(1,4,5-trisubstituted-1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids and their derivatives, their salts and their use as herbicides

Abstract

The present invention relates to novel herbicidally active (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids of general formula (I) and their derivatives, as well as their agriculturally compatible / acceptable salts, N-oxides, hydrates and hydrates of said salts and N-oxides, processes for their preparation and their use for controlling broadleaf and grassy weeds in crops of useful plants and generally for controlling broadleaf and grassy weeds in areas where the growth of plants is undesirable. The derivatives of (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids include in particular their esters and / or amides.

Description

[Technical field]

[0001] The present invention relates to novel (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids of general formula (I) having herbicidal activity and their derivatives, their agronomically compatible salts, N-oxides, hydrates, the hydrates of said salts and N-oxides, processes for their preparation and their use for controlling broadleaf and grassy weeds in crops of useful plants and generally for controlling broadleaf and grassy weeds in areas where the plant growth is problematic in the environment.

[0002] The derivatives of the (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids include in particular the esters, salts and / or amides thereof. [Background technology]

[0003] The prior art discloses the biological effects of substituted 1,5-diphenylpyrazolyl-3-oxoacetic acids and methods for preparing these compounds. DE 2828529 A1 describes a method for the preparation of 1,5-diphenylpyrazolyl-3-oxoacetic acids and their lipid-lowering action.

[0004] CN101284815 discloses 1,5-diphenylpyrazolyl-3-oxoacetic acids as bactericidal pesticides. Journal of Heterocyclic Chemistry (2012), 49(6), 1370-1375 describes further synthesis methods and bactericidal activity of 1,5-diphenylpyrazolyl-3-oxoacetic acids.

[0005] WO2008 / 083233A2 describes 1,5-diphenylpyrazolyl-3-oxyalkyl acids and their derivatives substituted at the 4-position of pyrazole as substances suitable for disintegrating cell aggregates. Ethyl [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetate is specifically disclosed.

[0006] WO2020 / 245044A1 describes 1-phenyl-5-azinylpyrazolyl-3-oxyalkyl acids and their derivatives in which the pyrazole is substituted at the 1-position as herbicidal substances. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] DE2828529A1 [Patent Document 2] CN101284815 [Patent Document 3] WO2008 / 083233A2 [Patent Document 4] WO2020 / 245044A1 [Non-patent literature]

[0008] [Non-Patent Document 1] Journal of Heterocyclic Chemistry (2012), 49(6), 1370-1375 [Non-Patent Document 2] European Journal of Organic Chemistry (2011), 2011 (27), 5323-5330 Summary of the Invention

[0009] The (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids and their derivatives of the present invention are 2 It differs from the already known 1,5-diphenylpyrazolyl-3-oxoacetic acids by the radicals methoxy and ethoxy.

[0010] Furthermore, the synthesis of some 4-chloro-1,5-diphenylpyrazolyl-3-oxyacetic acids and their ethyl esters is described in European Journal of Organic Chemistry (2011), 2011 (27), 5323-5330.

[0011] The object of the present invention is to provide novel pyrazole derivatives, i.e. (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids and their derivatives, which have good herbicidal action and broad spectrum efficacy against harmful plants and / or have a high degree of selectivity in crops of useful plants and can be used as herbicides or plant growth regulators.

[0012] The object is to provide (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids, in which the substituents R 2 = methoxy or ethoxy).

[0013] Surprisingly, these compounds are highly effective against a wide range of economically important grass weeds and broadleaf weeds. At the same time, the compounds show good crop plant compatibility. Therefore, they can be selectively used in crop plants when they have good efficacy against harmful plants.

[0014] Thus, the present invention relates to a compound represented by the general formula (I) [ka]

[0015] [During the ceremony, A is A1, A2 and A3: [ka]

[0016] selected from the group consisting of; Q is Q1-Q16: [ka]

[0017] selected from the group consisting of; R 1 OR 1a , N.R. 9 R 10 and; R 1a is hydrogen, or (C1-C6)-alkyl, (C3-C6)-cycloalkyl, which are unsubstituted or in any case are not substituted by COOR 5 , independently substituted with "m" groups selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, cyano and nitro; or (C2-C4)-alkenyl, (C2-C4)-alkynyl, or (C1-C6)-alkyl-SO-(C1-C6)-alkyl-, (C1-C6)-alkyl-SO2-(C1-C6)-alkyl- or heterocyclyl, heteroaryl, aryl, or heterocyclyl-(C1-C4)-alkyl-, heteroaryl-(C1-C4)-alkyl-, aryl-(C1-C4)-alkyl-, which are unsubstituted or substituted, in each case, independently with "m" groups selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl; R 9 is hydrogen, (C1-C 12 )-alkyl; R 10 is hydrogen, aryl, heteroaryl, heterocyclyl, (C1-C 12 )-alkyl, (C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C7)-alkyl-, (C2-C 12)-alkenyl, (C5-C7)-cycloalkenyl, (C2-C 12 )-Alkynyl, S(O) n R 5 , Cyano, OR 5 , SO2NR 6 R 7 , CO2R 8 , C.O.R. 8 [wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl groups are unsubstituted or optionally mono- or polysubstituted aryl, halogen, cyano, nitro, OR 5 , S(O) n R 5 , SO2NR 6 R 7 , CO2R 8 ,CONR 6 R 8 , C.O.R. 6 , N.R. 6 R 8 , N.R. 6 COR 8 , N.R. 6 CONR 8 R 8 , N.R. 6 CO2R 8 , N.R. 6 SO2R 8 , N.R. 6 SO2NR 6 R 8 , C(R 6 )=NOR 8 each independently substituted with "m" groups selected from the group consisting of: Or, R 9 and R 10 together with the nitrogen atom to which they are attached form a saturated or partially unsaturated or fully unsaturated 5-, 6- or 7-membered ring, wherein the ring is selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, OR 5 , S(O) n R 5 , CO2R 8 ,CONR 6 R 8 , C.O.R. 6 and C(R 6 )=NOR8 and wherein the ring, in addition to the nitrogen atom, contains [r] carbon atoms, "o" oxygen atoms, "p" sulfur atoms, and NR 7 , CO and NCOR 7 containing as ring atoms "q" members selected from the group consisting of: R 5 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, aryl; R 6 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, aryl; R 7 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C4)-alkenyl, (C3-C4)-alkynyl; R 8 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C4)-alkenyl, (C1-C6)-alkyl-COO(C1-C2)-alkyl or (C3-C4)-alkynyl; R 2 is methoxy, ethoxy; R 3 is halogen, cyano, isocyano, nitro, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, (C3-C6)-halocycloalkyl, (C1-C6)-alkylcarbonyl-, (C1-C6)-haloalkylcarbonyl-, (C1-C6)-alkyloxycarbonyl-, (C2-C3)-alkenyl, (C2-C3)-haloalkenyl, (C2-C3)-alkynyl, (C2-C3)-haloalkynyl, (C1-C6)-alkyl-S(O) n and (C1-C6)-haloalkyl-S(O) n , CHO and NH2; R 12 is halogen, cyano, nitro, (C1-C6)-alkyl, (C1-C6)-haloalkyl; R 13is halogen, cyano, nitro, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl, (C1-C6)-alkoxycarbonyl, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C6)-alkylS(O) n , (C2-C3)-alkenyl, (C2-C3)-haloalkenyl, (C2-C3)-alkynyl, (C2-C3)-haloalkynyl; h is 0, 1 or 2; i is 0, 1, 2 or 3; k is 0, 1, 2, 3 or 4; m is 0, 1 or 2; n is 0, 1 or 2; o is 0, 1 or 2; p is 0 or 1; q is 0 or 1; r is 3, 4, 5 or 6; s is 0, 1, 2, 3, 4 or 5. The present invention provides (1,4,5-trisubstituted 1H-pyrazol-3-yl)oxy-2-alkoxyalkyl acids and derivatives thereof represented by the following formula:

[0018] Preferred, particularly preferred and very particularly preferred definitions of the individual substituents are set out below.

[0019] This provides various embodiments of the compounds of general formula (I).

[0020] preferable The compound represented by the general formula (I) A is A1-1, A1-2, A1-3, A1-4, A2-1, A3-1, A3-2, A3-3, A3-4 and A3-5 [Table 1]

[0021] and; Q is Q1, Q2, Q9 and Q16 [ka]

[0022] selected from the group consisting of; R 1 OR 1a , N.R. 9 R 10 and; R 1a is hydrogen, or (C1-C6)-alkyl, (C3-C6)-cycloalkyl, which are unsubstituted or in any case are not substituted by COOR 5 , independently substituted with "m" groups selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, cyano and nitro; or (C2-C4)-alkenyl, (C2-C4)-alkynyl, or (C1-C6)-alkyl-SO-(C1-C6)-alkyl-, (C1-C6)-alkyl-SO2-(C1-C6)-alkyl-, aryl-(C1-C4)-alkyl-, which are unsubstituted or substituted, in each case, independently with "m" groups selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl; R 9 is hydrogen, (C1-C6)-alkyl; R 10 is hydrogen, phenyl, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C4)-alkyl-, (C2-C4)-alkenyl, (C5-C7)-cycloalkenyl, (C2-C4)-alkynyl, S(O) n R 5 , Cyano, OR 5 , SO2NR 6 R7 , CO2R 8 , C.O.R. 8 [wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl groups are unsubstituted or mono- or polysubstituted phenyl, halogen, cyano, nitro, OR 5 , S(O) n R 5 , SO2NR 6 R 7 , CO2R 8 ,CONR 6 R 8 , C.O.R. 6 , N.R. 6 R 8 , N.R. 6 COR 8 , N.R. 6 CONR 8 R 8 , N.R. 6 CO2R 8 and each independently is substituted with "m" groups selected from the group consisting of: Or, R 9 and R 10 together with the nitrogen atom to which they are attached form a saturated or partially unsaturated or fully unsaturated 5-, 6- or 7-membered ring, wherein the ring is selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, OR 5 , S(O) n R 5 , CO2R 8 ,CONR 6 R 8 , C.O.R. 6 and C(R 6 )=NOR 8 and wherein the ring, in addition to the nitrogen atom, contains [r] carbon atoms, "o" oxygen atoms, "p" sulfur atoms, and NR 7 , CO and NCOR 7 containing as ring atoms "q" members selected from the group consisting of: R 5is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl or phenyl; R 6 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl or phenyl; R 7 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C4)-alkenyl or (C3-C4)-alkynyl; R 8 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C4)-alkenyl or (C3-C4)-alkynyl; R 2 is methoxy, ethoxy; R 3 is halogen, cyano, isocyano, nitro, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, (C3-C6)-halocycloalkyl, (C2-C3)-alkenyl, (C2-C3)-haloalkenyl, (C2-C3)-alkynyl, (C2-C3)-haloalkynyl; R 13 is halogen, cyano, nitro, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C6)-alkylS(O) n , (C2-C3)-alkenyl, (C2-C3)-haloalkenyl, (C2-C3)-alkynyl, (C2-C3)-haloalkynyl; i is 0, 1 or 2; k is 0, 1, 2, 3 or 4; m is 0, 1, 2; n is 0, 1, 2; o is 0, 1, 2; p is 0 or 1; q is 0 or 1; r is 3, 4, 5 or 6; s is 0, 1, 2, 4, 5. It is a compound represented by the formula:

[0023] Particularly preferred The compound represented by the general formula (I) A is A1-1, A1-2, A1-3, A1-4, A2-1, A3-1, A3-2, A3-3, A3-4 and A3-5 [Table 2]

[0024] and; Q is Q1, Q2, Q9 and Q16 [ka]

[0025] selected from the group consisting of; R 1 OR 1a , N.R. 9 R 10 and; R 1a is hydrogen, or (C1-C6)-alkyl, (C3-C6)-cycloalkyl, which are unsubstituted or in any case are not substituted by COOR 5 , halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl; or aryl-(C1-C4)-alkyl-, which is unsubstituted or substituted, in each case, independently with "m" groups selected from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl; R 9 is hydrogen; R 10 is (C1-C4)-alkyl, S(O) n R 5 , SO2NR 6 R 7 , CO2R 8 wherein the above groups are unsubstituted or substituted, such as phenyl, S(O) nR 5 , SO2NR 6 R 7 , CO2R 8 , N.R. 6 CO2R 8 each independently substituted with "m" groups selected from the group consisting of: R 5 is ethyl, methyl, CF3 or CH2CF3; R 6 is hydrogen; R 7 is hydrogen, methyl or ethyl; R 8 is methyl or ethyl; R 2 is methoxy, ethoxy; R 3 is halogen, cyano, nitro, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C3-C6)-halocycloalkyl; R 13 is fluorine, chlorine, bromine, cyano, methyl, ethyl, methoxy, ethoxy, CF3, OCF3; i is 0, 1 or 2; k is 0, 1 or 2; m is 0, 1 or 2; n is 0, 1 or 2; s is 0, 1 or 2. It is a compound represented by the formula:

[0026] Very particularly preferred The compound represented by the general formula (I) A is selected from the group consisting of A is A1-1, A1-2, A1-3, A1-4, A2-1, A3-1, A3-2, A3-3, A3-4 and A3-5 [Table 3] and;

[0027] Q is Q1, Q9 and Q16 [ka]

[0028] selected from the group consisting of; R 1 OR 1a and; R 1a is hydrogen, ethyl, methyl, -CH2CH(CH3)COOmethyl, -CH2CH2COOmethyl; R 2 is ethoxy, methoxy; R 3 is chlorine, bromine, iodine, cyano, cyclopropyl, CF2CF3, CHF2 or CF3; R 13 is fluorine, chlorine, methyl, MeS(O), MeS or CF3; i is 0, 1 or 2; k is 0, 1 or 2; s is 0, 1 or 2. It is a compound represented by the formula:

[0029] The present invention further relates to a compound of formula (Is) [ka]

[0030] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0031] The present invention further relates to a compound of formula (It) [ka]

[0032] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0033] The present invention further relates to a compound of formula (Iu) [ka]

[0034] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0035] The present invention further relates to a compound of formula (Iv) [ka]

[0036] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0037] The present invention further relates to a compound of formula (Iw) [ka]

[0038] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0039] The present invention further relates to a compound of formula (Ix) [ka]

[0040] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0041] The present invention further relates to a compound of formula (Iy) [ka]

[0042] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0043] The present invention further relates to a compound of formula (Iz) [ka]

[0044] The present invention provides a compound represented by the formula:

[0045] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention further relates to a compound of formula (V) [ka]

[0046] in which the above definitions apply, including all preferred, particularly preferred and very particularly preferred definitions. The present invention provides a compound represented by the formula:

[0047] In all formulas specified below, the substituents and symbols have the same meaning as described in formula (I), unless defined differently.

[0048] Combinations which are contrary to the laws of nature and therefore which a person skilled in the art would exclude based on his or her own knowledge are not included.

[0049] Alkyl represents a linear or branched saturated hydrocarbyl group, in each case having the specified number of carbon atoms, e.g., C-C 12-alkyl, preferably C1-C6-alkyl, such as, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl.

[0050] Halogen-substituted alkyl means linear or branched alkyl groups in which some or all of the hydrogen atoms can be replaced by halogen atoms, for example C1-C6-haloalkyl, preferably C1-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2-yl.

[0051] Alkenylstands for a straight-chain or branched unsaturated hydrocarbyl radical having in each case the indicated number of carbon atoms and one double bond in any position, for example C2-C8-alkenyl, preferably C2-C6-alkenyl, for example ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3- Pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3- Hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and 1-ethyl-2-methyl-2-propenyl.

[0052] Alkynyl represents a linear or branched hydrocarbyl group, in each case having the specified number of carbon atoms and one triple bond in any position, e.g., C-C 12 -Alkynyl, preferably C2-C6-alkynyl, for example ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, and the like.

[0053] Cycloalkylmeans a carbocyclic saturated ring system, preferably having 3 to 8 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, etc. In the case of cycloalkyl which may be substituted, ring systems having substituents are included, as well as ring systems having substituents with a double bond on the cycloalkyl group (e.g., alkylidene groups, e.g., methylidene).

[0054] In the case of optionally substituted cycloalkyl, polycyclic aliphatic systems such as bicyclo[1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl, bicyclo[2.1.0]pentan-5-yl, bicyclo[2.2.1]hept-2-yl (norbornyl), adamantan-1-yl and adamantan-2-yl are also included.

[0055] In the case of substituted cycloalkyl, spirocyclic aliphatic systems such as spiro[2.2]pent-1-yl, spiro[2.3]hex-1-yl and spiro[2.3]hex-4-yl, 3-spiro[2.3]hex-5-yl, and the like are also included.

[0056] Cycloalkenyl means a non-aromatic partially unsaturated carbocyclic ring system, preferably having 4 to 8 carbon atoms, such as 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1,4-cyclohexadienyl, and further includes substituents having a double bond on the cycloalkenyl group (for example, alkylidene groups, such as methylidene). In the case of optionally substituted cycloalkenyl, the explanations for substituted cycloalkyl apply accordingly.

[0057] Alkoxyis a straight-chain or branched saturated alkoxy radical having in each case the specified number of carbon atoms, for example C1-C6-alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, Examples of dimethylbutoxy include 1-methylpentoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, and 1-ethyl-2-methylpropoxy. Alkoxy substituted by halogen means linear or branched saturated alkoxy groups, in each case having the specified number of carbon atoms, in which some or all of the hydrogen atoms can be replaced by the halogen atoms specified above, such as, for example, C1-C2-haloalkoxy, such as, for example, chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-1,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy.

[0058] Arylmeans phenyl optionally substituted by 0 to 5 radicals selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, hydroxy, (C1-C3)-alkyl, (C1-C3)-alkoxy, (C3-C4)-cycloalkyl, (C2-C3)-alkenyl or (C2-C3)-alkynyl.

