-carboxamide, 5,8-difluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2-pyridinyl]oxy]phenyl]ethyl]-4-quinazolinamine, 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide,1-[4-[4-[5R-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl] acetone, N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide, 2,6-dimethyl-1H,5H-[1,4]dithiacyclohexadiene[2,3-c:5,6-c']dipyrrole-1,3,5,7-(2H,6H)-tetraone, 2[(3-ethynyl-6- Quinolinyl)oxy]-N-[1-hydroxymethyl-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide, 4-fluorophenyl N-[1-[[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)-methoxy]-4-pyrimidinamine, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine, (3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(benzene) [[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxypropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxocyclic nonane-3-yl]amino]carbonyl]-3-pyridyl]oxy]methyl 2-methylpropionate, [[6-[[[[(1-methyl-1H-tetrazole-5-yl)-phenyl]] [Methylene]amino]oxy]methyl]-2-pyridyl]amyl carbamate, N-[4-[[[[(1-methyl-1H-tetrazol-5-yl)-phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate, and N-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)]phenylmethylene]amino]oxy]methyl]-2-pyridyl]amyl carbamate and (1R)-1,2,3,4-tetrahydro-1-naphthyl 2-[1-[2-[3,5-di(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolyl carboxylic acid ester. Therefore, it is noteworthy that the fungicidal composition comprises, as component (a), a compound of formula 1 (or its N-oxide or salt) and as component (b), at least one fungicide selected from the foregoing list.

[0991] Of particular note is the compound of Formula 1 (or its N-oxide or salt) (i.e., component (a)) and the following compounds (i.e., component (b)) as components of the composition): azoxystrobin, benzyl-fluorouracil, bifenthiophanate-methyl, captan, cyprothiophanate-methyl, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyclophosphamide, ethoxysulfuron, oxadiazon, dimethomorph, flutriafol, thiamethoxam, chlorpyrifos, cyclothiophanate-methyl, fluazinam, fludioxonil, fluopyram, flusilazole, flufenoxuron, fluazinam, captan, iprodione, isopyram, pyraclostrobin, azoxystrobin, mancozeb, mandestrobin, chlorpyrifos, metalaxyl (including metalaxyl-M / (e.g., methomyl), tebuconazole, benomyl, cyproconazole, oxathiapiprolin, fluopyram, pyraclostrobin, phosphorous acid (including its salts, such as aluminum triethylphosphonate), azoxystrobin, propiconazole, propoxyquin, prothioconazole, azoxystrobin, pyrimethanil, fluopyram, spiroxamine, sulfur, tebuconazole, thiophanate-methyl, oxadiazon, benzyl benzoate, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl]-1H-1,2,4-triazole-1-ethanol, 2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, N-[2-(2,4-dichlorophenyl)] [-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazole-1-yl]acetone, 1,1-dimethylethyl N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, 2,6-dimethyl -1H,5H-[1,4]dithiacyclohexadiene[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone, 5-fluoro-2-[(4-fluorophenyl)-methoxy]-4-pyrimidinamine, 5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine, (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isooxazolyl]-3-pyridylmethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-(2,[4-Difluorophenyl)-2-epoxyethylene]methyl]-1,2-dihydro-3H-1,2,4-triazol-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-epoxyethylene]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole.

[0992] Examples of other bioactive compounds or reagents that can be formulated with the compounds of the present invention include: invertebrate pest control compounds or reagents, such as abamectin, acephate, acetamiprid, flufenoxuron, pyrethroid ([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxymethyl-4,6a,12b-trimethyl-11-oxo-9-(3-pyridyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate), sulfadiazine (S-1955). Avermectin, azadirachtin, glutathion, bifenthrin, bifenazate, pymetrozine, carbofuran, fenitrothion, chlorantraniliprole, brofenoxuron, difenoconazole, chlorpyrifos, methyl chlorpyrifos, cofenoxuron, conidine, cyantraniliprole (3-bromo-1-(3-chloro-2-pyridyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide), cyclobrombutamide (3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide), cyclobrombutamide ((5S,8R)-1-[(6-chloro-3-pyridyl)methyl]-2,3,5,6, 7,8-Hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azapyr), dicofol, cypermethrin, β-cypermethrin, deltamethrin, cypermethrin, λ-cypermethrin, cypermethrin, cypermethrin, cyromazine, deltamethrin, difenoconazole, diazinon, dieldrin, diflubenzuron, tetrafluoromethrin, dimethoate, fipronil, benzyl benzoate, emamectin benzoate, endosulfan, cis-cypermethrin, acetamiprid, fenthiocarb, fenoxycarb, cypermethrin, fipronil, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)phenylacetic acid methyl ester, flufensulfone ( 5-Chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole), butenpyroximate (1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carboxynitrile), flupyrflufenone (4-[[(6-chloro-3-pyridyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), cypermethrin, pyrimethanil (UR-50701), flufenoxuron, terbufos, chlorfenapyr, heptaflupyr ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl-2,2-dimethyl-3-[(1Z)-3,3,3-Trifluoro-1-propen-1-yl]cyclopropane carboxylate, flufenoxuron, flufenoxuron, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, chlorpyrifos ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate), cyhalofop-P-ethyl, metaldehyde, methamidophos, chlorpyrifos, Methomyl, Methoxypurine, Methoxydextrin, Methoxyfenozide, Methoxyfenozide, Milbemime, Methoxyfenozide ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl-3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate), Phosphorus, Nicotine, Acetaminophen, Niethoxythiazole, Diphenylfluorourea, Polyfluorourea (XDE-007), Silane Pyrazosulfan, 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide, parathion, methyl parathion, permethrin, phorate, phosmet, phosmet, phosphamidon, fenpropathrin, propargite, flufenoxuron, pymetrozine Pyrimethanil, pyrethroids, acetamiprid, flufenoxuron, pyrimethanil ((αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)-phenylacetic acid methyl ester), pyriprole, fenprox, rotenone, lanyl base, spinosad, spinosad, spirodiclofen, spirodiclofen (BSM) 2060), spirotetramat, acetamiprid, thiophanate-methyl, tebufenozide, fenpropathrin, heptamethrin, terbufos, tetrachloroethylene, tetrafluoroethylene, thiamethoxam, thiamethoxam, thiamethoxam, sodium thiosulfate, fenpropathrin, tetrabromopyridaben, pymetrozine, trichlorfon, and chlorfenapyr; and biological agents, including entomopathogenic bacteria such as Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, and Bacillus thuringiensis-encapsulated Δ-endotoxins (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi such as Metarhizium anisopliae; and entomopathogenic viruses, including baculoviruses, nucleopolyhedroviruses (NPVs) such as HzNPV, AfNPV; and granuloviruses (GVs) such as CpGV.

[0993] The compounds and compositions thereof of the present invention can be applied to plants that have been genetically modified to express proteins toxic to invertebrate pests (e.g., Bacillus thuringiensis δ-endotoxin). The exogenously applied fungicidal compounds of the present invention can have a synergistic effect with the expressed toxic proteins.

[0994] General references for agricultural protectants (i.e., insecticides, fungicides, nematodes, acaricides, herbicides, and biological agents) include The Pesticide Manual, 13th edition, edited by CDSTomlin, British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd edition, edited by LGCopping, British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0995] For embodiments in which one or more of these different mixed pairings are used, the weight ratio of these various mixed pairings (total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. It is noteworthy that weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1) are acceptable. Those skilled in the art can readily determine, through simple experiments, the bioeffective amount of the active ingredient necessary for the desired bioactivity spectrum. It is evident that including these additional components can broaden the spectrum of diseases protected beyond those protected by the compound of Formula 1 alone.

[0996] In certain circumstances, the combination of the compounds of the present invention with other bioactive (specifically fungicidal) compounds or agents (i.e., active ingredients) can result in a greater than additive (i.e., synergistic) effect. Reducing the amount of active ingredient released into the environment while ensuring effective pest control is always desirable. When synergistic effects of fungicidal active ingredients occur at application rates that achieve agronomically satisfactory levels of fungal control, such combinations can be beneficial for reducing crop production costs and environmental impact.

[0997] In some cases, the combination of the compounds of the present invention with other bioactive compounds or reagents may result in a less-than-additive (i.e., safe) effect on organisms that are beneficial to the agronomic environment. For example, the compounds of the present invention may protect crop plants from herbicides or beneficial insect species (e.g., insect predators, pollinators such as bees) from pesticides.

[0998] Notable fungicides used to formulate with compounds of Formula 1 to provide mixtures suitable for seed treatment include, but are not limited to, indoxam, fluopyram, cymoxanil, carbendazim, carbendazim, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, fluazinam, iprodione, metalaxyl, metalaxyl-M, tebuconazole, cyprodinil, paclobutrazol, fluazinam, pyraclostrobin, prothioconazole, azoxystrobin, fluazinam, silthiamethoxam, tebuconazole, thiabendazole, thiophanate-methyl, thiram, azoxystrobin, and tebuconazole.