[0059] Heterocyclic groups (heterocyclyl)contains at least one heterocyclic ring (= a carbocyclic ring in which at least one carbon atom is replaced by a heteroatom, preferably a heteroatom selected from the group N, O, S, P), which may be saturated, unsaturated, partially saturated or aromatic and may be unsubstituted or substituted, where in this case the attachment site is located on a ring atom. If the heterocyclyl group or the heterocyclic ring is optionally substituted, it may be fused to another carbocyclic or heterocyclic ring. In the case of optionally substituted heterocyclyls, polycyclic systems such as, for example, 8-azabicyclo[3.2.1]octanyl, 8-azabicyclo[2.2.2]octanyl or 1-azabicyclo[2.2.1]heptyl are also included. Optionally substituted heterocyclyl also includes spirocyclic systems such as, for example, 1-oxa-5-aza-spiro[2.3]hexyl. Unless defined differently, the heterocyclic ring preferably contains 3 to 9 ring atoms (especially 3 to 6 ring atoms) and one or more (preferably 1 to 4, especially 1, 2 or 3) heteroatoms (preferably selected from the group N, O and S) in the heterocyclic ring (wherein, however, two oxygen atoms cannot be directly adjacent), for example having one heteroatom selected from the group N, O and S: 1- or 2- or 3-pyrrolidinyl, 3,4-dihydro-2H-pyrrol-2- or -3-yl, 2,3-dihydro-1H-pyrrol-1- or - ... -4- or -5-yl; 2,5-dihydro-1H-pyrrol-1- or -2- or -3-yl, 1- or 2- or 3- or 4-piperidinyl; 2,3,4,5-tetrahydropyridin-2- or -3- or -4- or -5-yl or -6-yl; 1,2,3,6-tetrahydropyridin-1- or -2- or -3- or -4- or -5- or -6-yl; 1,2,3,4-tetrahydropyridin-1- or -2- or -3- or -4- or -5- or -6-yl; 1,4-dihydropyridin-1- or -2- or -3- or -4-yl; 2,3-dihydropyridin-2- or -3- or -4- or -5- or -6-yl;2,5-Dihydropyridin-2- or -3- or -4- or -5- or -6-yl; 1- or 2- or 3- or 4-azepanyl; 2,3,4,5-tetrahydro-1H-azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,4,7-tetrahydro-1H-azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,6,7-tetrahydro-1H-azepin-1- or -2- or -3- or -4-yl; 3,4,5,6-tetrahydro-2H-azepin-2- or -3- or - 4- or -5- or -6- or -7-yl; 4,5-dihydro-1H-azepin-1- or -2- or -3- or -4-yl; 2,5-dihydro-1H-azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl; 2,7-dihydro-1H-azepin-1- or -2- or -3- or -4-yl; 2,3-dihydro-1H-azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl; 3,4-dihydro-2H-azepin-2- or -3- or -4- or -5- or -6- or -7-yl; 3,6-dihydro Hydro-2H-azepin-2- or -3- or -4- or -5- or -6- or -7-yl; 5,6-dihydro-2H-azepin-2- or -3- or -4- or -5- or -6- or -7-yl; 4,5-dihydro-3H-azepin-2- or -3- or -4- or -5- or -6- or -7-yl; 1H-azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl; 2H-azepin-2- or -3- or -4- or -5- or -6- or -7-yl; 3H-azepin-2- or -3- or -4- or -5- or -6- or - 7-yl; 4H-azepine-2- or -3- or -4- or -5- or -6- or -7-yl, 2- or 3-oxolanyl (= 2- or 3-tetrahydrofuranyl); 2,3-dihydrofuran-2- or -3- or -4- or -5-yl; 2,5-dihydrofuran-2- or -3-yl, 2- or 3- or 4-oxanyl (= 2- or 3- or 4-tetrahydropyranyl); 3,4-dihydro-2H-pyran-2- or -3- or -4- or -5- or -6-yl; 3,6-dihydro-2H-pyran-2- or -3- or -4- or -5- or -6-yl;2H-pyran-2- or -3- or -4- or -5- or -6-yl; 4H-pyran-2- or -3- or -4-yl, 2- or -3- or -4-oxepanyl; 2,3,4,5-tetrahydrooxepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,4,7-tetrahydrooxepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,6,7-tetrahydrooxepin-2- or -3- or -4-yl; 2,3-dihydrooxepin-2- or -3- or -4- or -5- or -6- or -7-yl; 4,5-dihydrooxepin-2- or -3- or -4-yl; 2,5-dihydrooxepin-2- or -3- or -4 - or -5- or -6- or -7-yl; oxepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2- or 3-tetrahydrothiophenyl; 2,3-dihydrothiophen-2- or -3- or -4- or -5-yl; 2,5-dihydrothiophen-2- or -3-yl; tetrahydro-2H-thiopyran-2- or -3- or -4-yl; 3,4-dihydro-2H-thiopyran-2- or -3- or -4- or -5- or -6-yl; 3,6-dihydro-2H-thiopyran-2- or -3- or -4- or -5- or -6-yl; 2H-thiopyran-2- or -3- or -4- or -5- or -6-yl; 4H-thiopyran-2- or -3- or -4-yl. Preferred 3- and 4-membered heterocycles are, for example, 1- or 2-aziridinyl, oxiranyl, thiiranyl, 1-, 2- or 3-azetidinyl, 2- or 3-oxetanyl, 2- or 3-thietanyl, 1,3-dioxetan-2-yl, and the like. Further examples of "heterocyclyl" are partially or fully hydrogenated heterocyclic groups having two heteroatoms selected from the group N, O and S, such as 1- or 2- or 3- or 4-pyrazolidinyl; 4,5-dihydro-3H-pyrazol-3- or -4- or -5-yl; 4,5-dihydro-1H-pyrazol-1- or -3- or -4- or -5-yl; 2,3-dihydro-1H-pyrazol-1- or -2- or -3- or -4- or -5-yl; 1- or -2- or -3- or -4-imidazolidinyl; 2,3-dihydro-1H-imidazol-1- or -2- or -3- or -4-yl;2,5-Dihydro-1H-imidazol-1- or -2- or -4- or -5-yl; 4,5-Dihydro-1H-imidazol-1- or -2- or -4- or -5-yl; Hexahydropyridazin-1- or -2- or -3- or -4-yl; 1,2,3,4-Tetrahydropyridazin-1- or -2- or -3- or -4- or -5- or -6-yl; 1,2,3,6-Tetrahydropyridazin-1- or -2- or -3- or -4- or -5- or -6-yl; 1,4,5,6-Tetrahydropyridazin-1- or -3- or -4- or -5- or 3,4,5,6-tetrahydropyridazin-3- or -4- or -5-yl;4,5-dihydropyridazin-3- or -4-yl;3,4-dihydropyridazin-3- or -4- or -5- or -6-yl;3,6-dihydropyridazin-3- or -4-yl;1,6-dihydropyridazin-1- or -3- or -4- or -5- or -6-yl;hexahydropyrimidin-1- or -2- or -3- or -4-yl;1,4,5,6-tetrahydropyrimidin-1- or -2- or -4- or -5- or -6-yl;1,2,5,6- Tetrahydropyrimidin-1- or -2- or -4- or -5- or -6-yl; 1,2,3,4-tetrahydropyrimidin-1- or -2- or -3- or -4- or -5- or -6-yl; 1,6-dihydropyrimidin-1- or -2- or -4- or -5- or -6-yl; 1,2-dihydropyrimidin-1- or -2- or -4- or -5- or -6-yl; 2,5-dihydropyrimidin-2- or -4- or -5-yl; 4,5-dihydropyrimidin-4- or -5- or -6-yl; 1,4-dihydropyrimidin-1- or -2- or -4- or -5- or -6-yl - or -5- or -6-yl; 1- or -2- or -3-piperazinyl; 1,2,3,6-tetrahydropyrazin-1- or -2- or -3- or -5- or -6-yl; 1,2,3,4-tetrahydropyrazin-1- or -2- or -3- or -4- or -5- or -6-yl; 1,2-dihydropyrazin-1- or -2- or -3- or -5- or -6-yl; 1,4-dihydropyrazin-1- or -2- or -3-yl; 2,3-dihydropyrazin-2- or -3- or -5- or -6-yl; 2,5-dihydropyrazin-2- or -3-yl;1,3-Dioxolane-2- or -4- or -5-yl;1,3-Dioxol-2- or -4- or -5-yl;1,3-Dioxan-2- or -4- or -5-yl;4H-1,3-Dioxin-2- or -4- or -5- or -6-yl;1,4-Dioxan-2- or -3- or -5- or -6-yl;2,3-Dihydro-1,4-dioxin-2- or -3- or -5- or -6-yl;1,4-Dioxin-2- or -3-yl;1,2-Dithiolane-3- or -4-yl;3H-1,2-Dithiol-3- or -4- or -5-yl;1, 3-Dithiolane-2- or -4-yl;1,3-Dithiol-2- or -4-yl;1,2-Dithiane-3- or -4-yl;3,4-Dihydro-1,2-dithiin-3- or -4- or -5- or -6-yl;3,6-Dihydro-1,2-dithiin-3- or -4-yl;1,2-Dithiin-3- or -4-yl;1,3-Dithiane-2- or -4- or -5-yl;4H-1,3-Dithiin-2- or -4- or -5- or -6-yl;Isoxazolidin-2- or -3- or -4- or -5-yl;2,3-Dihydroisoxazole -2- or -3- or -4- or -5-yl;2,5-dihydroisoxazol-2- or -3- or -4- or -5-yl;4,5-dihydroisoxazol-3- or -4- or -5-yl;1,3-oxazolidin-2- or -3- or -4- or -5-yl;2,3-dihydro-1,3-oxazol-2- or -3- or -4- or -5-yl;2,5-dihydro-1,3-oxazol-2- or -4- or -5-yl;4,5-dihydro-1,3-oxazol-2- or -4- or -5-yl;1,2-oxazinane-2 - or -3- or -4- or -5- or -6-yl; 3,4-dihydro-2H-1,2-oxazin-2- or -3- or -4- or -5- or -6-yl; 3,6-dihydro-2H-1,2-oxazin-2- or -3- or -4- or -5- or -6-yl; 5,6-dihydro-2H-1,2-oxazin-2- or -3- or -4- or -5- or -6-yl; 5,6-dihydro-4H-1,2-oxazin-3- or -4- or -5- or -6-yl; 2H-1,2-oxazin-2- or -3- or -4- or -5- or -6-yl;6H-1,2-oxazin-3- or -4- or -5- or -6-yl; 4H-1,2-oxazin-3- or -4- or -5- or -6-yl; 1,3-oxazinan-2- or -3- or -4- or -5- or -6-yl; 3,4-dihydro-2H-1,3-oxazin-2- or -3- or -4- or -5- or -6-yl; 3,6-dihydro-2H-; 1,3-Oxazin-2- or -3- or -4- or -5- or -6-yl;5,6-Dihydro-2H-1,3-oxazin-2- or -4- or -5- or -6-yl;5,6-Dihydro-4H-1,3-oxazin-2- or -4- or -5- or -6-yl;2H-1,3-oxazin-2- or -4- or -5- or -6-yl;6H-1,3-oxazin-2- or -4- or -5- or -6-yl;4H-1,3-oxazin-2- or -4- or -5- or -6-yl;Morpholine-2- or -3- or -4-yl;3,4-Dihydro 2H-1,4-oxazin-2- or -3- or -4- or -5- or -6-yl; 3,6-dihydro-2H-1,4-oxazin-2- or -3- or -5- or -6-yl; 2H-1,4-oxazin-2- or -3- or -5- or -6-yl; 4H-1,4-oxazin-2- or -3-yl; 1,2-oxazepane-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,4,5-tetrahydro-1,2-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,4,7-tetrahydro-1,2-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; Hydro-1,2-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,6,7-tetrahydro-1,2-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,5,6,7-tetrahydro-1,2-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 4,5,6,7-tetrahydro-1,2-oxazepin-3- or -4- or -5- or -6- or -7-yl; 2,3-dihydro-1,2-oxazepin-2- or -3- or -4- or -5- or is -6- or -7-yl; 2,5-dihydro-1,2-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,7-dihydro-1,2-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 4,5-dihydro-1,2-oxazepin-3- or -4- or -5- or -6- or -7-yl; 4,7-dihydro-1,2-oxazepin-3- or -4- or -5- or -6- or -7-yl; 6,7-dihydro-1,2-oxazepin-3- or -4- or -5- or -6- or -7-yl;1,2-Oxazepin-3- or -4- or -5- or -6- or -7-yl; 1,3-Oxazepan-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,4,5-Tetrahydro-1,3-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,4,7-Tetrahydro-1,3-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,6,7-Tetrahydro-1,3-oxazepin-2- or -3- or -4- or -5- or -6- or -7 -yl;2,5,6,7-tetrahydro-1,3-oxazepin-2- or -4- or -5- or -6- or -7-yl;4,5,6,7-tetrahydro-1,3-oxazepin-2- or -4- or -5- or -6- or -7-yl;2,3-dihydro-1,3-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl;2,5-dihydro-1,3-oxazepin-2- or -4- or -5- or -6- or -7-yl;2,7-dihydro-1,3-oxazepin-2- or -4- or -5- or -6- or - 7-yl;4,5-dihydro-1,3-oxazepin-2- or -4- or -5- or -6- or -7-yl;4,7-dihydro-1,3-oxazepin-2- or -4- or -5- or -6- or -7-yl;6,7-dihydro-1,3-oxazepin-2- or -4- or -5- or -6- or -7-yl;1,3-oxazepin-2- or -4- or -5- or -6- or -7-yl;1,4-oxazepan-2- or -3- or -5- or -6- or -7-yl;2,3,4,5-tetrahydro-1,4-oxazepin-2- or is -3- or -4- or -5- or -6- or -7-yl; 2,3,4,7-tetrahydro-1,4-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 2,3,6,7-tetrahydro-1,4-oxazepin-2- or -3- or -5- or -6- or -7-yl; 2,5,6,7-tetrahydro-1,4-oxazepin-2- or -3- or -5- or -6- or -7-yl; 4,5,6,7-tetrahydro-1,4-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl;2,3-dihydro-1,4-oxazepin-2- or -3- or -5- or -6- or -7-yl; 2,5-dihydro-1,4-oxazepin-2- or -3- or -5- or -6- or -7-yl; 2,7-dihydro-1,4-oxazepin-2- or -3- or -5- or -6- or -7-yl; 4,5-dihydro-1,4-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl; 4,7-dihydro-1,4-oxazepin-2- or -3- or -4- or -5- or -6- or -7-yl;6,7-dihydro-1,4-oxazepin-2- or -3- or -5- or -6- or -7-yl;1,4-oxazepin-2- or -3- or -5- or -6- or -7-yl;isothiazolidine-2- or -3- or -4- or -5-yl;2,3-dihydroisothiazol-2- or -3- or -4- or -5-yl;2,5-dihydroisothiazol-2- or -3- or -4- or -5-yl;4,5-dihydroisothiazol-3- or -4- or -5-yl; 1,3-Thiazolidine-2- or -3- or -4- or -5-yl;2,3-dihydro-1,3-thiazol-2- or -3- or -4- or -5-yl;2,5-dihydro-1,3-thiazol-2- or -4- or -5-yl;4,5-dihydro-1,3-thiazol-2- or -4- or -5-yl;1,3-thiazinane-2- or -3- or -4- or -5- or -6-yl;3,4-dihydro-2H-1,3-thiazin-2- or -3- or -4- or -5- or -6-yl;3,6-di Hydro-2H-1,3-thiazin-2- or -3- or -4- or -5- or -6-yl; 5,6-dihydro-2H-1,3-thiazin-2- or -4- or -5- or -6-yl; 5,6-dihydro-4H-1,3-thiazin-2- or -4- or -5- or -6-yl; 2H-1,3-thiazin-2- or -4- or -5- or -6-yl; 6H-1,3-thiazin-2- or -4- or -5- or -6-yl; 4H-1,3-thiazin-2- or -4- or -5- or -6-yl, etc. Further examples of "heterocyclyl" are partially or fully hydrogenated heterocyclic groups having three heteroatoms selected from the group N, O and S, such as 1,4,2-dioxazolidin-2- or -3- or -5-yl;1,4,2-dioxazol-3- or -5-yl; 1,4,2-dioxazinan-2- or -3- or -5- or -6-yl; 5,6-dihydro-1,4,2-dioxazin-3- or -5- or -6-yl; 1,4,2-dioxazin-3- or -5- or -6-yl; 1,4,2-dioxazepan-2- or -3- or -5- or -6- or -7-yl; 6,7-dihydro-5H-1,4,2-dioxazepine-3- or -5 - or -6- or -7-yl; 2,3-dihydro-7H-1,4,2-dioxazepin-2- or -3- or -5- or -6- or -7-yl; 2,3-dihydro-5H-1,4,2-dioxazepin-2- or -3- or -5- or -6- or -7-yl; 5H-1,4,2-dioxazepin-3- or -5- or -6- or -7-yl; 7H-1,4,2-dioxazepin-3- or -5- or -6- or -7-yl, etc. Examples of structures of optionally substituted heterocycles are also described below: [Table 4] TIFF2024524230000020.tif236160TIFF2024524230000021.tif209160

[0060] The heterocycles mentioned above are preferably, for example, hydrogen, halogen, alkyl, haloalkyl, hydroxyl, alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroaryl, heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, hydroxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, alkoxycarbonylalkyl, arylalkoxycarbonyl, arylalkoxycarbonylalkyl, alkynyl, alkynylalkyl, alkylalkynyl, trisalkylsilylalkynyl, nitro, amino, cyano, haloalkoxy, halocycloalkyl ... and is substituted by alkylthio, alkylthio, hydrothio, hydroxyalkyl, oxo, heteroarylalkoxy, arylalkoxy, heterocyclylalkoxy, heterocyclylalkylthio, heterocyclyloxy, heterocyclylthio, heteroaryloxy, bisalkylamino, alkylamino, cycloalkylamino, hydroxycarbonylalkylamino, alkoxycarbonylalkylamino, arylalkoxycarbonylalkylamino, alkoxycarbonylalkyl(alkyl)amino, aminocarbonyl, alkylaminocarbonyl, bisalkylaminocarbonyl, cycloalkylaminocarbonyl, hydroxycarbonylalkylaminocarbonyl, alkoxycarbonylalkylaminocarbonyl, arylalkoxycarbonylalkylaminocarbonyl.

[0061] If a base structure is substituted with "one or more radicals" selected from a list of radicals (=groups) or a generically defined group of radicals, this in each case includes simultaneous substitution with several identical radicals and / or structurally different radicals.

[0062] In the case of a partially or fully saturated nitrogen heterocycle, it may be attached to the remainder of the molecule through a carbon or through the nitrogen.

[0063] Suitable substituents for substituted heterocyclic groups are the above-mentioned substituents, and also oxo and thioxo. An oxo group as a substituent on a ring carbon atom is, for example, a carbonyl group in the heterocyclic ring. As a result, lactones and lactams are also preferably included. The oxo group can also be present on a ring heteroatom, which can be present in various oxidation states, for example, in the case of N and S, and then they form, for example, divalent -N(O)-, -S(O)- (also abbreviated as "SO") and -S(O)2- (also abbreviated as "SO2") groups in the heterocyclic ring. In the case of -N(O)- and -S(O)- groups, in each case, both enantiomers are included.

[0064] According to the present invention, the expression "heteroaryl" denotes a heteroaromatic compound, i.e. a fully unsaturated aromatic heterocyclic compound, preferably a 5- to 7-membered ring having 1 to 4 (preferably 1 or 2) identical or different heteroatoms (preferably O, S or N). Heteroaryl according to the present invention is, for example, 1H-pyrrol-1-yl; 1H-pyrrol-2-yl; 1H-pyrrol-3-yl; furan-2-yl; furan-3-yl; thien-2-yl; thien-3-yl, 1H-imidazol-1-yl; 1H-imidazol-2-yl; 1H-imidazol-4-yl; 1H-imidazol-5-yl; 1H-pyrazol-1-yl; 1H-pyrazol-3-yl; 1H-pyrazol-4-yl; 1H-pyrazol- 5-yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, 2H-1,2,3-triazol-2-yl, 2H-1,2,3-triazol-4-yl, 1H-1,2,4-triazol-1-yl, 1H-1,2,4-triazol-3-yl, 4H-1,2,4-triazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol azepinyl, pyridinyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrazin-2-yl, pyrazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-3-yl, pyridazin-4-yl, 1,3,5-triphenyl, pyridinyl, pyridinyl-5-yl, pyridazin-3-yl, pyridazin-4-yl, pyridazinyl-5-yl, pyridazinyl-3-yl, pyridazinyl ... Triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl, 1,2,3-triazin-4-yl, 1,2,3-triazin-5-yl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,3-oxazol-2-yl, 1,3-oxazol-4-yl, 1,Examples of heteroaryl groups include 3-oxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,3-thiazol-2-yl, 1,3-thiazol-4-yl, 1,3-thiazol-5-yl, oxepinyl, thiepinyl, 1,2,4-triazolonyl, and 1,2,4-diazepinyl, 2H-1,2,3,4-tetrazol-5-yl, 1H-1,2,3,4-tetrazol-5-yl, 1,2,3,4-oxatriazol-5-yl, 1,2,3,4-thiatriazol-5-yl, 1,2,3,5-oxatriazol-4-yl, 1,2,3,5-thiatriazol-4-yl, etc. The heteroaryl groups of the present invention can also be substituted with one or more identical or different groups. When two adjacent carbon atoms are part of a further aromatic ring, the system is a fused heteroaromatic system, for example a benzofused heteroaromatic compound or a polyannelated heteroaromatic compound. Preferred examples are quinolines (e.g., quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl); isoquinolines (e.g., isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, isoquinolin-8-yl); quinoxaline; quinazoline; cinnoline; 1,5-naphthyridine; 1,6-naphthyridine; 1,7-naphthyridine; 1,8-naphthyridine; 2,6-naphthyridine; 2,7-naphthyridine; phthalazine; pyridopyrazines; pyridopyrimidines; pyridopyridazines; pteridines; pyrimidopyrimidines. Examples of heteroaryl are also 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl, 1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl, 1H-indazol-1-yl, 1H-indazol-3-yl, 1H-indazol-4-yl, 1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl, 2H-indazol-2-yl, 2H-indazol-3-yl, 2H-indazol-4-yl, 2H-indazol-5-yl, 2H-indazol-6-yl, 2H -indazol-7-yl, 2H-isoindol-2-yl, 2H-isoindol-1-yl, 2H-isoindol-3-yl, 2H-isoindol-4-yl, 2H-isoindol-5-yl, 2H-isoindol-6-yl; 2H-isoindol-7-yl, 1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl, 1H-benzimidazol-5-yl, 1H-benzimidazol-6-yl, 1H-benzimidazol-7-yl 1,3-benzoxazol-2-yl, 1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl, 1,3-benzoxazol-7-yl, 1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl, 1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl, 1,2-benzoisoxazol-3-yl, 1,2-benzoisoxazol-4-yl, 1,A 5- or 6-membered benzo-fused ring selected from the group consisting of 2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl, 1,2-benzisothiazol-3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, and 1,2-benzisothiazol-7-yl.

[0065] The term "halogen" means fluorine, chlorine, bromine or iodine. When the term is used in reference to a group, "halogen" means a fluorine, chlorine, bromine or iodine atom.

[0066] The compounds of formula (I) have acidic properties, depending on the type of the substituents as defined above, and can form salts, if appropriate inner salts, or adducts with inorganic or organic bases or with metal ions. If the compounds of formula (I) have hydroxyl, carboxyl or other groups which induce acidic properties, such compounds can react with bases to produce salts. Suitable bases are, for example, hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals, in particular hydroxides, carbonates and hydrogen carbonates of sodium, potassium, magnesium and calcium, as well as ammonia, primary, secondary and tertiary amines with C1-C4-alkyl groups, mono-, dialkanolamines and trialkanolamines of C1-C4-alkanols, choline and chlorocholine, and organic amines such as trialkylamines, morpholine, piperidine or pyridine. These salts include compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, such as metal salts, in particular alkali metal or alkaline earth metal salts, in particular sodium and potassium salts, or ammonium salts, salts with organic amines or quaternary ammonium salts, for example salts of the formula [NRRR'R''R'''] +wherein R to R'" are each independently an organic group, in particular alkyl, aryl, aralkyl, or alkylaryl. Also useful are alkylsulfonium salts and alkylsulfoxonium salts, such as (C1-C4)-trialkylsulfonium salts and (C1-C4)-trialkylsulfoxonium salts.

[0067] The compounds of formula (I) can form salts by addition of a suitable inorganic or organic acid (e.g., a mineral acid such as HCl, HBr, H2SO4, H3PO4 or HNO3, or an organic acid such as a carboxylic acid such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid, or a sulfonic acid such as p-toluenesulfonic acid) to a basic group (e.g., amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino). These salts therefore contain the conjugate base of the acid as the anion.

[0068] Suitable substituents that exist in deprotonated form (eg, sulfonic or carboxylic acids) can form inner salts with groups that can themselves be protonated (eg, amino groups).

[0069] When a group is polysubstituted with a group, this means that the group is substituted with one or more identical or different groups selected from the groups listed above.

[0070] In all formulas specified below, the substituents and symbols have the same meaning as described in formula (I) unless defined differently. Arrows in chemical formulas represent the points of attachment to the remainder of the molecule.

[0071] In the following, preferred, particularly preferred and very particularly preferred definitions for each of the individual substituents are set out. Any other substituents not specified below in the general formula (I) have the definitions given above.

[0072] The compounds of the present invention represented by the general formula (I) have the following structure at the second carbon of the alkyl acid structure: * ) has a chiral carbon atom, represented by: [ka]

[0073] According to the rules of Cahn, Ingold and Prelog (CIP rules), this carbon atom can have either the (R) or the (S) configuration.

[0074] The present invention encompasses both compounds of formula (I) having the (S) configuration and compounds of formula (I) having the (R) configuration. This means that the present invention relates to compounds of formula (I) (1) in the (R) configuration; or (2) (S) Configuration have The present invention is intended to include compounds represented by the following formula:

[0075] Further within the scope of the present invention are: (3) Any mixture of a compound represented by general formula (I) having the (R) configuration (compound represented by general formula (I-(R)) and a compound represented by general formula (I) having the (S) configuration (compound represented by general formula (I-(S))); the present invention also encompasses a racemic mixture of a compound represented by general formula (I) having the (R) configuration and a compound represented by general formula (I) having the (S) configuration.

[0076] In addition, depending on the selected individual groups, further stereoelements may be present in the compounds of general formula (I) according to the invention. [Table 5] TIFF2024524230000024.tif248161TIFF2024524230000025.tif248162TIFF20245242300 00026.tif248162TIFF2024524230000027.tif248161TIFF2024524230000028.tif186161

[0077] A further aspect of the present invention relates to the preparation of the compounds of the present invention represented by general formula (I).The compounds of the present invention can be prepared in a variety of ways.

[0078] Compounds of general formula (Ib) according to the present invention are synthesized via amide coupling of acids of general formula (Ia) with amines of general formula (II) in the presence of amide coupling reagents such as T3P, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide, N,N'-carbonyldiimidazole, 2-chloro-1,3-dimethylimidazolium chloride or 2-chloro-1-methylpyridinium iodide, as shown in Scheme 1 (see Chemistry of Peptide Synthesis, Ed. N. Leo Benoiton, Taylor & Francis, 2006, ISBN-10: 1-57444-454-9). Polymer-supported reagents such as polymer-supported dicyclohexylcarbodiimide are also suitable for this coupling reaction. The reaction is preferably carried out in a suitable solvent (e.g., dichloromethane, acetonitrile, N,N-dimethylformamide, or ethyl acetate) in the presence of a base (e.g., triethylamine, N,N-diisopropylethylamine, or 1,8-diazabicyclo[5.4.0]undec-7-ene) at a temperature range of 0° C. to 80° C. For T3P peptide coupling conditions, see Organic Process Research & Development 2009, 13, 900-906.

[0079] [ka]

[0080] The acid of formula (Ia) is synthesized by subjecting the compound of formula (Ic) to ester hydrolysis in a manner similar to that known to those skilled in the art (Scheme 2). The hydrolysis can be carried out in the presence of a base or a Lewis acid. The base can be a hydroxide salt of an alkali metal (e.g., lithium, sodium or potassium), and the hydrolysis reaction is preferably carried out at a temperature range of room temperature to 120°C.

[0081] [ka]

[0082] The compound of general formula (Ic) is synthesized by alkylating the hydroxypyrazole of general formula (III) with an α-halocarboxylic acid ester of general formula (IV) in the presence of a base, or similarly by methods known to those skilled in the art (see scheme 3). The base used can be an alkali metal carbonate. The base is preferably an alkali metal carbonate selected from the group consisting of lithium, sodium, potassium and cesium, and the reaction is preferably carried out in a suitable solvent (e.g., dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate) at a temperature range of room temperature to 150°C. See, for example, J. Med. Chem. 2011, 54(16), 5820-5835 and WO2010 / 010154. The "X" group is, for example, chlorine, bromine or iodine.

[0083] [ka]

[0084] Scheme 4 illustrates a compound of general formula (VII, R 3=Cl, Br, I) by reacting a 3-hydroxypyrazole of general formula (V) with an electrophilic halogenating reagent of general formula (VI) (e.g., N-chlorosuccinimide (VI, X=Cl), N-bromosuccinimide (VI, X=Br) or N-iodosuccinimide (VI, X=I)). In a similar manner, other electrophiles, such as electrophilic nitrating reagents (e.g., nitrating acid, nitronium tetrafluoroborate, or ammonium nitrate / trifluoroacetic acid) (R 3 = nitro) or an electrophilic fluorination reagent (e.g., DAST, Selectfluor, or N-fluorobenzenesulfonimide) (R 3 =F) can also be used. The reaction is preferably carried out in a suitable solvent (e.g., N,N-dimethylformamide, 1,2-dichloroethane, or acetonitrile) at a temperature range of 0°C to 120°C.

[0085] [ka]

[0086] Scheme 5 describes the synthesis of halogenated pyrazoles of general formula (Ie), where the method is by reacting 4H-pyrazoles of general formula (Id) with halosuccinimides of general formula (VI) in a suitable solvent (e.g., N,N-dimethylformamide).

[0087] [ka]

[0088] 4-Cyanopyrazoles of general formula (If) can be prepared, for example, by reacting a compound of formula (Ie) with a metal cyanide M-CN or M(CN)2(VIII) in a suitable solvent, preferably at elevated temperature in an organic solvent (e.g., 1,2-dimethoxyethane or N,N-dimethylformamide) with the addition of a suitable amount of a transition metal catalyst (e.g., particularly a palladium catalyst, e.g., palladium(0)tetrakis(triphenylphosphine) or palladium diacetate or bis(triphenylphosphine)palladium(II)dichloride) (Scheme 5). Alternatively, a nickel catalyst (e.g., nickel(II)acetylacetonate or bis(triphenylphosphine)nickel(II)chloride) is used, preferably at elevated temperature in an organic solvent (e.g., 1,2-dimethoxyethane or N,N-dimethylformamide). The "M" group in the metal cyanide M-CN or M(CN)2(VIII) represents, for example, zinc, lithium, potassium or sodium. Generally suitable cross-coupling methods are those described in RD Larsen, Organometallics in Process Chemistry 2004 Springer Verlag, I. Tsuji, Palladium Reagents and Catalysts 2004 Wiley and M. Beller, C. Bolm, Transition Metals for Organic Synthesis 2004 VCH-Wiley. Further suitable synthesis methods are described in Chem. Rev. 2006, 106, 2651, Platinum Metals Review, 2009, 53, 183, Platinum Metals Review 2008, 52, 172 and Acc. Chem. Res. 2008, 41, 1486.

[0089] The 3-hydroxypyrazoles (V) can be prepared analogously to methods known from the literature, for example as described in Adv. Synth. Catal. 2014, 356, 3135-3147, in a two-step synthesis from 3-azinylpropionic acid derivatives and phenylhydrazines (XI) (Scheme 6). Compounds of general formula (XII) are synthesized via amide coupling of acids of general formula (X) with arylhydrazines or hetarylhydrazines of general formula (XI) in the presence of amide coupling reagents such as T3P, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide, N,N'-carbonyldiimidazole, 2-chloro-1,3-dimethylimidazolium chloride or 2-chloro-1-methylpyridinium iodide (see Chemistry of Peptide Synthesis, Ed. N. Leo Benoiton, Taylor & Francis, 2006, ISBN-10: 1-57444-454-9). Polymer-bound reagents such as polymer-bound dicyclohexylcarbodiimide are also suitable for this coupling reaction. The reaction is preferably carried out in a suitable solvent (e.g., dichloromethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or ethyl acetate) in the presence of a base (e.g., triethylamine, N,N-diisopropylethylamine, or 1,8-diazabicyclo[5.4.0]undec-7-ene) at a temperature range of 0° C. to 80° C. (see Scheme 6). For T3P peptide coupling conditions, see Organic Process Research & Development 2009, 13, 900-906.

[0090] This is followed by cyclization of the hydrazide (XII) in the presence of a copper halide (e.g., copper(I) iodide, copper(I) bromide) or an acid (e.g., methanesulfonic acid). The reaction is preferably carried out in a suitable solvent (e.g., 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, n-propanol, or ethyl acetate) at a temperature range of 0° C. to 120° C.

[0091] [ka]

[0092] Alternatively, the general formula (V;R 3 Hydroxypyrazoles represented by the formula (III) (=H) are synthesized from substituted azinylacrylic acid derivatives (XIII) and phenylhydrazines (XI) as shown in Scheme 7, for example, as described in J. Heterocyclic Chem., 49, 130 (2012).

[0093] [ka]

[0094] Compounds of general formula (XIV) can be synthesized via amide coupling of substituted propionic acids of general formula (XIII) with aryl or hetaryl hydrazines of general formula (XI) in the presence of an amide coupling reagent (e.g., T3P, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide, N,N'-carbonyldiimidazole, 2-chloro-1,3-dimethylimidazolium chloride or 2-chloro-1-methylpyridinium iodide). The reaction is preferably carried out in a suitable solvent (e.g., dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate) in the presence of a base (e.g., triethylamine, N,N-diisopropylethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene) at a temperature range of 0°C to 80°C (see Scheme 7). In the second reaction step, the 3-hydroxypyrazole of formula (V) is synthesized by reacting the compound of formula (XIV) in the presence of an iron halide (e.g., iron(III) chloride). The reaction is preferably carried out in a suitable solvent (e.g., 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide or ethyl acetate) at a temperature range of 0°C to 120°C.

[0095] N-arylpyrazoles of general formula (XVII) can be prepared by N-arylation of protected 3-hydroxypyrazoles of general formula (XV) with aryl halides of general formula (XVI) in the presence of copper halides (e.g., copper(I) iodide). The reaction is preferably carried out in a suitable solvent (e.g., acetonitrile or N,N-dimethylformamide) in the presence of a base (e.g., triethylamine, cesium carbonate) at a temperature range of 0°C to 120°C (see Scheme 8). Protected 3-hydroxypyrazoles of general formula (XV) useful as starting materials can be prepared by methods similarly known to those skilled in the art (Chem. Med. Chem. 2015, 10, 1184-1199).

[0096] [ka]

[0097] Subsequently, 5-iodopyrazole of general formula (XVIII) is synthesized by reacting N-arylpyrazole of general formula (XVII) in the presence of a base (e.g., lithium diisopropylamide) and iodine. The reaction is preferably carried out in a suitable solvent (e.g., diethyl ether or tetrahydrofuran) at a temperature range of -78°C to -60°C (see Scheme 8).

[0098] Bisarylpyrazoles of formula (XIX) can be prepared, for example, by reacting iodopyrazoles of formula (XVIII) with the reagent MA in a suitable solvent and with the addition of a suitable amount of a transition metal catalyst (in particular a palladium catalyst, such as palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride, or a nickel catalyst, such as nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride), preferably in an organic solvent (e.g. 1,2-dimethoxyethane) at elevated temperature, where the "M" group can be, for example, B(OR b )(OR c ) (wherein, b and R c The groups are independently, for example, hydrogen or (C1-C4)-alkyl, or the group R b and R c are bonded to each other, they together represent ethylene or propylene (Scheme 9).

[0099] [ka]

[0100] 5-Aminopyrazoles of general formula (XX) can be synthesized by alkylating compounds of general formula (XIII) with α-halocarboxylic acid esters of general formula (IV) in the presence of a base (see Scheme 10 below) using methods known to those skilled in the art or in analogy thereto. The base can be an alkali metal (e.g., lithium, sodium, potassium or cesium) carbonate, and the reaction is preferably carried out in a suitable solvent (e.g., dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate) at a temperature range of room temperature to 150°C.

[0101] [ka]

[0102] The 5-aminopyrazole of general formula (XX) is then diazotized by reacting with a conventional organic or inorganic nitrite (e.g., 1,1-dimethylethyl nitrite, tert-butyl nitrite, or isoamyl nitrite) in the presence of copper(I) bromide and / or copper(II) chloride, copper(I) iodide, or elemental iodine, to synthesize the 5-halopyrazole of general formula (XXI), similarly as shown in Scheme 10. The reaction is preferably carried out in a suitable solvent (e.g., dichloromethane, acetonitrile, N,N-dimethylformamide, or N,N-dimethylacetamide) at a temperature range of 0° C. to 120° C. The "X" group of the 5-halopyrazole of general formula (XXI) is, for example, chlorine, bromine, or iodine. The subsequent conversion to the compound of formula (Ic) is carried out by reacting the 5-halopyrazole of general formula (XXI) with the (het)aryl derivative AM in a suitable solvent with the addition of a suitable amount of a transition metal catalyst (in particular a palladium catalyst, such as palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride, or a nickel catalyst, such as nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride), preferably in an organic solvent, such as 1,2-dimethoxyethane, at elevated temperature, where the group "M" is, for example, Mg-Hal, Zn-Hal, Sn((C1-C4)alkyl), lithium, copper or B(OR b )(OR c ) (wherein, b and R c The groups are independently, for example, hydrogen, (C1-C4)-alkyl, or the R b Groups and R c When the groups are bonded to each other, they together represent ethylene or propylene.

[0103] Selected detailed synthetic examples of the compounds of the present invention represented by general formula (I) are shown below. The example numbers listed correspond to the numbers listed in Table A below. The chemical examples are reported in the following sections. 1 H NMR, 13 C-NMR and 19 F-NMR spectroscopic data ( 1 For H NMR, 400 MHz and 13 For C NMR, 150 MHz and 19 For F NMR, 375 MHz; solvent: CDCl3, CD3OD, or d6-DMSO; internal standard: tetramethylsilane δ=0.00 ppm) was obtained on a Bruker instrument, and the signals listed have the meanings given below: br=broad; s=singlet, d=doublet, t=triplet, dd=doublet of doublets, ddd=doublet of doublets of doublets, m=multiplet, q=quartet, quint=quintet, sext=sextet, sept=septet, dq=doublet of quartets, dt=doublet of triplets. In the case of diastereomeric mixtures, the signals reported are either the important signals for each of the two diastereomers or the characteristic signal of the major diastereomer. The abbreviations used for the chemical groups have, for example, the following meanings: Me=CH3, Et=CH2CH3, t-Hex=C(CH3)2CH(CH3)2, t-Bu=C(CH3)3, n-Bu=unbranched butyl, n-Pr=unbranched propyl, i-Pr=branched propyl, c-Pr=cyclopropyl, c-Hex=cyclohexyl.

[0104] 3-(3,4-difluorophenyl)prop-2-ynoic acid: [ka]

[0105] To 5.00 g (20.83 mmol) of 1,2-difluoro-4-iodobenzene in 30 mL of dry tetrahydrofuran under an argon atmosphere, the following are successively added: 1.46 g (20.83 mmol) of propiolic acid, 0.29 g (0.42 mmol) of bis(triphenylphosphine)palladium(II) dichloride, 0.16 g (0.83 mmol) of copper(I) iodide, and 7.38 g (72.92 mmol) of diisopropylamine. The mixture is stirred at room temperature for 2 hours, the reaction mixture is added to water, 15.00 mL of 2N hydrochloric acid is added, and the mixture is repeatedly extracted with ethyl acetate. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. After purification by silica gel column chromatography with heptane / ethyl acetate (starting with heptane / ethyl acetate=95:5 and increasing to heptane / ethyl acetate=40:60 within 15 min), 2.89 g (76%) of the product (m / z=183 [M+]) is obtained.

[0106] 1 H NMR (400 MHz, d6-DMSO): δ = 7.56 (m, 2H), 7.86 (m, 1H), 13.95 (bs, 1H). 3-(3,4-difluorophenyl)-N'-(3-fluoropyridin-2-yl)prop-2-yne hydrazide [ka]

[0107] To a solution of 2.20 g (12.08 mmol) of 3-(3,4-difluorophenyl)prop-2-ynoic acid, 1.77 g (13.90 mmol) of 2-fluoro-6-hydrazinopyridine and 3.06 g (30.20 mmol) of triethylamine in 180 mL of THF, 15.34 g (24.16 mmol) of a 50% solution of propanephosphonic anhydride in THF is added dropwise and the mixture is stirred at room temperature for 1 h. For workup, H2O is added, the organic phase is removed and the aqueous phase is repeatedly extracted with CHCl2. The combined organic phases are dried over NaSO4 and concentrated. 3.20 g (72%) of crude product (80% pure) is obtained, which is used in the next reaction step without further purification.

[0108] 5-(3,4-difluorophenyl)-1-(3-fluoropyridin-2-yl)-1H-pyrazol-3-ol [ka]

[0109] 151 mg (0.79 mmol) CuI is added to a solution of 3.20 g (9.89 mmol) of 3-(3,4-difluorophenyl)-N'-(3-fluoropyridin-2-yl)prop-2-yne hydrazide in 50 mL of acetonitrile and 8 mL of DMF, and the mixture is refluxed for 3 hours. It is then filtered off, concentrated and the crude product is purified by column chromatography on silica gel with heptane / ethyl acetate (3:7). 1.96 g (67%) of the product is thus obtained in solid form.

[0110] 1 H NMR (400MHz, DMSO-d6): δ 6.15 (s, 1H), 6.95 (m, 1H), 7.30-7.40 (m, 2H), 7.55 (m, 1H), 7.95 (m, 1H), 8.25 (m, 1H). Ethyl (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetate (I-01) Ethyl (2RS)-ethoxy{[1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}acetate [ka]

[0111] To a solution of 0.25 g (0.91 mmol) of 5-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-ol in 10 mL of acetonitrile, 253 g (1.83 mmol) of K2CO3 and 186 mg (1.83 mmol) of ethyl (2RS)-chloro(ethoxy)acetate are added in sequence, and the mixture is stirred at reflux for 4 hours. CHCl2 and H2O are then added to the reaction mixture (about 10 mL each). The phases are separated using a separator cartridge, and the organic phase is concentrated under reduced pressure. Purification by column chromatography on silica gel with heptane / ethyl acetate gives 237 mg (63% yield) of the target product.

[0112] 1 H NMR (400 MHz, CDCl3): δ 1.31 (t, 6H), 3.84-4.02 (br m, 2H), 4.30 (m, 2H), 5.94 (s, 1H), 6.16 (s, 1H), 6.87 (dd, 1H), 7.22 (t, 1H), 7.37 (m, 1H), 7.44 (dt, 1H), 7.59 (dt, 1H), 8.08 (m, 1H). Ethyl (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetate (I-01) [ka]

[0113] 156 mg (0.87 mmol) of N-bromosuccinimide are added to a solution of 118 mg (0.29 mmol) of ethyl (2RS)-ethoxy{[1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}acetate in 5 mL of acetonitrile, and the mixture is stirred under reflux for 3 hours. The reaction mixture is then left overnight at room temperature, and CHCl and HO are added to the reaction mixture (approximately 10 mL each). The phases are separated using a separator cartridge, and the organic phase is then concentrated under reduced pressure. Column chromatography purification using silica gel with heptane / ethyl acetate gives 141 mg (98%) of ethyl (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetate (I-1).

[0114] 1 H NMR (400 MHz, CDCl3): δ 1.32 (pseudo q, 6H), 3.86-4.06 (br m, 2H), 4.30 (m, 2H), 5.96 (s, 1H), 6.92 (dd, 1H), 7.02 (dt, 1H), 7.22 (dt, 1H), 7.35 (m, 1H), 7.39 (dt, 1H), 7.74 (dt, 1H), 8.10 (m, 1H). Methyl (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-04) Methyl (2RS)-methoxy{[1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}acetate [ka]

[0115] 253 mg (1.83 mmol) of K2CO3 and 139 mg (1.83 mmol) of methyl (2RS)-chloro(methoxy)acetate are added in sequence to a solution of 0.25 g (0.91 mmol) of 5-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-ol in 10 mL of acetonitrile, and the mixture is stirred at reflux for 4 hours. CHCl2 and H2O are then added to the reaction mixture (approximately 10 mL each). The phases are separated using a separator cartridge, and the organic phase is concentrated under reduced pressure. Purification by column chromatography on silica gel with heptane / ethyl acetate gives 240 mg (69% yield) of the target product.

[0116] 1 H NMR (400 MHz, CDCl3): δ 3.66 (s, 3H), 3.85 (s, 3H), 5.93 (s, 1H), 6.17 (s, 1H), 6.85 (dd, 1H), 7.06 (dt, 1H), 7.24 (dt, 1H), 7.35 (m, 1H), 7.44 (dt, 1H), 7.59 (dt, 1H), 8.09 (m, 1H). Methyl (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-04) [ka]

[0117] 171 mg (0.95 mmol) of N-bromosuccinimide is added to a solution of 120 mg (0.32 mmol) of methyl (2RS)-methoxy{[1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}acetate in 5 mL of acetonitrile, and the mixture is stirred under reflux for 6 hours. The reaction mixture is then cooled to room temperature, and then CHCl and H0 are added (approximately 10 mL each). The phases are separated using a separator cartridge, and the organic phase is concentrated under reduced pressure. Column chromatography purification on silica gel with heptane / ethyl acetate gives 134 mg (91%) of methyl (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-1).