[0999] Compounds of Formula 1 can be formulated together to provide mixtures of invertebrate pest control compounds or agents for seed treatment, including but not limited to: abamectin, acetamiprid, flufenoxuron, bispyribac-methyl, amitraz, abamectin, azadirachtin, chlorfenapyr, bifenthrin, pymetrozine, thion, carbofuran, fenitrothion, chlorantraniliprole, brofenoxuron, chlorpyrifos, conidine, cyantraniliprole, and cyclohexane. Brofenoxam, cypermethrin, β-cypermethrin, deltamethrin, γ-cypermethrin, λ-cypermethrin, cypermethrin, α-cypermethrin, ζ-cypermethrin, cyromazine, deltamethrin, dieldrin, fipronil, benzyl ether, emamectin, endosulfan, cis-cypermethrin, acetamiprid, permethrin, etoxazole, bensulfuron-methyl, fenoxycarb, cypermethrin, fipronil, flufenoxuron, flupyradifurone, flufenoxuron, flufenoxuron Amide, flufenoxuron, flufenoxuron, butenpyroximate, flupyrflufenoxuron, lambda-cyhalothrin, chlorpyrifos, thiamethoxam, heptamethrin, flufenoxuron, fenpyroximate, imidacloprid, indoxacarb, lufenuron, cyfluthrin, cyhalofop-p-ethyl, methomyl, methomyl, methoxyfenozide, momfluorothrin, acetamiprid, nitenpyram, flufenoxuron, pyrflubumi de, pymetrozine, pyrethroids, pyridaben, pyrimethanil, trifluralin, pyriproxyfen, raniline, spinosad, spinosad, spirodiclofen, spirotetramat, acetamiprid, tebufenozide, pyrethroid, tetraflufenoxam, thiamethoxam, thiamethoxam, thiamethoxam, chlorpyrifos, tetrabromopyrethrin, pymetrozine, fenpropathrin, pymetrozine, fenpropathrin, fenpropathrin, fenpropathrin, fenpropathrin, Bacillus thuringiensis δ-endotoxin, Bacillus thuringiensis strains and nucleopolyhedrovirus strains.

[1000] Compositions containing a compound of Formula 1 for seed treatment may further contain bacteria and fungi possessing the ability to provide protection against the harmful effects of plant pathogenic fungi or bacteria and / or terrestrial animals such as nematodes. Bacteria exhibiting nematicidal properties may include, but are not limited to, *Bacillus firmus*, *Bacillus cereus*, *Bacillus subtiliis*, and *Pasteuria penetrans*. A suitable Bacillus strain is strain CNCM I-1582 (GB-126), which can be used as a BioNem... TM Commercially available. Suitable Bacillus cereus strain NCMM I-1592 is recommended. Both strains are disclosed in US 6,406,690. Other suitable bacteria exhibiting nematicidal activity are Bacillus amyloliquefaciens IN937a and Bacillus subtilis strain GB03. Bacteria exhibiting fungicidal properties may include, but are not limited to, Bacillus pumilus strain GB34. Fungal species exhibiting nematicidal properties may include, but are not limited to, Myrothecium verrucaria, Paecilomyces lilacinus, and Purpureocillium lilacinum.

[1001] Seed treatments may also include one or more naturally derived nematicides, such as harpins, which are activating proteins isolated from certain bacterial plant pathogens such as Erwinia amylovora. An example is N-Hibit (trade name). TM Gold CST has acquired Harpin-N-Tek seed treatment technology.

[1002] Seed treatment agents may also include one or more leguminous rhizobia, such as the microsymbiotic nitrogen-fixing bacterium *Bradyrhizobium japonicum*. These inoculants may optionally contain one or more lipid deacetylated chitosans (LCOs), which are nodation factors produced by the rhizobia during nodule formation on the bean roots. For example, Brand seed treatment technology will incorporate LCO Promoter Technology TM It binds to the inoculation agent.

[1003] Seed treatment agents may also include one or more isoflavones, which can increase the root colonization level of mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing root uptake of nutrients such as water, sulfate, nitrate, phosphate, and metals. Examples of isoflavones include, but are not limited to, genistein, chickpea sprout extract A, gentianin, daidzein, hesperidin, naringenin, and praseidin. Gentianin can be used as an inoculum product such as PHC. The active ingredients of AG were obtained.