[0118] 1 H NMR (400 MHz, CDCl3): δ 3.69 (s, 3H), 3.86 (s, 3H), 5.96 (s, 1H), 6.93 (dd, 1H), 7.03 (dt, 1H), 7.21 (dt, 1H), 7.35 (m, 1H), 7.41 (dt, 1H), 7.74 (dt, 1H), 8.11 (m, 1H). Methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (I-101) and Methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfinyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (I-104) 3-(6-fluoropyridin-3-yl)prop-2-ynoic acid [ka]

[0119] To 20.00 g (130.05 mmol, 1.0 equiv.) of 2-fluoro-5-iodopyridine in 400 mL of dry tetrahydrofuran under an argon atmosphere was added the following in sequence: 10.02 g (143.06 mmol, 1.10 equiv.) of propiolic acid, 1.83 g (2.60 mmol, 0.20 equiv.) of bis(triphenylphosphine)palladium(II) dichloride, 0.99 g (5.02 mmol, 0.04 equiv.) of copper(I) iodide, and 63.80 mL (455.19 mmol, 3.50 equiv.) of diisopropylamine. The mixture was stirred at room temperature for 2 hours, diluted with ethyl acetate (300 mL), and the reaction mixture was added to ice-water (200 mL), 2N hydrochloric acid was added, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. The residue was stirred with a mixture of ethyl acetate and n-heptane (1:1) and filtered with suction. The filter cake was dried under reduced pressure and used in the next synthetic step without further purification. 19.96 g (74%, 80% purity) of 3-(6-fluoropyridin-3-yl)prop-2-ynoic acid was obtained in the form of a brown solid.

[0120] 1 H NMR (400 MHz, d 6 -DMSO δ, ppm) 14.03 (bs, 1H), 8.57 (d, 1H), 8.32 (m, 1H), 7.32 (m, 1H). 2-Hydrazino-3-(methylsulfanyl)pyridine [ka]

[0121] 2-Fluoro-3-(methylsulfanyl)pyridine (10.0 g, 69.84 mmol, 1.0 equiv) was suspended in tert-butanol (50 mL), then hydrazine hydrate (14.61 mL, 300.32 mmol, 4.30 equiv.) and potassium carbonate (8.10 g, 58.61 mmol, 0.83 equiv.) were added. The suspension was heated to boiling overnight. After cooling to room temperature, the mixture was diluted with water (200 mL) and extracted three times with dichloromethane (200 mL each time). The combined organic phases were washed with saturated sodium chloride solution and dried over sodium sulfate. The solvent was then removed under reduced pressure. Final purification of the crude product obtained by column chromatography (ethyl acetate / heptane gradient) allowed 2-hydrazino-3-(methylsulfanyl)pyridine to be isolated in the form of a beige solid (10.12 g, 88% of theory).

[0122] 1 H NMR (400 MHz, d 6 -DMSO δ, ppm) 7.98 (m, 1H), 7.47 (m, 1H), 7.01 (bs, 1H), 6.64 (m, 1H), 4.21 (bs, 2H), 2.36 (s, 3H). 3-(6-fluoropyridin-3-yl)-N'-[3-(methylsulfanyl)pyridin-2-yl]prop-2-yne hydrazide [ka]

[0123] 3-(6-Fluoropyridin-3-yl)prop-2-ynoic acid (2.40 g, 14.53 mmol, 1.0 equiv) was dissolved in THF (100 mL) and 2-hydrazino-3-(methylsulfanyl)pyridine (2.48 g, 15.99 mmol, 1.1 equiv.) and triethylamine (6.08 mL, 43.60 mmol, 3.0 equiv.) were added. At 10° C., a 50% T3P solution in THF (17.30 mL, 29.07 mmol, 2.0 equiv.) was added within 20. The resulting reaction mixture was stirred overnight at room temperature. Then the solvent was removed under reduced pressure and ethyl acetate (200 mL) and 1M pH=4.65 buffer (40 mL) were added. The organic phase was washed with saturated sodium chloride solution (20 mL), dried over sodium sulfate and the solvent was removed under reduced pressure. Final purification of the crude product obtained by column chromatography (ethyl acetate / heptane gradient) allowed the isolation of 3-(6-fluoropyridin-3-yl)-N'-[3-(methylsulfanyl)pyridin-2-yl]prop-2-ine hydrazide in the form of a brown solid (1.83 g, 39% of theory).

[0124] 1 H NMR (400 MHz, d 6 -DMSO δ, ppm) 10.60 (bs, 1H), 8.56 (s, 1H), 8.26 (m, 1H), 8.18 (bs, 1H), 7.97 (m, 1H), 7.61 (d, 1H), 7.21 (dd, 1H), 6.81 (m, 1H), 2.46 (s, 3H). 5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-ol [ka]

[0125] 3-(6-Fluoropyridin-3-yl)-N'-[3-(methylsulfanyl)pyridin-2-yl]prop-2-yne hydrazide (4.00 g, 13.23 mmol, 1.0 equiv.) was dissolved in a mixture of DMF (50 mL) and 1,2-dichloroethane (150 mL). Copper(I) iodide (0.50 g, 2.65 mmol, 0.20 equiv.) was added to the solution. The brown reaction mixture obtained was heated to 90° C. for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure. The crude product obtained was finally purified by column chromatography (ethyl acetate / heptane gradient) to isolate 5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-ol in the form of a brown solid (1.79 g, 42% of theory).

[0126] 1 H NMR (400 MHz, d 6 -DMSO δ, ppm) 10.33 (bs, 1H), 8.17 (m, 1H), 8.02 (m, 1H), 7.90 (d, 1H), 7.66 (m, 1H), 7.49 (m, 1H), 7.13 (dd, 1H), 6.17 (bs, 1H), 2.43 (s, 3H). Methyl ({5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate [ka]

[0127] 5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-ol (277 mg, 0.92 mmol, 1.0 equiv) was dissolved in acetonitrile (20 mL), then methyl chloro(methoxy)acetate (190 mg, 1.37 mmol, 1.50 equiv.) and potassium carbonate (380 mg, 2.75 mmol, 3.0 equiv.) were added. The suspension was heated to 90° C. for 3 hours. After cooling, the solid was filtered off with suction, the residue was washed twice with acetonitrile (4 mL each time) and the solvent was removed under reduced pressure. Final purification of the crude product obtained by column chromatography (ethyl acetate / heptane gradient) allowed the isolation of methyl ({5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate in the form of a brown solid (330 mg, 84% of theory).

[0128] 1 H NMR (400 MHz, CDCl3δ, ppm) 8.17 (m, 1H), 8.06 (d, 1H), 7.68-7.61 (m, 21H), 7.30 (dd, 1H), 6.85 (dd, 1H), 6.19 (s, 1H), 5.99 (s, 1H), 3.84 (s, 3H), 3.66 (s, 3H), 2.38 (s, 3H). Methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (I-101) and Methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfinyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (I-104) [ka]

[0129] Methyl ({5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (180 mg, 0.44 mmol, 1.0 equiv) was dissolved in acetonitrile (12 mL) and 1,3-diiodo-5,5-dimethylimidazolidine-2,4-dione (101 mg, 0.27 mmol, 0.6 equiv.) was added at room temperature. The reaction was stirred at room temperature overnight. Then, one drop of concentrated sulfuric acid was added to the reaction mixture, which was stirred at room temperature overnight. After checking the reaction by thin layer chromatography, another drop of concentrated sulfuric acid was added and the mixture was stirred at room temperature for 3 hours. Then, water (5 mL) and saturated sodium bicarbonate solution were added to the reaction solution, which was extracted twice with dichloromethane (70 mL). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. Final purification of the crude product obtained by column chromatography (ethyl acetate / heptane gradient) allowed methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate to be isolated in the form of a white solid (130 mg, 52% of theory) and methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfinyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate to be isolated in the form of a white solid (83 mg, 32% of theory).

[0130] I-101: Methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate 1H NMR (400 MHz, CDCl3δ, ppm) 8.15-8.10 (m, 2H), 7.85 (m, 1H), 7.58 (m, 1H), 7.27 (m, 1H), 6.91 (m, 1H), 5.99 (m, 1H), 3.84 (s, 3H), 3.68 (s, 3H), 2.39 (s, 3H). I-104: Methyl ({5-(6-fluoropyridin-3-yl)-4-iodo-1-[3-(methylsulfinyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate 1 H NMR (400 MHz, CDCl3δ, ppm) 8.15-8.10 (m, 2H), 7.85 (m, 1H), 7.27-7.25 (m, 2H), 6.91 (m, 1H), 5.99 (m, 1H), 3.84 (s, 3H), 3.68 (s, 3H), 2.39 (s, 3H). Methyl {[4-chloro-1-(3-chloro-2-fluorophenyl)-5-(5-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-26): [ka]

[0131] Methyl {[1-(3-chloro-2-fluorophenyl)-5-(5-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (100 mg, 0.24 mmol, 1.0 equiv) was dissolved in acetonitrile (10 mL) and 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (29 mg, 0.14 mmol, 0.6 equiv.) was added at room temperature. The reaction was stirred overnight at room temperature. The reaction mixture was then stirred overnight at room temperature. Water (5 mL) and saturated sodium bicarbonate solution were then added to the reaction solution, which was extracted twice with dichloromethane (70 mL). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. Final purification of the crude product obtained by column chromatography (ethyl acetate / heptane gradient) allowed the isolation of methyl {[4-chloro-1-(3-chloro-2-fluorophenyl)-5-(5-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate in the form of a white solid (94 mg, 82% of theory).

[0132] 1 H NMR (400 MHz, CDCl3δ, ppm) 8.49 (d, 1H), 8.26 (d, 1H), 7.45-7.41 (m, 2H), 7.29 (m, 1H), 7.17 (m, 1H), 5.94 (s, 1H), 3.86 (s, 3H), 3.69 (s, 3H). Methyl ({4-chloro-5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfinyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (I-103) and Methyl {[4-chloro-1-{3-[(chloromethyl)sulfanyl]pyridin-2-yl}-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-102) [ka]

[0133] Methyl ({5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfanyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (60 mg, 0.14 mmol, 1.0 equiv) was dissolved in acetonitrile (5 mL) and 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (18 mg, 0.08 mmol, 0.6 equiv.) was added at room temperature. The reaction was stirred at room temperature overnight. The reaction mixture was then stirred at room temperature overnight. Water (5 mL) and saturated sodium bicarbonate solution were then added to the reaction solution, which was extracted twice with dichloromethane (70 mL). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. The crude product obtained was finally purified by column chromatography (ethyl acetate / heptane gradient) to isolate methyl ({4-chloro-5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfinyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate (11 mg, 15% of theory) and methyl {[4-chloro-1-{3-[(chloromethyl)sulfanyl]pyridin-2-yl}-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (20 mg, 27% of theory).

[0134] I-103: Methyl ({4-chloro-5-(6-fluoropyridin-3-yl)-1-[3-(methylsulfinyl)pyridin-2-yl]-1H-pyrazol-3-yl}oxy)(methoxy)acetate 1 H NMR (400 MHz, CDCl3δ, ppm) 8.59 (m, 1H), 8.23-8.17 (m, 2H), 7.81 (m, 1H), 7.45 (m, 1H), 6.98 (m, 1H), 5.84 (s, 1H), 3.89 (s, 3H), 3.68 (s, 3H), 2.94 (d, 3H). I-102: Methyl {[4-chloro-1-{3-[(chloromethyl)sulfanyl]pyridin-2-yl}-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate 1 H NMR (400 MHz, CDCl3δ, ppm) 8.25 (m, 1H), 8.13 (d, 1H), 8.05 (d, 1H), 7.83 (m, 1H), 7.35 (m, 1H), 6.9 (dd, 1H), 5.93 (s, 1H), 4.90 (s, 2H), 3.85 (s, 3H), 3.68 (s, 3H). (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetic acid (I-51) [ka]

[0135] 285.0 mg (0.591 mmol) of ethyl (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetate is initially charged in 3.6 mL of tetrahydrofuran and 1.2 mL of water, to which 49.5 mg (1.182 mmol) of lithium hydroxide monohydrate are added. The reaction mixture is stirred at room temperature for 2 hours. Ethyl acetate is added, the mixture is acidified with 0.6 mL (1.182 mmol) of 2 M aqueous hydrochloric acid and repeatedly extracted with ethyl acetate. The combined organic phases are dried and concentrated under reduced pressure. 265.8 mg (94% yield) of a yellowish oil (95% purity) is obtained.

[0136] Methyl 3-{[(2RS)-2-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}-2-ethoxyethanoyl]oxy}propanoate (I-59) Methyl 3-{[(2R * )-2-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}-2-ethoxyethanoyl]oxy}propanoate (Enantiomer 1, I-64) Methyl 3-{[(2R * )-2-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}-2-ethoxyethanoyl]oxy}propanoate (enantiomer 2, I-63) [ka]

[0137] 1000.0 mg (2.202 mmol) of (2RS)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetic acid is initially charged in 32.2 mL of tetrahydrofuran, to which 723.8 mg (6.605 mmol) of methyl 3-hydroxypropanoate, 2101.5 mg (3.302 mmol) of propylphosphonic anhydride (T3P), 2.7 mg (0.022 mmol) of 4-dimethylaminopyridine (DMAP) and 445.6 mg (4.403 mmol) of triethylamine are added in succession. The reaction mixture is stirred for 2 hours at 50° C. Methylene chloride and saturated aqueous ammonium chloride solution are added and the mixture is repeatedly extracted with methylene chloride. The organic phases are combined, separated using a phase separator, dried and concentrated under reduced pressure. The residue is taken up in a small amount of methylene chloride and chromatographed on a Biotage Isolera (column: MN Chromabond RS40, gradient: 10% to 90% EA in 8 runs). After a first round of 59.4 mg of colorless oil (which consists of a mixture of unknown components and is discarded), 737.0 mg (59% yield) of methyl 3-{[(2RS)-2-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}-2-ethoxyethanoyl]oxy}propanoate (I-59) is obtained in the form of a colorless oil.

[0138] This mixture is separated into its enantiomers by chiral supercritical fluid chromatography (SFC) in the following manner: Chir_C1_IC_B1_90CO2_MeOH_QDA1. After 2.904 min, 240.8 mg (20% yield) of a colorless oil (enantiomer 1, I-64) is obtained: 1H NMR (400 MHz, CDCl3): δ =1.30 (t, 3H), 2.70 (t, 2H), 3.65 (s, 3H), 3.85 (m, 1H), 4.05 (m, 1H), 4.50 (t, 2H), 5.95 (s, 1H), 6.95 (dd, 1H), 7.05 (dt, 1H), 7.20 (t, 1H), 7.35 (m, 1H), 7.45 (dt, 1H), 7.75 (dt, 1H), 8.10 (d, 1H) And, After 2.987 min, 320.9 mg (26% yield) of a colorless oil (enantiomer 2, I-63) is obtained: 1 H NMR (400 MHz, CDCl3): δ =1.30 (t, 3H), 2.70 (t, 2H), 3.65 (s, 3H), 3.85 (m, 1H), 4.05 (m, 1H), 4.50 (t, 2H), 5.95 (s, 1H), 6.95 (dd, 1H), 7.05 (dt, 1H), 7.20 (t, 1H), 7.35 (m, 1H), 7.45 (dt, 1H), 7.75 (dt, 1H), 8.10 (d, 1H) The enantiomerically pure double esters thus obtained are then each separately hydrolyzed and then separately re-esterified.

[0139] (2R * )-{[4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetic acid (enantiomer 1) In 5.0 mL of tetrahydrofuran and 2.0 mL of water, 120.4 mg (0.223 mmol) of methyl 3-{[(2R *)-2-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}-2-ethoxyethanoyl]oxy}propanoate (enantiomer 1) is charged to which 18.7 mg (0.446 mmol) of lithium hydroxide monohydrate is added. The reaction mixture is stirred at room temperature for 2 hours. Ethyl acetate is added, the mixture is acidified with 0.22 mL (0.446 mmol) of 2 M aqueous hydrochloric acid and repeatedly extracted with ethyl acetate. The combined organic phases are dried and concentrated under reduced pressure. 101.0 mg (97% yield) of a yellowish oil (98% purity) is obtained, which crystallizes after a while.

[0140] (2R * )-{[4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetic acid (enantiomer 2, I-65) In 5.0 mL of tetrahydrofuran and 2.0 mL of water, 214.0 mg (0.396 mmol) of methyl 3-{[(2R * )-2-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}-2-ethoxyethanoyl]oxy}propanoate (enantiomer 2) is initially charged, to which 33.2 mg (0.792 mmol) of lithium hydroxide monohydrate are added. The reaction mixture is stirred at room temperature for 2 hours. Ethyl acetate is added, the mixture is acidified with 0.40 mL (0.792 mmol) of 2 M aqueous hydrochloric acid and repeatedly extracted with ethyl acetate. The combined organic phases are dried and concentrated under reduced pressure. 188.9 mg (99% yield) of a yellowish oil (95% purity) is obtained, which crystallizes after a while.

[0141] Ethyl (2R * )-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetate (enantiomer 1, I-66) In 5.0 mL of tetrahydrofuran, 101.0 mg (0.222 mmol) of (2R *)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetic acid (enantiomer 1) is initially charged, to which 32.3 mg (0.667 mmol) of ethanol, 212.3 mg (0.334 mmol) of propylphosphonic anhydride (T3P), 0.27 mg (0.002 mmol) of 4-dimethylaminopyridine (DMAP) and 45.0 mg (0.445 mmol) of triethylamine are added successively. The reaction mixture is stirred for 2 hours at 50° C. Methylene chloride and saturated aqueous ammonium chloride solution are added and the mixture is repeatedly extracted with methylene chloride. The organic phases are combined, separated using a phase separator, dried and concentrated under reduced pressure. The residue is taken up in a small amount of methylene chloride and chromatographed on a Biotage Isolera (column: MN Chromabond RS40, gradient: 10% to 90% EA in 8 runs). 40.3 mg (36% yield) of a colorless oil (98% purity) is obtained.

[0142] Ethyl (2R*)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetate (Enantiomer 2, I-67) 100.0 mg (0.220 mmol) of (2R *)-{[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(ethoxy)acetic acid (enantiomer 2) is initially charged, to which 32.0 mg (0.660 mmol) of ethanol, 210.1 mg (0.330 mmol) of propylphosphonic anhydride (T3P), 0.27 mg (0.002 mmol) of 4-dimethylaminopyridine (DMAP) and 44.6 mg (0.440 mmol) of triethylamine are added successively. The reaction mixture is stirred for 2 hours at 50° C. Methylene chloride and saturated aqueous ammonium chloride solution are added and the mixture is repeatedly extracted with methylene chloride. The organic phases are combined, separated using a phase separator, dried and concentrated under reduced pressure. The residue is taken up in a small amount of methylene chloride and chromatographed on a Biotage Isolera (column: MN Chromabond RS40, gradient: 10% to 90% EA in 8 runs). 34.8 mg (32% yield) of a colorless oil (98% purity) is obtained.

[0143] Methyl (2RS)-{[4-(difluoromethyl)-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-120) 3-(Benzyloxy)-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazole-4-carbaldehyde [ka]

[0144] 6 mL of tetrahydrofuran are added under argon and the mixture is cooled to -70°C. A solution of isopropylmagnesium chloride-lithium chloride complex (0.7 mL, 0.971 mmol) is added dropwise to it. Then, 485.0 mg (0.971 mmol) of 5-[3-(benzyloxy)-1-(2-fluorophenyl)-4-iodo-1H-pyrazol-5-yl]-2-fluoropyridine dissolved in 3 mL of tetrahydrofuran are added dropwise. After stirring for 1 hour at -70°C, 177.5 mg (2.429 mmol) of N,N-dimethylformamide are added dropwise and the reaction mixture is stirred for 2 hours at room temperature. Then, a saturated aqueous solution of ammonium chloride is added to the reaction mixture and it is extracted twice with ethyl acetate. The organic phases are combined, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue is taken up in a small amount of methylene chloride and chromatographed (Biotage Isolera, column: MN Chromabond RS40, 8 runs, 5%→50% EA) to obtain 303.6 mg (79% yield) of an oil (99% purity).

[0145] 1 H NMR (400 MHz, CDCl3): δ =5.40 (s, 2H), 6.95 (dd, 1H), 7.05 (dt, 1H), 7.25 (dt, 1H), 7.35-7.45 (m, 4H), 7.45-7.55 (m, 3H), 7.85 (dt, 1H), 8.05 (m, 1H), 9.90 (s, 1H) Methyl (2RS)-{[4-(difluoromethyl)-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-120) [ka]

[0146] 248.0 mg (0.604 mmol) of methyl (2RS)-{[1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-4-formyl-1H-pyrazol-3-yl]oxy}(methoxy)acetate thus obtained are initially charged in 10.0 mL of methylene chloride, which is cooled to 0° C. Then, 291.8 mg (1.811 mmol) of diethylaminosulfur trifluoride (DAST) are added dropwise and the reaction mixture is slowly brought to room temperature. Water is added and the mixture is repeatedly extracted with methylene chloride. The combined organic phases are removed using a phase separator, dried and concentrated under reduced pressure. The residue is taken up in a small amount of methylene chloride and chromatographed (Biotage Isolera, column: MN Chromabond RS40, 9 runs, 5% → 65% EA). 239.3 mg (88% yield) of a colourless oil (95% purity) are obtained.