[1004] Seed treatment may also include one or more plant activators that induce systemic resistance in plants upon exposure to pathogens. An example of a plant activator that induces such a protective mechanism is aramid-phenyl-S-methyl.

[1005] The following tests demonstrate the protective efficacy of the compounds of the present invention against specific pathogens. However, the pathogen protection provided by the compounds is not limited to these substances. Descriptions of the compounds are given in Index Tables A to T below. The following abbreviations are used in the index tables: Me refers to methyl, CN to cyano, N2 to nitro, Et to ethyl, n-Pr to n-propyl, i-Pr to isopropyl, c-Pr to cyclopropyl, i-Bu to isobutyl, t-Bu to tert-butyl, Ph to phenyl, MeO to methyloxy, EtO to ethoxy, and Ac to acetyl. The abbreviation “Cmpd.No.” represents “Compound Number,” and the abbreviation “Ex.” represents “Example,” with the following number indicating in which example the compound was prepared. Unless otherwise specified, 19 FNMR values ​​are recorded in ppm relative to a solution of trichlorofluoromethane in CDCl3. Values ​​recorded in the "MS" column are obtained by adding H+ to the molecule with the highest isotopic abundance. + The highest isotopic abundance of the positively charged parent ion (M+1) formed from (molecular weight 1), or from H + The molecular weight of the highest isotopic abundance negatively charged ion (M-1) formed by the loss of (molecular weight 1). Molecular ions containing one or more higher atomic weight isotopes with lower abundance are not recorded (e.g., 37 Cl、 81 The presence of Br was observed. The recorded MS peaks were observed by mass spectrometry using either electroinjection ionization (ESI) or atmospheric pressure chemical ionization (APCI).

[1006] Index Table A

[1007]

[1008] (R 2 ) x The dash "-" in the text means that R does not exist. 2Substituents and the remaining carbon valence is occupied by hydrogen atoms. In column L, the atom on the right is attached to the benzene ring, and the atom on the left is attached to the pyrazolium ring.

[1009]

[1010]

[1011]

[1012]

[1013]

[1014] a.19 F NMR in DMSO-d6 solution.

[1015] Index Table B

[1016]

[1017] (R 2 ) x The dash "-" in the text means that R does not exist. 2 Substituents and the remaining carbon valence is occupied by hydrogen atoms.

[1018]

[1019]

[1020] Index Table C

[1021]

[1022]

[1023]

[1024] Index Table D

[1025]

[1026]

[1027] Index Table E

[1028]

[1029]

[1030] Index table F

[1031]

[1032]

[1033] Index table G

[1034]

[1035]

[1036] Index table H

[1037]

[1038] R 2 The dash "-" in the column means that R does not exist. 2 Substituents and the remaining carbon valence is occupied by hydrogen atoms.

[1039]

[1040] Index Table I

[1041]

[1042]

[1043] Index Table J

[1044]

[1045]

[1046]

[1047] Index table K

[1048]

[1049] In column L, the atom on the right is attached to the thiophene ring, and the atom on the left is attached to R. 1 .

[1050]

[1051]

[1052] Index Table L

[1053]

[1054]

[1055] Index table M

[1056]

[1057]

[1058]

[1059] In column L, the atom on the right is attached to the benzene ring, and the atom on the left is attached to R. 1 ring.

[1060]

[1061]

[1062]

[1063] Index table O

[1064]

[1065] (R 2 ) x The dash "-" in the column means that R does not exist. 2 Substituents and the remaining carbon valence is occupied by hydrogen atoms. In column L, the atom on the right is attached to the J benzene ring, and the atom on the left is attached to the ring with (R) 2 ) x R 1 Benzene ring.

[1066]

[1067] Index table P

[1068]

[1069]

[1070] Index table Q

[1071]

[1072]

[1073] Index table R

[1074]

[1075] In column J, the left-hand bond connects to L and the right-hand bond connects to the oxadiazole ring.

[1076]

[1077]

[1078] Index table S

[1079]

[1080]

[1081]

[1082]

[1083]

[1084]

[1085]

[1086] Index table T

[1087]

[1088] Biological Examples of the Invention

[1089] The general procedure for preparing the test suspension for testing AC is as follows: First, dissolve the test compound in acetone in an amount equal to 3% of the final volume. Then, suspend it at the desired concentration (in ppm) in acetone and purified water (mixed 50 / 50 by volume) containing 250 ppm of surfactant PEG400 (polyol ester). The resulting test suspension is then used to test AC.