[0147] Methyl {[4-cyclopropyl-1-(2,5-difluorophenyl)-5-(5-fluoropyridin-3-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-31) [ka]

[0148] To 0.530 g (0.970 mmol) of methyl {[1-(2,5-difluorophenyl)-5-(5-fluoropyridin-3-yl)-4-iodo-1H-pyrazol-3-yl]oxy}(methoxy)acetate in 25.0 mL of dioxane, under nitrogen, 0.250 g (2.909 mmol) of cyclopropylboronic acid, 0.295 g (1.939 mmol) of cesium fluoride and 0.079 g (0.097 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (complex with dichloromethane) were added, and the mixture was stirred at reflux for 3 h. The reaction mixture was concentrated under reduced pressure, the residue was taken up in dichloromethane and water, the aqueous phase was repeatedly extracted with dichloromethane, the combined organic phases were dried over sodium sulfate and the solvent was removed under reduced pressure. After purification by silica gel column chromatography with heptane / ethyl acetate, 0.424 g (96% of theory) of an oil was obtained.

[0149] Methyl {[1-(3-fluoropyridin-2-yl)-5-(6-fluoropyridin-3-yl)-4-(trifluoromethyl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate (I-41) [ka]

[0150] To 0.500 g (0.996 mmol) of methyl {[1-(3-fluoropyridin-2-yl)-5-(6-fluoropyridin-3-yl)-4-iodo-1H-pyrazol-3-yl]oxy}(methoxy)acetate in 25.0 mL of dimethylacetamide, 0.956 g (4.978 mmol) of methyl difluoro(fluorosulfonyl)acetate and 0.379 g (1.991 mmol) of copper(I) iodide were added and the mixture was stirred at 85° C. for 5 hours. Ethyl acetate was added to the reaction mixture, it was filtered, the filtrate was concentrated under reduced pressure, the residue was taken up in dichloromethane and water, the aqueous phase was repeatedly extracted with dichloromethane, the organic phases were combined, dried over sodium sulfate and the solvent was removed under reduced pressure. After purification by silica gel column chromatography using heptane / ethyl acetate, 0.241 g (52% of theory) of an oil was obtained.

[0151] {[4-Chloro-5-(6-fluoropyridin-3-yl)-1-(pyrazin-2-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetic acid (I-42) [ka]

[0152] To 0.180 g (0.457 mmol) of methyl {[4-chloro-5-(6-fluoropyridin-3-yl)-1-(pyrazin-2-yl)-1H-pyrazol-3-yl]oxy}(methoxy)acetate in 10.0 mL of tetrahydrofuran was added a solution of 0.027 g (1.143 mmol) of lithium hydroxide in 3 mL of water and the mixture was stirred for 2 h at 25° C. The aqueous phase was adjusted to pH=2-3 with 2 M aqueous hydrochloric acid, the solvent was removed under reduced pressure, the residue was taken up in water and extracted three times with dichloromethane. The combined organic phases were dried over sodium sulfate and the solvent was removed under reduced pressure. A colorless solid (0.179 g, 96% of theory) was obtained.

[0153] The compounds of the present invention represented by formula (I) (and / or salts thereof) (hereinafter collectively referred to as "compounds of the present invention") exhibit excellent herbicidal activity against a wide range of economically important monocotyledonous and dicotyledonous annual harmful plants.

[0154] The present invention therefore also provides a method for controlling undesirable plants or regulating plant growth, preferably in crop plants, in which one or more compounds according to the invention are applied to the plant (e.g., a harmful plant, such as a monocotyledonous or dicotyledonous weed, or an undesirable crop plant) or to a seed (e.g., a grain, a seed, or a vegetative propagation organ, such as a tuber or a shoot part having a bud) or to an area in which the plant is growing (e.g., an arable land). The compounds of the present invention can be used, for example, before planting (and, if appropriate, by incorporation into the soil), before emergence or after emergence. Specific examples of some representative monocotyledonous and dicotyledonous weed floras that can be controlled by the compounds of the present invention are as follows, but such listing is not intended to be limited to a particular species.

[0155] Monocotyledonous harmful plants of the following genera:: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, The genera Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, and Sorghum.

[0156] Dicotyledonous weeds of the following genera:: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirrus sium), Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium dium), Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, and Rotala), Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica,Viola, Xanthium.

[0157] When the compounds of this invention are applied pre-emergence to the soil surface, emergence of weed seedlings is either completely prevented or the weeds grow until they reach the cotyledon stage and then cease growth.

[0158] If the active ingredients are applied post-emergence to the green parts of the plants, growth stops after the treatment and the harmful plants either remain in the growth stage present at the time of application or die completely after a certain period of time, so that in this way competition with weeds which are harmful to the crop plants is eliminated very early and permanently.

[0159] The compounds of the invention can be selective among useful plant crops and can also be used as non-selective herbicides.

[0160] The active ingredients can also be used to control harmful plants in crops of known or to be developed transgenic plants by their herbicidal and plant growth regulating properties. In general, transgenic plants are characterized by certain advantageous properties, such as resistance to certain active ingredients (particularly certain herbicides) used in the agrochemical industry, resistance to plant diseases or pathogens of plant diseases (e.g., certain insects or microorganisms, such as fungi, bacteria or viruses). Another specific property relates, for example, to the quantity, quality, storability, composition and specific components of the harvest. For example, there are known transgenic plants with increased starch content or modified starch quality, or with different fatty acid composition in the harvest. A further specific property is tolerance or resistance to abiotic stress factors, such as heat, low temperature, drought, salinity and UV light.

[0161] Preferably, the compounds of formula (I) or salts thereof are used in economically important transgenic crops of useful and ornamental plants.

[0162] The compounds of formula (I) can be used as herbicides in crops of useful plants which are resistant, or have been made resistant by genetic engineering, to the phytotoxic effects of the herbicides in question.

[0163] Conventional methods for generating new plants with modified properties compared to existing plants are, for example, conventional cultivation methods and the generation of mutants. Alternatively, new plants with altered properties can be generated using recombinant methods (see, for example, EP 0221044, EP 0131624). For example, several cases have been described relating to the genetic modification of crop plants with the aim of modifying the starch synthesized in the plant (for example WO 92 / 011376A, WO 92 / 014827A, WO 91 / 019806A); transgenic crop plants, e.g. Optimum β-lactam ... TM GAT TM (Glyphosate ALS Tolerant) trade name or designation, such as corn or soybean; · transgenic crop plants (e.g. cotton) capable of producing Bacillus thuringiensis toxins (Bt toxins) that render the plants resistant to certain pests (EP 0142924A, EP 0193259A); · Transgenic crop plants with altered fatty acid composition (WO 91 / 013972A); · Genetically modified crop plants with novel components or secondary metabolites (e.g. novel phytoalexins that improve disease resistance) (EP 0309862A, EP 0464461A); · Transgenic plants with reduced photorespiration with higher yields and higher stress tolerance (EP 0305398A); · Transgenic crop plants producing proteins of pharma- ceutical or diagnostic importance ("molecular pharming"); · Transgenic crop plants characterized by higher yields or better quality; · Transgenic crop plants, distinguished by combinations of novel properties, e.g. as described above ("gene stacking").

[0164] Many molecular biological techniques are known in principle that can be used to generate new transgenic plants with modified properties; see, for example, I. Potrykus and G. Spangenberg (eds), Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, “Trends in Plant Science” 1 (1996) 423-431.

[0165] For such genetic manipulation, nucleic acid molecules that allow sequence changes by mutagenesis or recombination of DNA sequences can be introduced into plasmids. Using standard methods, for example, base exchanges can be performed, subsequences can be removed, or natural or synthetic sequences can be added. Adapters or linkers can be added to DNA fragments to link them together; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd edition, 1996.

[0166] For example, the generation of plant cells with reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, or by expressing a sense RNA to achieve a cosuppression effect, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of said gene product. For this purpose, it is possible to use DNA molecules that contain the entire coding sequence of the gene product, including all possible flanking sequences, and also to use DNA molecules that contain only parts of the coding sequence, in which case these parts must be long enough to have an antisense effect in the cell. Furthermore, DNA sequences that are highly homologous to the coding sequences of the gene products, but are not completely identical to them, can also be used.

[0167] When expressing a nucleic acid molecule in a plant body, the synthesized protein can be localized in any desired compartment of the plant cell. However, to localize in a specific compartment, it is possible, for example, to link the coding region to a DNA sequence that ensures localization in a specific compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227, Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850, Sonnewald et al., Plant J. 1 (1991), 95-106). Furthermore, such nucleic acid molecules can be expressed in organelles of plant cells.

[0168] The transgenic plant cells can be regenerated by known techniques to give rise to whole plants. In principle, the transgenic plants can be of any desired plant species, i.e., not only can they be monocotyledonous, but also dicotyledonous.

[0169] In this way, transgenic plants can be obtained which have properties altered by overexpression, suppression or inhibition of a homologous (= natural) gene or gene sequence or by expression of a heterologous (= foreign) gene or gene sequence.

[0170] The compounds (I) of the present invention can be preferably used in transgenic crops resistant to growth regulators (e.g. 2,4-D, dicamba) or to herbicides inhibiting essential plant enzymes (e.g. acetolactate synthase (ALS), EPSP synthase, glutamine synthase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD)), or in transgenic crops resistant to herbicides selected from the group of sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and similar active ingredients, or in transgenic plants resistant to any desired combination of these active ingredients.

[0171] The compounds of the present invention can be particularly preferably used in transgenic crop plants that are resistant to a combination of glyphosates and glufosinates, or to a combination of glyphosates and sulfonylureas or imidazolinones.Most preferably, the compounds of the present invention can be used in transgenic crop plants (e.g., corn or soybean) that have, for example, the trade name or designation Optimum™ GAT™ (glyphosate ALS resistance).

[0172] The use of the active ingredients of the invention in transgenic crops not only results in the effects against harmful plants observed in other crops, but in many cases also in effects specific to the application in a particular transgenic crop, such as a modified or especially expanded spectrum of weeds that can be controlled, modified application rates that can be used for said application, preferably better combinability with herbicides to which the transgenic crop is resistant, as well as effects on the growth and yield of the transgenic crop plants.

[0173] The present invention therefore also relates to the use of the compounds of formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

[0174] The compounds of the present invention can be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in conventional formulations.Thus, the present invention also provides herbicidal compositions and plant growth regulating compositions comprising the compounds of the present invention.

[0175] The compounds of the invention can be formulated in various ways depending on the biological and / or physicochemical parameters required. Possible formulations include, for example, wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water emulsions and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), dressings, granules for broadcast and granules for soil application, granules in the form of microgranules (GR), spray granules, absorption granules and impregnated granules. granules), water dispersible granules (WG), water-soluble granules (SG), microdustable formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in Winnacker-Kuchler, “Chemische Technologie” [Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, NY, 1973, K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

[0176] The necessary formulation auxiliaries, such as inert substances, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd ed., Darland Books, Caldwell NJ; Hv Olphen, “Introduction to Clay Colloid Chemistry”, 2nd ed., J. Wiley & Sons, NY; C. Marsden, “Solvents Guide”, 2nd ed., Interscience, NY 1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood NJ; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., NY 1964; Schonfeldt, “Grenzflachenaktive Athylenoxidaddukte” [Interface-active Ethylene Oxide Winnacker-Kuchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th ed. 1986”.

[0177] On the basis of these formulations, it is also possible to prepare combinations with further active ingredients (e.g. insecticides, acaricides, herbicides, fungicides) and also with safeners, fertilizers and / or growth regulators, for example in the form of finished formulations or as tank mixes.

[0178] Combination partners that can be used in combination with the compounds of the present invention in mixed formulations or tank mixes are, for example, known active ingredients based on inhibiting, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II or protoporphyrinogen oxidase, for example, as known from Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006 and the references cited therein. Known herbicides or plant growth regulators that can be combined with the compounds of the present invention are, for example, the following, where the active ingredients are indicated by their "common name" according to the International Organization for Standardization (ISO), or by their chemical name, or by their code number. They always include all use forms, such as acids, salts, esters, etc., even if not explicitly mentioned, and also include all isomeric forms, such as stereoisomers and optical isomers.

[0179] Examples of such herbicidal admixture partners are: Acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, aminopyralid-dimethylammonium, Aminopyralid-trypromine, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Asulam-potassium, Asulam-sodium, Atrazine, Azafenidine, Azimsulfuron, Beflubutamid, (S)-(-)-Beflubutamid, Beflubutamid-M, Benazolin, Benazolin-ethyl, Benazolin-dimethylammonium, Benazolin-potassium, Benfluralin, Benfuresate, Bensulfuron, Bensulfuron-methyl, Bensulide, Bentazon, Bentazon-sodium, Benzobicyclon, Benzofenap, Bicyclo Ropyrone, Bifenox, Biranaphos, Biranaphos-sodium, Bipyrazone, Bispyribac, Bispyribac-sodium, Bixlozone, Bromacil, Bromacil-lithium, Bromacil-sodium, Bromobutide, Bromophenoxime, Bromoxynil, Bromoxynil-butyrate, -potassium, -heptanoate and -octanoate, Busoxinon, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butyrate, Cafenstrole, Cambendichlor, Carbetami do, carfentrazone, carfentrazone-ethyl, chloramben, chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium, chloramben-sodium, chlorbromuron, chlorfenac, chlorfenac-ammonium, chlorfenac-sodium, chlorfenprop, chlorfenprop-methyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron,Chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, cinidon, cinidon-ethyl, symmetryn, exo-(+)-symmetryn, i.e., (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptane, exo-(-)-symmetryn, i.e., (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptane, cinosulfuron, clasifos, cleto Dim, clodinafop, clodinafop-ethyl, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-trypomine, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D (which includes the following salts of 2,4-D: ammonium salt, -butotyl salts, -butyl salts, -choline salts, -diethylammonium salts, -dimethylammonium salts, -diolamine salts, -doboxyl salts, -dodecylammonium salts, -ethexyl salts, -ethyl salts, -2-ethylhexyl salts, -heptylammonium salts, -isobutyl salts, -isooctyl salts, -isopropyl salts, -isopropylammonium salts, -lithium salts, -meptyl salts, -methyl salts, -potassium salts, -tetradecylammonium salts, -triethylammonium salts, -triisopropanolammonium salts, -tryplomine salts and -trolamine salts). 2,4-DB, 2,4-DB-butyl, -dimethylammonium, -isooctyl, -potassium and -sodium, daimuron (dymron), dalapon, dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet, dazomet-sodium, n-decanol, 7-deoxy-d-sedoheptulose, desmedipham, detosyl-pyrazolate (dTP), dicamba and its salts, such as dicamba-biproamine, dicamba-N,N-bis(3-aminopropyl)methylamine, dicamba-butotyl,Dicamba choline, Dicamba diglycolamine, Dicamba dimethylammonium, Dicamba diethanolamine ammonium, Dicamba diethylammonium, Dicamba isopropylammonium, Dicamba methyl, Dicamba monoethanolamine, Dicamba olamine, Dicamba potassium, Dicamba sodium, Dicamba triethanolamine, Dicamba triethanolamine, Dichlobenil, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, Dichlorprop, Dichlorprop-butotyl, Dichlorprop Prop-dimethylammonium, dichlorprop-ethexyl, dichlorprop-ethylammonium, dichlorprop-isooctyl, dichlorprop-methyl, dichlorprop-potassium, dichlorprop-sodium, dichlorprop-P, dichlorprop-P-dimethylammonium, dichlorprop-P-ethexyl, dichlorprop-P-potassium, dichlorprop-sodium, diclofop, diclofop-methyl, diclofop-P, diclofop-P-methyl, diclosulam, difenzoquat, Difenzoquat-methylsulfate, Diflufenican, Diflufenzopyr, Diflufenzopyr-sodium, Dimefurone, Dimepiperate, Dimethasulfazate, Dimethachlor, Dimethamethrin, Dimethenamid, Dimethenamid-P, Dimetrasulfuron, Dinitramine, Dinoterb, Dinoterb-acetate, Diphenamide, Diquat, Diquat-dibromide, Diquat-dichloride, Dithiopyr, Diuron, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, Endothal, Endothal-diammoni um, endothal-dipotassium, endothal-disodium, epirifenacil (S-3100), ePTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyphene, ethoxyphene-ethyl, ethoxysulfuron, etobenzanide, F-5231, i.e., N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1yl]-phenyl]ethanesulfonamide, F-7967, i.e.,3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M- Methyl, Flazasulfuron, Florasulam, Florpyrauxifen, Florpyrauxifen-benzyl, Fluazifop, Fluazifop-butyl, Fluazifop-methyl, Fluazifop-P, Fluazifop-P-butyl, Flucarbazone, Flucarbazone-sodium, Flucetosulfuron, Fluchloralin, Flufenacet, Flufenpyr, Flufenpyr-ethyl, Flumetsulam, Flumicrac, Flumicrac-pentyl, Flumioxazin, Fluometuron, Flurenol, Flurenol-butyl, -di Methylammonium and -methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupropanate-sodium, flupyrsulfuron, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butomethyl, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, foramsulfuron-sodium, fosamine, fosamine- Ammonium, glufosinate, glufosinate-ammonium, glufosinate-sodium, L-glufosinate-ammonium, L-glufosinate-sodium, glufosinate-P-sodium, glufosinate-P-ammonium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium, glyphosate-sesquisodium and -trimesium, H-9201, i.e., O-(2,4-dimethyl-6-nitrophenyl) O-ethyl isopropylphosphoramidothioate, halaxifen,Haloxifene-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, haloxyfop-sodium, hexazinone, HNPC-A8169, i.e., prop-2-yn-1-yl(2S)-2-{3-[(5-tert-butylpyridin-2-yl)oxy]phenoxy}propanoate, HW-02, i.e., 1-(dimethoxyphosphoryl)ethyl(2,4-dimethoxyphenyl ... rophenoxy) acetate, hydantocidin, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazaquin-methyl, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium, ioxyni , ioxynil-lithium, -octanoate, -potassium and -sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, carbutilate, KUH-043, i.e., 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole, ketospiradox, ketospiradox-potassium, lactofen, lenacil, linuron, M CPA, MCPA-butotyl, -butyl, -dimethylammonium, -diolamine, -2-ethylhexyl, -ethyl, -isobutyl, -isooctyl, -isopropyl, -isopropylammonium, -methyl, -olamine, -potassium, -sodium and -trolamine, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-butotyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethexyl, mecoprop-ethadyl, mecoprop-isooctyl, mecoprop-methyl,Mecoprop-potassium, mecoprop-sodium and mecoprop-trolamine, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mefluidide-diolamine, mefluidide-potassium, mesosulfuron, mesosulfuron-methyl, mesosulfuron-, Sodium, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozoline, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, methoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monolinuron, monosulfuron, monosulfuron-methyl, MT-5950, i.e., N-[3-chloro-4-(1-methylethyl)-2-propanol] methyl)phenyl]-2-methylpentanamide, NGGC-011, napropamide, NC-310, i.e., 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, NC-656, i.e., 3-[(isopropylsulfonyl)methyl]-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)[1,2,4]triazolo-[4,3-a]pyridine-8-carboxamide, nebulon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acid), orbencarb , Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefon, Oxyfluorfen, Paraquat, Paraquat-dichloride, Paraquat-dimethylsulfate, Pebulate, Pendimethalin, Penoxsulam, Pentachlorophenol, Pentoxazone, Petroxamide, Petroleum, Phenmedipham, Phenmedipham-ethyl, Picloram, Picloram-dimethylammonium, Picloram-ethexyl, Picloram-isooctyl, Picloram-methyl, Picloram-olamine, Picloram-ca lium, picloram-triethylammonium, picloram-tryplomine, picloram-trolamine, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen,Pyraflufen-ethyl, pyrasulfotole, pyrazolinate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinclorac-dimethylammonium, quinclorac-methyl, quinmerac, quinoclamine, quizalofop , Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, QYM201, i.e., 1-{2-chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6-(trifluoromethyl)phenyl}piperidin-2-one, Rimsulfuron, Saflufenacil, Sethoxydim, Siduron, Simazine, Simetryne, SL-261, Sulcotrione, Sulfentrazone, Sulfometuron, Sulfometuron-methyl, Sulfosulfuron, SYP-249, i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid) and its salts, e.g. TCA-ammonium, TCA-calcium, TCA-ethyl, TCA-magnesium, T CA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, tetflupyrolimet, thaxtomin, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, thiaphenacyl, torpiralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron,Triaziflam, tribenuron, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-choline, triclopyr-ethyl, triclopyr-triethylammonium, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, i.e., 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidine-1 (2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 3-chloro-2-[3-(difluoromethyl)isoxazolyl-5-yl]phenyl 5-Chloropyrimidin-2-yl ether, 2-(3,4-dimethoxyphenyl)-4-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-6-methylpyridazin-3(2H)-one, 2-({2-[(2-methoxyethoxy)methyl]-6-methylpyridin-3-yl}carbonyl)cyclohexane-1,3-dione, (5-hydroxy-1-methyl-1H-pyrazol-4-yl)(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophen-5-yl)methanone, 1-methyl-4-[(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophen-5-yl)carbonyl]-1H-pyrazol-5-yl Propane-1-sulfonate, 4-{2-chloro-3-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-4-(methylsulfonyl)benzoyl}-1-methyl-1H-pyrazol-5-yl 1,3-dimethyl-1H-pyrazole-4-carboxylate, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate cyanomethyl,4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate prop-2-yn-1-yl, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate methyl, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid benzyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, ethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylate, methyl ...6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate, methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylate, -amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylate methyl, 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)-1H-indol-6-yl]pyridine-2-carboxylate methyl, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate potassium, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate potassium, sodium chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, 3-(5-tert-butyl-1,2-oxazol-3-yl)-4-hydroxy-1-methylimidazolidin-2-one.

[0180] Examples of plant growth regulators as possible mixing partners are: Abscisic acid, acibenzolar, acibenzolar-S-methyl, 1-aminocycloprop-1-yl carboxylic acid and its derivatives, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, brassinolide, brassinolide-ethyl, catechin, chitooligosaccharides (CO; COs differ from LCOs in that they do not have the pendant fatty acid chains characteristic of LCOs. COs, sometimes referred to as N-acetylchitooligosaccharides, are also composed of GlcNAc groups, but with decorated side chains that allow them to be attached to the chitin molecule [(CH 13 No. 5) n , CAS No. 1398-61-4] and chitosan molecule [(C 11 No. 4) n, CAS-No.9012-76-4]), chitin compounds, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propionic acid, daminozide, dazomet, dazomet-sodium, n-decanol, dikegluc, dikegluc-sodium, endothal, endothal-dipotassium, -disodium and mono(N,N-dimethylalkylammonium), ethephon, fumarate Lumetraline, fluorenol, fluorenol-butyl, fluorenol-methyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic acid or its derivatives (e.g., methyl jasmonate), lipochitooligosaccharides (LCOs, sometimes also referred to as symbiotic nodulation (Nod) signals (or Nod factors) or Myc factors, and β-linked fatty acyl chains having condensed N-linked fatty acyl chains at the non-reducing termini It consists of an oligosaccharide backbone of 1,4-linked N-acetyl-D-glucosamine ("GlcNAc") residues. As known to those skilled in the art, LCOs differ in the number of GlcNAc groups in their backbone, in the length and degree of saturation of the fatty acyl chains, and in the substitutions in the reducing and non-reducing sugar moieties), linoleic acid or its derivatives, linolenic acid or its derivatives, maleic acid hydrazide, mepiquat chloride, mepiquat pentaborate, 1-methylcyclopropene, 3'-methylabscisic acid, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-(1-naphthyl)acetamide ... -Naphthyloxyacetic acid, nitrophenolate mixture, 4-oxo-4-[(2-phenylethyl)amino]butyric acid, paclobutrazol, 4-phenylbutyric acid, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, methyl salicylate, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine.

[0181] Safeners which can be used in combination with the compounds of the invention of formula (I) and, optionally, with further active ingredients (e.g. the fungicides, herbicides, acaricides, insecticides mentioned above) are preferably selected from the group consisting of:

[0182] (S1) Equation (S1) [ka]

[0183] wherein the symbols and indices are defined as follows: n A is a natural number from 0 to 5, preferably a natural number from 0 to 3; R A 1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl; W A is an unsubstituted or substituted divalent heterocyclic group selected from the group of partially unsaturated or aromatic 5-membered heterocycles having 1 to 3 ring heteroatoms selected from the group of N and O, in which at least one nitrogen atom and at most one oxygen atom is present in the ring, preferably (W A 1 )~(W A 4 ) [ka]

[0184] is a group selected from the group m A is 0 or 1; R A 2 OR A 3 , S.R. A 3 Or NR A 3 R A4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to three heteroatoms, preferably selected from the group consisting of O and S, which is bonded to the carbonyl group in (S1) via a nitrogen atom and which is unsubstituted or substituted with a group selected from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy or optionally substituted phenyl, preferably of the formula OR A 3 , formula NHR A 4 or a group of formula N(CH3)2, in particular a group of formula OR A 3 is a group represented by the formula: R A 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon group (preferably having a total of 1 to 18 carbon atoms); R A 4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl; R A 5 is H, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C8)-alkyl, cyano or COOR A 9 (where R A 9 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C 12 )-cycloalkyl or tri-(C1-C4)-alkylsilyl); R A 6 , R A 7 , R A 8are the same or different and are selected from hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C3-C 12 )-cycloalkyl or substituted or unsubstituted phenyl. A compound represented by the formula: Preferably: (a) Compounds of the type dichlorophenylpyrazoline-3-carboxylic acid (S1 a ), preferably compounds such as: 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) ("mefenpyr-diethyl") and related compounds, which are described in WO-A-91 / 07874; (b) Derivatives of dichlorophenylpyrazole carboxylic acid (S1 b ), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4) and related compounds, which are described in EP-A-333131 and EP-A-269806; (c) Derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1 c ), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related compounds (which are described, for example, in EP-A-268554); (d) Triazole carboxylic acid type compounds (S1 d), preferably compounds such as: fenchlorazole (-ethyl ester), i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate (S1-7) and related compounds (which are described in EP-A-174562 and EP-A-346620); (e) Compounds of the type 5-benzyl-2-isoxazoline-3-carboxylic acid or 5-phenyl-2-isoxazoline-3-carboxylic acid or of the type 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 e ), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds, which are described in WO-A-91 / 08202, or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-11) ("isoxadifen-ethyl") or n-propyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13), which are described in patent application WO-A-95 / 07897.

[0185] (S2) Formula (S2) [ka]

[0186] wherein the symbols and indices have the following meanings: R B 1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl; n B is a natural number from 0 to 5, preferably a natural number from 0 to 3; R B2 OR B 3 , S.R. B 3 Or NR B 3 R B 4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to three heteroatoms, preferably selected from the group O and S, which is bonded to the carbonyl group in (S2) via a nitrogen atom and which is unsubstituted or substituted with a group selected from the group (C1-C4)-alkyl, (C1-C4)-alkoxy or optionally substituted phenyl, preferably of the formula OR B 3 , formula NHR B 4 or a group of formula N(CH3)2, in particular a group of formula OR B 3 is a group represented by the formula: R B 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon group (preferably having a total of 1 to 18 carbon atoms); R B 4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl; T B is a (C1 or C2)-alkanediyl chain, which is unsubstituted or substituted by one or two (C1-C4)-alkyl groups or by [(C1-C3)-alkoxy]carbonyl; A quinoline derivative represented by the formula: Preferably: (a) Compounds of the 8-quinolineoxyacetic acid type (S2 a ), preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate ("cloquintocet-mexyl") (S2-1), (5-chloro-8-quinolinoxy)acetic acid (1,3-dimethyl-but-1-yl) (S2-2), (5-chloro-8-quinolinoxy)acetic acid 4-allyloxybutyl (S2-3), (5-chloro-8-quinolinoxy)acetic acid 1-allyloxyprop-2-yl (S2-4), (5-chloro-8-quinolinoxy)ethyl acetate (S2-5), (5-chloro-8-quinolinoxy)methyl acetate (S2-6), (5-chloro-8-quinolinoxy)allyl acetate (S2-7), 2-(2-propylideneiminooxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxoprop-1-yl (5-chloro-8-quinolinoxy)acetate (S2-9) and related compounds, which are described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0492366, and also (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and salts, for example its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, which are described in WO-A-2002 / 34048; (b) (5-chloro-8-quinolinoxy)malonic acid type compounds (S2 b ), preferably compounds such as diethyl (5-chloro-8-quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methylethyl (5-chloro-8-quinolinoxy)malonate and related compounds, which are described in EP-A-0582198.

[0187] (S3) Equation (S3) [ka]

[0188] wherein the symbols and indices are defined as follows: R C 1 is (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C3-C7)-cycloalkyl, preferably dichloromethyl; R C 2 , R C 3 are the same or different and are hydrogen, (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C1-C4)haloalkyl, (C2-C4)haloalkenyl, (C1-C4)alkylcarbamoyl-(C1-C4)alkyl, (C2-C4)alkenylcarbamoyl-(C1-C4)alkyl, (C1-C4)alkoxy-(C1-C4)alkyl, dioxolanyl-(C1-C4)alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, or substituted or unsubstituted phenyl, or R C 2 and R C 3 together form a substituted or unsubstituted heterocyclic ring (preferably an oxazolidine ring, a thiazolidine ring, a piperidine ring, a morpholine ring, a hexahydropyrimidine ring or a benzoxazine ring). A compound represented by the formula: Preferably: Active ingredients of the dichloroacetamide type, which are often used as pre-emergence safeners (soil-acting safeners), e.g. "Dichlormid" (N,N-diallyl-2,2-dichloroacetamide) (S3-1), "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) [supplied by Stauffer] (S3-2), "R-28725" (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) [supplied by Stauffer] (S3-3), "Benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292" (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) (supplied by PPG Industries) (S3-5), "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) [supplied by Sagro-Chem] (S3-6), "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azaspiro[4.5]decane) [supplied by Nitrokemia or Monsanto] (S3-7), "TI-35" (1-dichloroacetylazepane) [supplied by TRI-Chemical RT] (S3-8), "diclonon" (dicyclonone) or "BAS 145138" or "LAB 145138" (S3-9), ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) [supplied by BASF], "Furilazol" or "MON 13900" ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10) and its (R)-isomer (S3-11).

[0189] (S4) Equation (S4) [ka]

[0190] wherein the symbols and indices are defined as follows: A D is SO2-NR D 3 -CO or CO-NR D 3 -SO2; X D is CH or N; R D 1 is CO-NR D 5 R D6 or NHCO-R D 7 and; R D 2 is halogen, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl; R D 3 is hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl or (C2-C4)-alkynyl; R D 4 is halogen, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, phenyl, (C1-C4)-alkoxy, cyano, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl; R D 5 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)-cycloalkenyl, phenyl or 3-6 membered heterocyclyl, where the heterocyclyl is selected from the group consisting of nitrogen, oxygen and sulfur. D containing 10 heteroatoms, wherein the last seven radicals mentioned are selected from the group consisting of halogen, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C2)-alkylsulfinyl, (C1-C2)-alkylsulfonyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkylcarbonyl and phenyl, and, in the case of cyclic radicals, are additionally selected from the group consisting of (C1-C4)-alkyl and (C1-C4)-haloalkyl, D is substituted with a substituent; R D 6 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl, where the last three mentioned radicals are selected from the group consisting of halogen, hydroxyl, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio. D or R D 5 and R D 6 together with the nitrogen atom bearing them form a pyrrolidinyl or piperidinyl group; R D 7 is hydrogen, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, where the last two mentioned radicals are selected from the group consisting of halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio, and in the case of cyclic radicals are additionally selected from the group consisting of (C1-C4)-alkyl and (C1-C4)-haloalkyl, v D is substituted with a substituent; n D is 0, 1 or 2; m D is 1 or 2; v D is 0, 1, 2 or 3. N-acylsulfonamides represented by the following formula (I) and salts thereof; Among these, for example, those known from WO-A-97 / 45016, for example those of the formula (S4 a ) [ka]

[0191] [During the ceremony, R D 7is (C1-C6)-alkyl or (C3-C6)-cycloalkyl, where the last two mentioned radicals are selected from the group consisting of halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio, and in the case of cyclic radicals are additionally selected from the group consisting of (C1-C4)-alkyl and (C1-C4)-haloalkyl, v D is substituted with a substituent; R D 4 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy or CF3; m D is 1 or 2; v D is 0, 1, 2 or 3. Preferred are compounds of the N-acylsulfonamide type represented by and, For example, compounds of the formula (S4 b ) [ka]

[0192] For example, in the above formula, R D 5 = cyclopropyl, and (R D 4 ) = 2-OMe ("cyprosulfamide", S4-1); R D 5 = cyclopropyl, and (R D 4 ) = 5-Cl-2-OMe (S4-2); R D 5 = ethyl, and (R D 4 )=2-OMe(S4-3); R D 5 = isopropyl, and (R D4 ) = 5-Cl-2-OMe (S4-4); and R D 5 = isopropyl, and (R D 4 )=2-OMe(S4-5); Also preferred are and, For example, the compound of the formula (S4 c ) [ka]

[0193] [During the ceremony, R D 8 and R D 9 is independently hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl or (C3-C6)-alkynyl; R D 4 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3; m D is 1 or 2. Compounds of the N-acylsulfamoylphenylurea type represented by the formula: 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea; 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea; 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea; Also preferred are: and, For example, the compound of formula (S4 d ) [ka]

[0194] For example, N-phenylsulfonyl terephthalamide represented by the above formula: R D 4 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3; m D is 1 or 2; R D 5 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)-cycloalkenyl; N-phenylsulfonyl terephthalamide and the like are also preferred.

[0195] (S5) Active ingredients (S5) selected from the class of hydroxyaromatic compounds and aromatic-aliphatic carboxylic acid derivatives, such as, for example, ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid (which are described in WO-A-2004 / 084631, WO-A-2005 / 015994, WO-A-2005 / 016001).

[0196] (S6) Active ingredients (S6) selected from the class of the 1,2-dihydroquinoxalin-2-ones, such as 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one (which are described in WO-A-2005 / 112630).

[0197] (S7) Formula (S7) (which is described in WO-A-1998 / 38856) [ka]

[0198] wherein the symbols and indices are defined as follows: R E 1 , R E 2 are independently halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, nitro; A E COOR E 3 or COSR E 4 and; R E 3 , R E 4 are independently hydrogen, (C1-C4)-alkyl, (C2-C6)-alkenyl, (C2-C4)-alkynyl, cyanoalkyl, (C1-C4)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium; n E 1 is 0 or 1; n E 2 , n E 3 are independently 0, 1 or 2. A compound represented by the formula: Preferably: Diphenyl methoxy acetic acid, Ethyl diphenylmethoxyacetate, Methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1).

[0199] (S8) Formula (S8) (which is described in WO-A-98 / 27049) [ka]

[0200] [During the ceremony, X F is CH or N; n F X F =N is an integer from 0 to 4; and n F X F When =CH, it is an integer from 0 to 5; R F 1 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkylthio, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy; R F 2 is hydrogen or (C1-C4)-alkyl; R F 3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, each of which is unsubstituted or substituted with one or more (preferably up to three) identical or different groups selected from the group consisting of halogen and alkoxy. or a salt thereof; Preferably, in the above formula: X F is CH; n F is an integer between 0 and 2; R F 1 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy; R F 2 is hydrogen or (C1-C4)-alkyl; R F 3is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, in which each of said carbon-containing groups is unsubstituted or substituted with one or more (preferably up to three) identical or different groups selected from the group consisting of halogen and alkoxy; A compound or a salt thereof.

[0201] (S9) An active ingredient (S9) selected from the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones, such as 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 95855-00-8), which are described in WO-A-1999 / 000020.

[0202] (S10) Formula (S10 a ) or formula (S10 b ) (these are described in WO-A-2007 / 0237190 and WO-A-2007 / 023764) [ka]

[0203] [During the ceremony, R G 1 is halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3; Y G , Z G represent, independently of each other, O or S; n G is an integer from 0 to 4; R G 2 is (C1-C 16 )-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl, benzyl, halobenzyl; R G 3 is hydrogen or (C1-C6)-alkyl. A compound represented by the formula:

[0204] (S11) Active ingredients of the oxyimino compound type (S11) (these are known as seed dressing agents), e.g. "Oxabetrinil" ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed dressing safener for foxtail millet / sorghum against injury by metolachlor; "Fluxofenim" (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as a seed dressing safener for foxtail millet / sorghum against injury by metolachlor; and "Siometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is a known seed dressing safener for foxtail millet / sorghum against injury by metolachlor.

[0205] (S12) Active ingredients (S12) selected from the class of isothiochromanones, such as methyl [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No. 205121-04-6) (S12-1) and related compounds (WO-A-1998 / 13361).

[0206] (S13) One or more compounds selected from the following group: "Naphthalic anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a seed dressing safener for corn against injury by thiocarbamate herbicides; "Fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as a safener for pretilachlor in sown rice; "Flurazole" (benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), which is known as a seed dressing safener for foxtail millet and sorghum against injury by alachlor and metolachlor; "CL 304415" (CAS Reg. No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) (supplied by American Cyanamid), which is known as a safener for corn against injury by imidazolinones; "MG 191" (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) [supplied by Nitrokemia] (known as a safener for corn); "MG 838" (CAS Reg. No. 133993-74-5) (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) [Supplied by: Nitrokemia]; "Disulfoton" (O,O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7); "Dietholate" (O,O-diethyl O-phenylphosphorothioate) (S13-8); “Mephenate” (4-chlorophenyl methylcarbamate) (S13-9).

[0207] (S14) Active ingredients that have a herbicidal effect against harmful plants and also a phytotoxicity reducing effect against crop plants such as rice, e.g. "Dimepyrate" or "MY 93" (S-1-methyl 1-phenylethylpiperidine-1-carbothioate), known as a safener for rice against injury by the herbicide molinate; "Dymron" or "SK 23" (1-(1-methyl-1-phenylethyl)-3-p-tolyl urea), known as a safener for rice against injury caused by the herbicide imazosulfuron; "Cumyluron" = "JC 940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea; see JP-A-60087254) (which is known as a safener for rice against injury by some herbicides); "Methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone) (which is known as a safener for rice against injury caused by some herbicides); "CSB" (1-Bromo-4-(chloromethylsulfonyl)benzene) [Supplied by: Kumiai] (CAS Reg. No. 54091-06-4), which is known as a safener for injury by some herbicides in rice.

[0208] (S15) Formula (S15) (which is described in WO-A-2008 / 131861 and WO-A-2008 / 131860) [ka]

[0209] [During the ceremony, R H 1 is a (C1-C6)-haloalkyl group; and R H 2 is hydrogen or halogen; and R H 3 , R H 4 are independently hydrogen, (C1-C 16 )-Alkyl, (C2-C 16 )-alkenyl or (C2-C 16)-alkynyl, in which the last three radicals are each unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxyl, cyano, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl and unsubstituted or substituted heterocyclyl, or (C3-C6)-cycloalkyl, (C4-C6)-cycloalkenyl, (C3-C6)-cycloalkyl, in which the cycloalkyl is fused on one side of the ring to a 4- to 6-membered saturated or unsaturated carbocyclic ring, or (C4-C6)-cycloalkenyl, which is fused to a 4-6-membered saturated or unsaturated carbocyclic ring on one side of the ring, in which the last four groups mentioned are each unsubstituted or substituted by one or more groups selected from the group consisting of halogen, hydroxyl, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl and unsubstituted or substituted heterocyclyl; Or, R H 3 is (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C6)-alkynyloxy or (C2-C4)-haloalkoxy; and R H 4 is hydrogen or (C1-C4)-alkyl; or R H 3 and R H 4 is, together with the nitrogen atom to which it is directly attached, a 4-8 membered heterocyclic ring which, in addition to the nitrogen atom, can also contain further ring heteroatoms (preferably up to two further ring heteroatoms selected from the group N, O and S) and which is unsubstituted or substituted with one or more groups selected from the group halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy and (C1-C4)-alkylthio. or a tautomer thereof.

[0210] (S16) Active compounds which are primarily used as herbicides but also have a safening effect on crop plants, e.g. (2,4-Dichlorophenoxy)acetic acid (2,4-D); (4-Chlorophenoxy)acetic acid; (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); (4-chloro-o-tolyloxy)acetic acid (MCPA); 4-(4-chloro-o-tolyloxy)butyric acid; 4-(4-chlorophenoxy)butyric acid; 3,6-Dichloro-2-methoxybenzoic acid (dicamba); 3,6-Dichloro-2-methoxybenzoate 1-(ethoxycarbonyl)ethyl (lactidichloro-ethyl).

[0211] Particularly preferred safeners are mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl, dichlormid and metcamifen.

[0212] Wettable powders are preparations capable of being homogeneously dispersed in water, which contain, in addition to the active ingredient and apart from diluents or inert substances, also surfactants of ionic and / or nonionic type (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoyl methyl taurate. To prepare wettable powders, the herbicidal active ingredient is pulverized in conventional equipment, such as hammer mills, blower mills and air jet mills, and simultaneously or subsequently mixed with formulation auxiliaries.

[0213] Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent (such as butanol, cyclohexanone, dimethylformamide, xylene or aromatic substances or hydrocarbons with relatively high boiling points) or a mixture of such organic solvents and adding one or more surfactants (emulsifiers), ionic and / or non-ionic. Examples of emulsifiers that can be used are: calcium alkylarylsulfonates, such as calcium dodecylbenzenesulfonate, or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensates, alkyl polyethers, sorbitan esters, such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as polyoxyethylene sorbitan fatty acid esters.

[0214] Dusting products are obtained by grinding the active ingredient with finely distributed solid matter, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

[0215] Suspension formulations can be aqueous or oil-based. They can be prepared, for example, by wet-milling using a commercial bead mill, and optionally with the addition of a surfactant (such as those already mentioned above for the different formulation types).

[0216] Emulsions, e.g. oil-in-water emulsions (EW), can be prepared, for example, using aqueous organic solvents and, optionally, surfactants (e.g. those already mentioned above for the other formulation types), using stirrers, colloid mills and / or static mixers.

[0217] Granules can be prepared by spraying the active ingredient onto the surface of an adsorbent granular inert material, or by applying an active ingredient concentrate onto the surface of a carrier material (e.g., sand, kaolinite, or granular inert material) with an adhesive (e.g., polyvinyl alcohol, sodium polyacrylate, or mineral oil). It is also possible to granulate suitable active ingredients (as a mixture with fertilizer, if necessary) in a manner customary for producing fertilizer granules.

[0218] Water dispersible granules are generally prepared by conventional methods such as spray drying, fluid bed granulation, pan granulation, mixing with high speed mixers, and extrusion without the use of solid inert materials.