[1090] Test A

[1091] The test suspension was sprayed onto the runoff points on soybean seedlings. The next day, the seedlings were inoculated with a spore suspension of soybean rust fungus (Phakopsorapachyrhizi) (the pathogen of Asian soybean rust) and incubated at 22°C in saturated atmosphere for 24 hours. They were then moved to a growth chamber at 22°C and maintained therefore for 8 days, after which visual disease assessment was performed.

[1092] Test B

[1093] The test suspension was sprayed onto the runoff points on wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Zymoseptoriatritici (the pathogen of wheat leaf spot) and cultured at 24°C in saturated atmosphere for 48 hours. They were then moved to a growth chamber at 20°C and maintained there for 17 days, after which visual disease assessment was performed.

[1094] Test C

[1095] The test suspension was sprayed onto the runoff points on the wheat seedlings. The next day, the seedlings were inoculated with wheat leaf rust fungus (Puccinia recondita f.sp. tritici) (the pathogen of wheat leaf rust); and cultured at 20°C in saturated atmosphere for 24 hours, and then transferred to a growth chamber at 20°C for 6 days, after which visual disease assessment was performed.

[1096] Test D

[1097] The test suspension was sprayed onto the runoff points on wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of *Erysiphegraminis f.sp. tritici* (the pathogen of wheat powdery mildew) and incubated at 20°C under saturated pressure for 8 days, after which visual disease assessment was performed. Among the compounds tested, the following provided very good to excellent disease control (80% or greater): 85, 192, 263, 282, 337, 353, 455, 454, 490, and 497.

[1098] The results of AC testing are given in Table A. In this table, a grade of 100 indicates 100% disease control, while a grade of 0 indicates no disease control (relative to control). A dash (—) indicates that the compound was not tested. Unless otherwise specified, the test suspension was sprayed at the concentration listed in the “Ratio, in ppm” column. An asterisk “*” next to the grade indicates the use of 250 ppm of test suspension, a double asterisk “**” next to the grade indicates the use of 100 ppm of test suspension, and a triple asterisk “***” next to the grade indicates the use of 50 ppm of test suspension.

[1099] Table A

[1100]

[1101]

[1102]

[1103]

[1104]

[1105]

[1106]

[1107]

[1108]

[1109]

[1110]

Claims

1. A compound selected from formula 3 and its salts, in R 1 for The floating bond therein is connected to L in Formula 3 via any available carbon or nitrogen atom of the ring shown; x is 1 or 2; L is CH2; J is The bond extending to the left is connected to L, and the bond extending to the right is connected to the C≡N group of Formula 3; R 5a For H; Each R 2 Independently -C(=O)NR 3a R 3b ; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkoxycarbonyl, or C4-C7 cycloalkoxycarbonyl, each optionally substituted with at most one substituent selected from R 10 ; Each R 3a For H; Each R 3b It is independently a C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl or C2-C4 alkoxyalkyl; Each R 10 Independently, it is halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, or -C(R 13 )=NOR 14 ; Each R 13 Independently H, halogen, methyl, or methoxy; and Each R 14 It can be independently H, methyl, halomethyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

2. The compound according to claim 1, wherein: R 1 For U-2; Each R 2 Independently -C(=O)NR 3a R 3b ; or C2-C6 alkoxycarbonyl, each optionally substituted with at most one substituent selected from R 10 ;and Each R 10 It is independently a halogen, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkyl carbonyl, C2-C4 haloalkyl carbonyl or C2-C5 alkoxy carbonyl.

3. The compound according to claim 2, wherein: R 1 U-2 is connected to L at its 2nd position; and Each R 2 Independently -C(=O)NR 3a R 3b Or C2-C6 alkoxycarbonyl; and x is 1.

4. The compound according to claim 1, which is in: R 2 It is ClCH2CH2NHC(=O); and Z is O; or R 2 F2CHCH2NHC (=O); and Z is O; or R 2 It is MeOCH2CH2NHC(=O); and Z is O; or R 2 It is CF3CH2CH2NHC(=O); and Z is O; or R 2 It is FCH2CH2NHC(=O); and Z is O; or R 2 It is CF3CH2NHC (=O); and Z is O.

5. The compound according to claim 4, wherein it is:

6. The compound according to claim 1, wherein the compound is:

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