[0219] For the preparation of bread, fluid bed, extrusion and spray granules, see, for example, the methods described in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff.; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. For further details regarding the formulation of crop protection compositions, see, for example, GC Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

[0220] The agrochemical preparations generally contain 0.1% to 99% by weight, in particular 0.1% to 95% by weight, of the compound of the invention. In wettable powders, the concentration of the active ingredient is, for example, about 10% to 90% by weight, the remainder up to 100% by weight being made up of conventional formulation ingredients. In emulsifiable concentrates, the concentration of the active ingredient can be about 1% to 90% by weight, preferably 5% to 80% by weight. Formulations in the form of powders contain 1% to 30% by weight of active ingredient, preferably usually 5% to 20% by weight; sprayable solutions contain about 0.05% to 80% by weight, preferably 2% to 50% by weight of active ingredient. In the case of wettable powders, the content of the active ingredient depends in part on whether the active ingredient is present in liquid or solid form, and in part on what granulation aids, fillers, etc. are used. In the water dispersible granule, the content of the active ingredient is, for example, 1 to 95% by weight, or preferably 10 to 80% by weight.

[0221] In addition, the above formulations of the active ingredients optionally contain the respective customary adhesives, wetting agents, dispersing agents, emulsifying agents, penetrating agents, preservatives, antifreeze agents, as well as solvents, extenders, carriers, as well as dyes, antifoaming agents, evaporation retardants, and agents for influencing pH and viscosity.

[0222] On the basis of these formulations, it is also possible to prepare combinations with other pesticidal active substances (e.g. insecticides, acaricides, herbicides, fungicides) and also with safeners, fertilizers and / or growth regulators, for example in the form of finished formulations or as tank mixes.

[0223] For application, the commercial formulations are, where appropriate, diluted in the customary manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersions and water dispersible granules. Dust-type preparations, granules for soil application or broadcast granules and sprayable solutions are usually not further diluted with other inert substances before application.

[0224] The required application rate of the compounds of formula (I) and their salts varies depending on the external conditions (such as, inter alia, temperature, humidity and the type of herbicide used). It can vary within a wide range, for example, within the range of 0.001 to 10.0 kg / ha or more of active substance. However, it is preferably 0.005 to 5 kg / ha, more preferably 0.01 to 1.5 kg / ha, more preferably 0.05 to 1 kg / ha. This applies both to pre-emergence and post-emergence application.

[0225] A carrier is a natural or synthetic organic or inorganic substance that is mixed or combined with the active ingredient to improve applicability, especially for application to plants or plant parts or seeds. Such carriers can be solid or liquid, but should generally be inert and suitable for use in agriculture.

[0226] Useful solid or liquid carriers include, for example, ammonium salts, and natural rock flours, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flours, such as micronized silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohol, in particular butanol, organic solvents, mineral oils and vegetable oils, and derivatives thereof. Mixtures of such carriers may also be used. Useful solid carriers for granules include, for example, crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meal, and also granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stems.

[0227] Suitable liquefied gas extenders or carriers are liquids that are gases at standard temperature and atmospheric pressure, such as aerosol propellants, for example, halogenated hydrocarbons, or butane, propane, nitrogen, and carbon dioxide.

[0228] In the above formulations, tackifiers can be used, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders or granules or latex, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids, etc. Further additives can be mineral and vegetable oils.

[0229] When the extender used is water, for example, organic solvents can also be used as auxiliary solvents.Useful liquid solvents are essentially the following: aromatic compounds, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons, such as cyclohexane or paraffins, such as mineral oil fractions, mineral oils and vegetable oils, alcohols, such as butanol or glycols and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, and also water.

[0230] The compositions of the present invention may additionally contain further ingredients, such as, for example, surfactants. Useful surfactants are emulsifiers and / or foam formers, dispersants or wetting agents having ionic or non-ionic properties, or mixtures of such surfactants. Examples of these are: salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide and fatty alcohols or fatty acids or polycondensates of ethylene oxide and fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of said compounds containing sulfate, sulfonate and phosphate anions, such as alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, protein hydrolysates, lignosulfite waste liquors and methylcellulose. If one of the active ingredients and / or one of the inert carriers is water-insoluble and application is carried out in water, it is necessary to have a surfactant present. The proportion of the surfactant is 5 to 40% by weight of the composition of the present invention. Colorants such as inorganic pigments, such as iron oxide, titanium oxide, and Prussian Blue, as well as organic dyes, such as alizarin dyes, azo dyes, and metal phthalocyanine dyes, as well as trace nutrients, such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum salts, and zinc salts, can be used.

[0231] If appropriate, additional other ingredients may also be present, such as protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrating agents, stabilizers, sequestering agents, complexing agents, etc. In general, the active ingredient can be combined with any solid or liquid additive commonly used for formulation purposes. In general, the compositions and formulations of the present invention contain 0.05% to 99% by weight, 0.01% to 98% by weight, preferably 0.1% to 95% by weight, more preferably 0.5% to 90% by weight, and most preferably 10% to 70% by weight of the active ingredient. The active ingredients or compositions of the invention can be used as they are or in the form of their formulations or in the use forms prepared therefrom, depending on their individual physical and / or chemical properties, such as, for example, aerosols, capsule suspensions, cold-fogging concentrates, warm-fogging concentrates, encapsulated granules, fine granules, seed treatment flowables, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, large granules, fine granules, oil-dispersible powders, oil-miscible flowables, oil-miscible liquids, foams, pastes, pesticide-coated seeds, suspension concentrates, suspoemulsions, soluble concentrates, suspensions, sprayable powders, soluble powders. powders, dusts and granules, water-soluble granules or tablets, water-soluble powders for seed treatment, wettable powders, natural products and synthetic substances impregnated with the active ingredient, and also those microencapsulated in polymeric substances and in coating substances for seeds, and also ULV cold-fogging formulations and ULV warm-fogging formulations.

[0232] The formulations can be prepared in a manner known per se, for example by mixing the active ingredient with at least one customary extender, solvent or diluent, emulsifier, dispersant and / or binder or fixative, wetting agent, water repellent, optionally drying agents and UV stabilizers, and optionally dyes and pigments, defoamers, preservatives, secondary thickeners, tackifiers, gibberellins and further processing auxiliaries.

[0233] The compositions of the present invention include not only formulations which are ready for use and can be applied to plants or seeds using appropriate equipment, but also commercial concentrates which require dilution with water before use.

[0234] The active ingredient of the present invention may be present on its own or in its (commercially standard) formulation or in a use form prepared from such a formulation, as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners or semiochemicals.

[0235] The treatment of plants and plant parts according to the invention with the active ingredients or compositions is carried out by customary treatment methods, for example directly by immersion, spraying, spraying, irrigation, vaporization, dusting, fume, broadcasting, foaming, painting, spreading-on, watering (drenching), drip irrigation, etc., or by applying the active ingredients or compositions to the surroundings, habitat or storage space of the plants and plant parts, and also, in the case of propagation material, in particular seeds, by dry seed treatment, by wet seed treatment, by slurry treatment, by incrustation, by coating with one or more layers. Furthermore, the active ingredients can also be deployed by ultra-low volume methods or the active ingredient preparations or the active ingredients themselves can be injected into the soil.

[0236] As also described below, the treatment of transgenic seeds with the active ingredient or composition of the present invention is particularly important. This concerns the seeds of plants that contain at least one heterologous gene that allows the expression of a polypeptide or protein with insecticidal properties. The heterologous gene in the transgenic seeds can be derived from, for example, a microorganism of Bacillus sp., Rhizobium sp., Pseudomonas sp., Serratia sp., Trichoderma sp., Clavibacter sp., Glomus sp. or Gliocladium sp. This heterologous gene is preferably derived from Bacillus sp., and in that case, its gene product is effective against European corn borer and / or Western corn rootworm. More preferably, the heterologous gene is derived from Bacillus thuringiensis.

[0237] In the context of the present invention, the composition according to the invention is applied to the seeds alone or in a suitable formulation. Preferably, the seeds are treated in a sufficiently stable state so that no damage occurs during the treatment. In general, the seeds can be treated at any time between harvesting and sowing. Conventionally, seeds that are separated from the plant and do not have cobs, husks, petioles, husks, hairs or flesh are used. For example, seeds that have been harvested, cleaned and dried to a moisture content of less than 15% by weight can be used. Alternatively, seeds that have been treated after drying, for example with water, and then dried again can be used.

[0238] In general, when treating seeds, care must be taken with regard to the selection of the amount of the composition of the invention and / or the amount of further additives applied to the seeds so that the germination of the seeds is not impaired and the plants resulting from the seeds are not damaged, especially in the case of active ingredients that may show phytotoxic effects at certain application rates.

[0239] The composition of the present invention can be applied directly, i.e. without containing other components and without dilution.Generally, the composition is preferably applied to seeds in the form of a suitable formulation.Suitable formulations and methods for treating seeds are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417A, US 4,245,432A, US 4,808,430, US 5,876,739, US 2003 / 0176428A1, WO 2002 / 080675A1, WO 2002 / 028186A2.

[0240] The active ingredients of the present invention can be converted into conventional seed dressing formulations, such as solutions, emulsions, suspensions, dusts, foams, slurries or other coating compositions for seeds, and further into ULV formulations.

[0241] These formulations are prepared in known manner by mixing the active ingredient with the customary additives, such as customary extenders and solvents or diluents, colorants, wetting agents, dispersants, emulsifiers, antifoaming agents, preservatives, secondary thickeners, adhesives, gibberellins, and the like, and further mixing with water.

[0242] Colorants that may be present in the seed dressing formulations that can be used according to the invention are all colorants that are customary for such purposes. Both pigments that are sparingly soluble in water and dyes that are soluble in water can be used. Examples include the colorants known under the names "Rhodamin B", "CI Pigment Red 112" and "CI Solvent Red 1".

[0243] Useful wetting agents that can be present in the seed dressing formulations that can be used according to the invention are all substances that promote wetting that are customary for the formulation of agrochemical active ingredients. Preferably, alkylnaphthalenesulfonates, such as diisopropylnaphthalenesulfonate or diisobutylnaphthalenesulfonate, can be used.

[0244] Suitable dispersants and / or emulsifiers that may be present in the seed dressing formulations that can be used according to the invention are all nonionic, anionic and cationic dispersants that are customary for the formulation of agrochemical active ingredients. Preference may be given to using nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Suitable nonionic dispersants include, in particular, ethylene oxide / propylene oxide block copolymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers, as well as their phosphorylated or sulfated derivatives. Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylates and arylsulfonate-formaldehyde condensates.

[0245] Antifoaming agents that may be present in the seed dressing formulations that can be used according to the invention are all foam-inhibiting substances that are customary for the formulation of agrochemically active ingredients. Preferably, silicone antifoaming agents and magnesium stearate can be used.

[0246] Preservatives which may be present in the seed dressing formulations which may be used according to the invention are all substances which may be used for this purpose in agrochemical compositions, examples of which include dichlorophene and benzyl alcohol hemiformal.

[0247] Secondary thickeners that may be present in the seed dressing formulations that can be used according to the invention are all substances that can be used for this purpose in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.

[0248] Useful adhesives that can be present in the seed dressing formulations that can be used according to the invention are all conventional binders that can be used in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.

[0249] The seed dressing formulations which can be used according to the invention can be used directly or after prior dilution with water to treat a wide range of different seeds, including those of transgenic plants, where additive synergistic effects may occur in interaction with the substances formed by expression.

[0250] For the treatment of seeds with the seed dressing formulation that can be used according to the present invention or the preparation prepared from the seed dressing formulation by adding water, the useful equipment is all the mixing equipment that can be used for seed dressing.Specifically, the seed dressing procedure is to put seeds into a mixer, add a specific amount of the seed dressing formulation that is desired, either as is or after diluting it with water in advance, and mix them until the formulation is distributed homogeneously on the surface of the seed.If appropriate, a drying step is then carried out.

[0251] The active ingredients of the present invention are suitable for protecting plants and plant organs, for increasing yield, and for improving the quality of harvested crops, when they show good compatibility with plants, have desirable toxicity to homeotherms, and have good compatibility with the environment.They can preferably be used as crop protection agents.They are active against normal sensitive and resistant species, and are active against all or specific developmental stages.

[0252] Plants which can be treated according to the invention include the following main crop plants: corn, soybean, cotton, Brassica oil seeds, such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassica carinata, rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet and sorghum, triticale, flax, grapes, as well as various fruits and vegetables belonging to different botanical taxa, such as Rosaceae sp. (e.g. pome fruits, such as apple and pear, as well as stone fruits, such as apricot, cherry, almond and peach, and berries, such as strawberry), Ribesioidae sp. sp.), Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (e.g. lemons, oranges and grapefruit); Solanaceae sp. (e.g., tomato, potato, pepper, eggplant), Liliaceae sp., Compositae sp. (e.g., lettuce, artichoke, and chicory (which includes root chicory, endive, or common chicory)), Umbelliferae sp.) (e.g. carrot, parsley, celery and celeriac), Cucurbitaceae sp. (e.g. cucumber (which includes gherkin), pumpkin, watermelon, gourd and melon), Alliaceae sp. (e.g. leek and onion), Cruciferae sp. (e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, Chinese cabbage, kohlrabi, radish, horseradish, cress and Chinese cabbage), Leguminosae sp. (e.g. peanut, pea and Phaseolus vulgaris (e.g. common bean and fava bean)), Chenopodiaceae sp. sp. (e.g. Swiss chard, fodder beet, spinach, beetroot), Malvaceae (e.g. okra), Asparagaceae (e.g. asparagus); useful and ornamental plants in gardens and forests; and, in each case, genetically modified versions of these plants.

[0253] As stated above, all plants and their parts can be treated according to the invention. In a preferred embodiment, wild plant species and plant cultivars or plant species and cultivars obtained by conventional biological breeding methods such as crossing or protoplast fusion, as well as their parts, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, where appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above. Particularly preferred according to the invention is the treatment of plants of the respective plant cultivars that are commercially conventional or in use. Plant cultivars are understood to mean plants with new properties ("traits") that have been cultivated by conventional breeding or by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, biotypes and genotypes.

[0254] The treatment method of the invention can also be used to treat genetically modified organisms (GMOs), such as plants or seeds. A genetically modified plant (or transgenic plant) is a plant in which a heterologous gene has been stably integrated into its genome. The term "heterologous gene" essentially means a gene, supplied or constructed outside the plant, which, when introduced into the nuclear, chloroplast or mitochondrial genome, confers new or improved agronomic properties or other traits to the transformed plant, either by expressing a protein or polypeptide of interest, or by down-regulating or switching off another gene or genes present in the plant (e.g. using antisense, co-suppression or RNAi technology [RNA interference], etc.). A heterologous gene present in the genome is also called a transgene. A transgene, defined by its specific presence in the plant genome, is called a transformation or transgenesis event.

[0255] Depending on the plant species or plant varieties, their growing location and growing conditions (soil, climate, growing season, nutrients (diet)), the treatment of the present invention may also produce effects that are more than additive ("synergistic effects"). For example, the following effects beyond the actual expected effects are possible: reduced application rate and / or broadening of the activity spectrum and / or increased efficacy of the active ingredients and compositions that can be used according to the present invention, improved plant growth, improved resistance to high or low temperatures, improved resistance to drought or salts contained in water or soil, improved flowering ability, improved ease of harvesting, accelerated maturation, increased yield, increased fruit size, increased plant height, improved green leaf color, earlier flowering, improved quality and / or increased nutritional value of harvested products, increased sugar content in fruits, improved storage stability and / or improved processability of harvested products.

[0256] Plants and plant cultivars which are preferably treated according to the invention include all plants (whether obtained by breeding and / or by biotechnological means) which have genetic material that confers particularly advantageous and useful traits to the plant.

[0257] Examples of nematode-resistant plants are described, for example, in the following U.S. patent applications: 11 / 765,491, 11 / 765,494, 10 / 926,819, 10 / 782,020, 12 / 032,479, 10 / 783,417, 10 / 782,096, 11 / 657,964, 12 / 192,904, 1 1 / 396,808, 12 / 166,253, 12 / 166,239, 12 / 166,124, 12 / 166,209, 11 / 762,886, 12 / 364,335, 11 / 763,947, 12 / 252,453, 12 / 209,354, 12 / 491,396, and 12 / 497,221.

[0258] Plants that may be treated according to the invention are hybrid plants that already exhibit the properties of hybrid vigor or hybrid effect, which generally result in increased yield, improved vigor, improved health and improved resistance to biotic and abiotic stress factors. Such plants are typically produced by crossing a male-sterile inbred parent line (female cross breeding parent) with another male-fertile inbred parent line (male cross breeding parent). Hybrid seeds are typically harvested from the male-sterile plants and sold to growers. Male-sterile plants can sometimes (e.g. in corn) be produced by detasseling (i.e. by mechanically removing the male reproductive organs or male flowers). However, more typically, male sterility is the result of genetic determinants within the plant genome. In that case, and especially when seeds are the desired product to be harvested from a hybrid plant, it is typically beneficial to ensure that male fertility is fully restored in the hybrid plant that contains the genetic determinants responsible for male sterility. This can be achieved by ensuring that the male cross breeding parent has a suitable fertility restorer gene that can restore male fertility in the hybrid plant that contains the genetic determinants responsible for male sterility. The genetic determinants for male sterility can be present in the cytoplasm. Examples of cytoplasmic male sterility (CMS) have been described, for example, for Brassica species. However, the genetic determinants for male sterility can also be present in the nuclear genome. Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful method for obtaining male-sterile plants is described in WO 89 / 10396, in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells within the stamens. Fertility can then be restored by expressing a ribonuclease inhibitor such as barstar in the tapetum cells.

[0259] Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated according to the invention are herbicide-tolerant plants, i.e. plants that have been made tolerant to one or more given herbicides. Such plants can be obtained by genetic transformation or by selecting plants that contain a mutation that confers resistance to the herbicide in question.

[0260] Herbicide-resistant plants are, for example, glyphosate-resistant plants, i.e. plants that have been made tolerant to the herbicide glyphosate or its salts. Plants can be made tolerant to glyphosate by various methods. Thus, for example, glyphosate-resistant plants can be obtained by transforming plants with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutation CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the EPSPS-encoding gene of Petunia (Shah et al., 1986, Science 233, 478-481), the EPSPS-encoding gene of tomato (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289) or the EPSPS-encoding gene of Eleusine (WO 01 / 66704). It can be a mutant EPSPS. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate oxidoreductase enzyme. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally occurring mutations of the above genes. Plants expressing an EPSPS gene that confers glyphosate tolerance have been described. Plants expressing another gene (e.g., a decarboxylase gene) that confers glyphosate tolerance have been described.

[0261] Another herbicide-resistant plant is, for example, a plant that has been made tolerant to herbicides that inhibit the enzyme glutamine synthase (e.g., bialaphos, phosphinothricin or glufosinate). Such plants can be obtained by expressing an enzyme that detoxifies the herbicide in question or by expressing a mutant glutamine synthase enzyme that is resistant to inhibition. One example of such an effective detoxifying enzyme is an enzyme that codes for phosphinothricin acetyltransferase (e.g., the bar or pat proteins from Streptomyces species). Plants expressing exogenous phosphinothricin acetyltransferase have been described.

[0262] Further herbicide-resistant plants are also plants that are made tolerant to herbicides that inhibit the enzyme hydroxyphenylpyruvate dioxygenase (HPPD). Hydroxyphenylpyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogentisate. Plants that are resistant to HPPD inhibitors can be transformed with a gene that codes for a naturally occurring resistant HPPD enzyme, or with a gene that codes for a mutant or chimeric HPPD enzyme, as described in WO 96 / 38567, WO 99 / 24585, WO 99 / 24586, WO 2009 / 144079, WO 2002 / 046387 or US 6,768,044. Resistance to HPPD inhibitors can also be obtained by transforming plants with a gene that codes for a specific enzyme that can form homogentisate despite the inhibition of the native HPPD enzyme by HPPD inhibitors. Such plants are described in WO 99 / 34008 and WO 02 / 36787. The resistance of plants to HPPD inhibitors can also be improved by transforming the plant with a gene encoding a prephenate dehydrogenase enzyme in addition to a gene encoding an HPPD resistance enzyme, as described in WO 2004 / 024928. Furthermore, plants can be made more resistant to HPPD inhibitors by inserting into their genome a gene encoding an enzyme that metabolizes or degrades HPPD inhibitors (e.g., a CYP450 enzyme) (see WO 2007 / 103567 and WO 2008 / 150473).

[0263] Another herbicide-resistant plant is a plant that is made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitors include, for example, sulfonylurea herbicides, imidazolinone herbicides, triazolopyrimidine herbicides, pyrimidinyloxy(thio)benzoate herbicides, and / or sulfonylaminocarbonyltriazolinone herbicides. Various mutations in the ALS enzyme (also known as "acetohydroxyacid synthase (AHAS)") are known to confer tolerance to various herbicides and groups of herbicides, as described, for example, in Tranel and Wright (Weed Science 2002, 50:700-712). The creation of sulfonylurea-resistant and imidazolinone-resistant plants has been described. Further sulfonylurea-resistant and imidazolinone-resistant plants have also been described.

[0264] Further plants which are tolerant to imidazolinones and / or sulfonylureas can be obtained by induced mutagenesis, by selection in cell culture in the presence of the herbicide or by mutation breeding (cf. e.g. US 5,084,082 for soybean, WO 97 / 41218 for rice, US 5,773,702 and WO 99 / 057965 for sugar beet, US 5,198,599 for lettuce or WO 01 / 065922 for sunflower).

[0265] Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are resistant to abiotic stress factors. Such plants can be obtained by genetic transformation or by selecting plants containing mutations that confer such stress resistance. Particularly useful stress-tolerant plants include: (a) a plant comprising a transgene capable of reducing the expression and / or activity of the poly(ADP-ribose) polymerase (PARP) gene in a plant cell or in the plant; (b) a plant containing a stress tolerance enhancing transgene capable of reducing the expression and / or activity of a PARG-encoding gene in the plant or plant cell; (c) a plant containing a stress tolerance-enhancing transgene encoding a plant-functional enzyme of the nicotinamide adenine dinucleotide salvage biosynthetic pathway, including nicotinamidase, nicotinic acid phosphoribosyltransferase, nicotinic acid mononucleotide adenyltransferase, nicotinamide adenine dinucleotide synthetase, or nicotinamide phosphoribosyltransferase.

[0266] Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention exhibit modified quantity, quality and / or storage stability of the harvested product and / or modified characteristics of certain components of the harvested product, for example: (1) transgenic plants which synthesize modified starches whose physicochemical properties, in particular the amylose content or amylose / amylopectin ratio, the degree of branching, the average chain length, the side chain distribution, the viscous behavior, the gelling strength, the starch granule size and / or the starch granule morphology, are altered compared to the starch synthesized in wild-type plant cells or plants, making them more suitable for certain applications; (2) transgenic plants which synthesize non-starch carbohydrate polymers or which synthesize non-starch carbohydrate polymers with altered properties compared to the non-genetically modified wild-type plants (examples are plants which produce polyfructose (in particular inulin- and levan-type polyfructose), plants which produce α-1,4-glucans, plants which produce α-1,6-branched α-1,4-glucans, and plants which produce alternan); (3) transgenic plants producing hyaluronan; (4) Transgenic or hybrid plants having properties such as "high soluble solids content," "low pungency" (LP) and / or "long shelf life" (LS), e.g., onion.

[0267] Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that may also be treated according to the invention are plants with modified fiber properties (for example cotton plants). Such plants can be obtained by genetic transformation or by selecting plants containing a mutation that confers such modified fiber properties. Such plants include: (a) a plant (e.g., a cotton plant) that contains an altered form of a cellulose synthase gene; (b) a plant (e.g., a cotton plant) that contains an altered form of an rsw2 homologous nucleic acid or an rsw3 homologous nucleic acid, e.g., a cotton plant having increased expression of sucrose phosphate synthase; (c) plants with increased expression of sucrose synthase (e.g., cotton plants); (d) plants in which the timing of fiber cell-based plasmodesmata gating has been altered (e.g., via downregulation of a fiber-selective β-1,3-glucanase) (e.g., cotton plants); (e) Plants (eg, cotton plants) having fibers whose responsiveness has been altered (eg, through expression of N-acetylglucosamine transferase genes, including nodC, and expression of chitin synthase genes).

[0268] Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that may also be treated according to the invention are plants (e.g. rapeseed plants or related Brassica plants) with altered oil profile characteristics. Such plants can be obtained by genetic transformation or by selecting plants containing mutations that confer such altered oil characteristics. Such plants include: (a) Plants that produce oil with a high oleic acid content (e.g., rapeseed plants); (b) plants that produce oils with low linolenic acid content (e.g., rapeseed plants); (c) Plants that produce oils with low levels of saturated fatty acids (e.g., rapeseed plants).

[0269] Plants or plant cultivars (obtainable by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants such as potato showing resistance to viruses (for example against potato virus Y (SY230 and SY233 events, Tecnoplant, Argentina)) or potato showing resistance to diseases (for example potato late blight) (for example the RB gene) or potato showing reduced cold-induced sweetness (which has the genes Nt-Inh, II-INV) or potato showing a dwarf phenotype (A-20 oxidase gene).

[0270] Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that may also be treated according to the invention are plants (e.g. rapeseed plants or related Brassica plants) with modified seed shattering characteristics. Such plants can be obtained by genetic transformation or by selecting plants containing mutations that confer such modified characteristics. Such plants include plants (e.g. rapeseed plants) in which seed shattering is delayed or reduced.

[0271] Particularly useful transgenic plants that may be treated according to the present invention are plants that contain a transformation event or combination of transformation events that are the subject of a grant or continuing application to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) for non-regulated status in the United States. Information relating thereto is available at any time from APHIS, 4700 River Road Riverdale, MD 20737, USA, for example via the website "http: / / www.aphis.usda.gov / brs / not_reg.html". As of the filing date of this application, the following applications have been granted or are pending with APHIS: - Application: The application identification number. A technical description of the transformation event can be found in the specific application documents available from APHIS on its website via the application number. Those descriptions are incorporated herein by reference.

[0272] - Extension of application: A reference to an earlier application in which an extension in scope or duration is being sought.

[0273] - Company: The name of the person submitting the application.

[0274] - Restricted item: the plant species in question.

[0275] - Transgenic phenotype: The trait conferred to a plant by a transformation event.

[0276] - Transformation event or line: the name of the event or events (sometimes also referred to as lines) for which a regulatory exemption is being claimed.

[0277] - APHIS Documents: Various documents that are relevant to the application and have been published by APHIS or are available from APHIS upon request.

[0278] Particularly useful transgenic plants that may be treated according to the present invention are plants that contain one or more genes encoding one or more toxins, such as transgenic plants sold under the following trade names: YIELD GARD® (e.g., corn, cotton, soybean), KnockOut® (e.g., corn), BiteGard® (e.g., corn), BT-Xtra® (e.g., corn), StarLink® (e.g., corn), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (e.g., corn), Protecta® and NewLeaf® (potato). Examples of herbicide-resistant plants that may be mentioned include corn, cotton and soybean varieties available under the following trade names: Roundup Ready (resistant to glyphosates, e.g., corn, cotton, soybean), Liberty Link (resistant to phosphinothricin, e.g., rapeseed), IMI (resistant to imidazolinones) and SCS (resistant to sulfonylureas, e.g., corn). Herbicide-resistant plants (plants bred in a conventional manner for herbicide resistance) that may be mentioned include varieties sold under the trade name Clearfield (e.g., corn).

[0279] NMR data of selected examples of the compound represented by formula (I): 1 H NMR data can be analyzed in two different ways: (a) by conventional NMR evaluation and interpretation, or (b) according to the method described below. 1 The data are given in the form of a 1 H NMR peak list.

[0280] (a) Conventional NMR interpretation Example No. I-10: 1H NMR (CDCl3δ, ppm): 1.20 (d, 3H), 2.85 (sext, 1H), 3.65 (d, 3H), 3.70 (s, 3H), 4.30 (dd, 1H), 4.45 (dd, 1H), 5.90 (s, 1H), 6.95 (m, 1H), 7.05 (t, 1H), 7.20 (t, 1H), 7.35 (m, 1H), 7.45 (t, 1H), 7.75 (m, 1H), 8.10 (s, 1H). Example No. I-12: 1 H NMR (d6-DMSO: δ, ppm): 3.55 (s, 3H), 5.80 (s, 1H), 7.25-7.35 (m, 3H), 7.50 (m, 1H), 7.60 (t, 1H), 7.95 (m, 1H), 8.20 (d, 1H). Example No. I-13: 1 H NMR (CDCl3δ, ppm): 3.70 (s, 3H), 3.85 (s, 3H), 5.95 (s, 1H), 7.15 (t, 1H), 7.30 (m, 1H), 7.45 (m, 2H), 8.30 (m, 1H), 8.50 (m, 1H). Example No. I-18: 1 H NMR (CDCl3δ, ppm): 3.70 (s, 3H), 3.85 (s, 3H), 5.95 (s, 1H), 7.15 (t, 1H), 7.30 (m, 1H), 7.45 (m, 2H), 8.30 (m, 1H), 8.50 (m, 1H). Example No. I-63: 1H NMR (CDCl3δ, ppm): 1.30 (t, 3H), 2.70 (t, 2H), 3.65 (s, 3H), 3.85 (m, 1H), 4.05 (m, 1H), 4.50 (t, 2H), 5.95 (s, 1H), 6.95 (dd, 1H), 7.05 (dt, 1H), 7.20 (t, 1H), 7.35 (m, 1H), 7.45 (dt, 1H), 7.75 (dt, 1H), 8.10 (d, 1H). Example No. I-64: 1 H NMR (CDCl3δ, ppm): 1.30 (t, 3H), 2.70 (t, 2H), 3.65 (s, 3H), 3.85 (m, 1H), 4.05 (m, 1H), 4.50 (t, 2H), 5.95 (s, 1H), 6.95 (dd, 1H), 7.05 (dt, 1H), 7.20 (t, 1H), 7.35 (m, 1H), 7.45 (dt, 1H), 7.75 (dt, 1H), 8.10 (d, 1H). (b) NMR peak list method The 1H NMR data of selected examples are presented in the form of a 1H NMR peak list. For each signal peak, the δ value (ppm) is listed first, followed by the signal intensity in parentheses. The δ value-signal intensity number pairs for the various signal peaks are listed, separated from each other by semicolons.

[0281] Thus, the peak list for one example takes the following form: δ1(Intensity 1);δ2(Intensity 2);...;δ i (Intensity i);...;δ n (strength n).

[0282] The intensity of the sharp signal correlates with the signal height (cm) in the printed example of the NMR spectrum, giving a true ratio of signal intensities. In the case of broad signals, several peaks or the center of the signal and their relative intensities can be shown in comparison to the most intense signal in the spectrum.

[0283] To calibrate the chemical shifts of 1H NMR spectra, tetramethylsilane is used and / or, especially if the spectrum is measured in DMSO, the chemical shifts of the solvent are used, so that in the NMR peak list, the tetramethylsilane peak may be present, but need not be.

[0284] The 1H NMR peak listing resembles a conventional 1H NMR printout and therefore includes all peaks that would normally be listed in a conventional NMR interpretation.

[0285] Moreover, they may also show, like a conventional 1H NMR printout, signals of the solvent, signals of stereoisomers of the target compound (which likewise form part of the subject matter of the present invention) and / or signals of impurity peaks.

[0286] In recording compound signals in the delta range of the solvent and / or water, our listing of 1H NMR peaks shows the usual solvent peaks, e.g., the DMSO peak in DMSO-D6, and the water peak (which usually have high intensity on average).

[0287] The peaks of stereoisomers of a target compound and / or the peaks of impurities usually have, on average, lower intensities than the peaks of the target compound (eg, a target compound having a purity of greater than 90%).

[0288] Such stereoisomers and / or impurities may be unique to a particular preparation method and therefore their peaks may help to confirm the reproducibility of our preparation method, in this case with respect to "by-product fingerprints".

[0289] The expert, calculating the peaks of the target compounds by known methods (MestreC, ACD simulations, and also using empirically evaluated expectation values), can separate the peaks of the target compounds, optionally using additional intensity filters, if necessary. This separation would be similar to picking relevant peaks in the conventional interpretation of 1H NMR.

[0290] Further details regarding the 1H NMR peak list can be found in Research Disclosure Database Number 564025. [Table 6] TIFF2024524230000075.tif241163TIFF2024524230000076.tif238162TIFF2024524230000077.tif243163TIFF2024524230000078.tif242162TIFF202 4524230000079.tif246162TIFF2024524230000080.tif245163TIFF2024524 230000081.tif238162TIFF2024524230000082.tif238162TIFF20245242300 00083.tif242162TIFF2024524230000084.tif237162TIFF2024524230000085.tif238162TIFF2024524230000086.tif240161TIFF2024524230000087.t if240164TIFF2024524230000088.tif243161TIFF2024524230000089.tif244162TIFF2024524230000090.tif236162TIFF2024524230000091.tif147162

[0291] B. Formulation Examples (a) A dusting product is obtained by mixing 10 parts by weight of a compound of formula (I) and / or its salt with 90 parts by weight of talc as an inert substance and grinding the mixture in an impact mill.

[0292] (b) A wettable powder which disperses easily in water can be obtained by mixing 25 parts by weight of a compound of formula (I) and / or its salt with 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent, and grinding in a pinned-disc mill.

[0293] (c) A dispersion concentrate which is easily dispersible in water can be obtained by mixing 20 parts by weight of the compound of formula (I) and / or its salt with 6 parts by weight of an alkylphenol polyglycol ether (Triton X 207®), 3 parts by weight of an isotridecanol polyglycol ether (8EO) and 71 parts by weight of a paraffinic mineral oil (boiling point range: for example, from about 255°C to more than about 277°C) and grinding in an attrition ball mill to a fineness of less than 5 microns.

[0294] (d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound represented by formula (I) and / or a salt thereof, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of oxethylated nonylphenol as an emulsifier.

[0295] (e) Water dispersible granules: 75 parts by weight of a compound represented by formula (I) and / or a salt thereof, 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol, and 7 parts by weight of kaolin The powder is obtained by mixing the above, grinding the mixture in a pin disc mill, and granulating the obtained powder in a fluidized bed by spraying water as a granulating liquid.

[0296] (f) Water dispersible granules may also be milled in a colloid mill: 25 parts by weight of a compound represented by formula (I) and / or a salt thereof, 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate, and 50 parts by weight of water and then grinding the mixture in a bead mill and spraying and drying the resulting suspension in a spray tower using a one-phase nozzle.

[0297] C. Biological Examples 1. Pre-emergence herbicidal activity and crop plant compatibility Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in plastic pots or organic cultivation pots and covered with soil. The surface of the covered soil is then sprayed with the compounds of the invention, formulated in the form of wettable powders (WP) or as emulsifiable concentrates (EC), as aqueous suspensions or emulsions with 0.5% additives, with a spray water volume equivalent to 600 L / ha. After treatment, the pots are placed in a greenhouse and maintained under good growing conditions for the test plants. After about 3 weeks, the effect of the preparation is visually evaluated as a percentage compared to the untreated control. For example, 100% activity = death of plants, 0% activity = same as control plants.

[0298] The following Tables 1a to 19c show the efficacy / crop suitability against various harmful plants of selected compounds of general formula (I) at application rates equivalent to 20 to 320 g / ha, obtained by the test procedures specified above. [Table 7]

[0299] 1. Pre-event effect As shown by the results in Tables 1a-19c, the compounds of the present invention exhibit good crop plant compatibility and good pre-emergence herbicidal efficacy against a broad range of grass and broadleaf weeds. [Table 8] TIFF2024524230000094.tif226125TIFF2024524230000095.tif231125TIFF2024524230 000096.tif245125TIFF2024524230000097.tif241125TIFF2024524230000098.tif23312 4TIFF2024524230000099.tif253127TIFF2024524230000100.tif218126TIFF2024524230 000101.tif250127TIFF2024524230000102.tif224128TIFF2024524230000103.tif42121

[0300] As shown by the above results, the compound of the present invention represented by the general formula (I) has an excellent antibacterial effect on Abutilon theophrasti, Alopecurus myosuroides, Amaranthus retroflexus, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis, Stellaria media, Tripleurospermum inodorum, Veronica persica and Fallopia japonica in pre-emergence treatment at an application rate of 0.020 to 0.320 kg of active substance per hectare. It has good herbicidal efficacy against harmful plants such as N. convolvulus, as well as good crop plant compatibility against organisms such as corn (Zea mays), rice (Oryza sativa), oilseed rape (Brassica napus), soybean (Glycine max) and bread wheat (Triticum aestivum) at application rates of up to 0.32 kg per hectare.

[0301] The compounds of the invention are therefore suitable for controlling undesirable plant growth by pre-emergence methods.

[0302] 2. Post-emergence herbicidal activity and crop plant compatibility Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in plastic or organic pots, covered with soil and cultivated under controlled growing conditions in a greenhouse. After 2-3 weeks from sowing, the test plants are treated at the one-leaf stage. The green parts of the plants are sprayed with the compounds of the invention, formulated in wettable powder (WP) form or as emulsifiable concentrate (EC), as aqueous suspensions or emulsions with 0.5% additive, with a spray water volume of 600 L / ha (converted). After maintaining the test plants in the greenhouse under optimal growing conditions for about 3 weeks, the activity of the preparations is visually assessed in comparison with untreated controls. For example, 100% activity = death of plants, 0% activity = same as control plants.

[0303] Tables 20a to 38c below show the efficacy / crop suitability against various harmful plants of selected compounds of general formula (I) at application rates equivalent to 20 to 320 g / ha, obtained by the test procedures specified above. [Table 9] TIFF2024524230000105.tif253105TIFF2024524230000106.tif252107TIFF2024524230000107.tif243107TIFF2024524230000108.tif251105TIFF2024524230000109.tif251106TIFF2024524230000110.tif253106TIFF2024524230000111.tif241109TIFF2024524230000112.tif235106TIFF2024524230000113.tif253107TIFF2024524230000114.tif253106TIFF2024524230000115.tif243104TIFF2024524230000116.tif254106TIFF2024524230000117.tif255105TIFF2024524230000118.tif255105TIFF2024524230000119.tif254105TIFF2024524230000120.tif244106TIFF2024524230000121.tif253104TIFF2024524230000122.tif253105TIFF2024524230000123.tif252106TIFF2024524230000124.tif252105TIFF2024524230000125.tif255105TIFF2024524230000126.tif236107TIFF2024524230000127.tif253105TIFF2024524230000128.tif251105TIFF2024524230000129.tif255106TIFF2024524230000130.tif252106TIFF2024524230000131.tif253105TIFF2024524230000132.tif253105TIFF2024524230000133.tif248104TIFF2024524230000134.tif252106TIFF2024524230000135.tif254105TIFF2024524230000136.tif253104TIFF2024524230000137.tif254106TIFF2024524230000138.tif255105TIFF2024524230000139.tif253106TIFF2024524230000140.tif248106TIFF2024524230000141.tif252105TIFF2024524230000142.tif251106TIFF2024524230000143.tif251106TIFF2024524230000144.tif249105TIFF2024524230000145.tif243104TIFF2024524230000146.tif253106TIFF2024524230000147.tif252106TIFF2024524230000148.tif255106TIFF2024524230000149.tif253104TIFF2024524230000150.tif253105TIFF2024524230000151.tif255103TIFF2024524230000152.tif254104TIFF2024524230000153.tif253106TIFF2024524230000154.tif253103TIFF2024524230000155.tif142104.

[0304] As shown by the above results, the compound of the present invention represented by the general formula (I) has an excellent antibacterial effect on Abutilon theophrasti, Alopecurus myosuroides, Amaranthus retroflexus, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis, Stellaria media, Tripleurospermum inodorum, Veronica persica and Fallopia japonica in post-emergence treatment at an application rate of 0.020 to 0.320 kg of active substance per hectare. It has good herbicidal efficacy against harmful plants such as N. convolvulus, as well as good crop plant compatibility against organisms such as corn (Zea mays), rice (Oryza sativa), oilseed rape (Brassica napus), soybean (Glycine max) and bread wheat (Triticum aestivum) at application rates of up to 0.32 kg per hectare.

[0305] The compounds of the invention are therefore suitable for controlling undesirable plant growth by post-emergence methods.

[0306] 3. Comparative herbicidal activity of the compound of the present invention (I-01) and structurally similar compounds of WO2020 / 245044 [Table 10] TIFF2024524230000157.tif65144

[0307] The following Tables 40a and 40b show the efficacy of the compound of the present invention (I-01) and structurally similar compounds (WO2020 / 245044) against various harmful plants at application rates equivalent to 320 g / ha or less, obtained by the test procedures specified below. Here, the compound of the present invention (I-01) is R 2With respect to groups, the structurally similar compounds differ by differences in important structural features.

[0308] Pre-emergence herbicidal efficacy and crop plant compatibility (PE) Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in plastic pots or organic cultivation pots and covered with soil. The surface of the covered soil is then sprayed with the compounds of the invention, formulated in the form of wettable powders (WP) or as emulsifiable concentrates (EC), as aqueous suspensions or emulsions with 0.5% additives, with a spray water volume equivalent to 600 L / ha. After treatment, the pots are placed in a greenhouse and maintained under good growing conditions for the test plants. After about 3 weeks, the effect of the preparation is visually evaluated as a percentage compared to the untreated control. For example, 100% activity = death of plants, 0% activity = same as control plants.

[0309] The efficacy / crop suitability against various harmful plants of selected compounds (Table 39) at application rates equivalent to 80-320 g / ha, obtained by the test procedures specified above, is shown in Tables 40a and 40b below. [Table 11]

[0310] As shown by the results shown in Tables 40a and 40b, the compound of the present invention (I-01) shows a clearly improved herbicidal activity against various harmful plants at application rates of 320 g / ha or less per hectare compared to structurally similar compounds. Tables 41a and 41b below show the effects of the compound of the present invention (I-01) and structurally similar compounds (WO2020 / 245044) against various harmful plants at application rates equivalent to 320 g / ha or less, obtained by the test procedures specified below. Here, the compound of the present invention (I-01) has a R 2 With respect to groups, the structurally similar compounds differ by differences in important structural features.

[0311] Post-emergence herbicidal efficacy and crop plant compatibility (PO) Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in plastic or organic pots, covered with soil and cultivated under controlled growing conditions in a greenhouse. After 2-3 weeks from sowing, the test plants are treated at the one-leaf stage. The green parts of the plants are sprayed with the compounds of the invention, formulated in wettable powder (WP) form or as emulsifiable concentrate (EC), as aqueous suspensions or emulsions with 0.5% additive, with a spray water volume of 600 L / ha (converted). After maintaining the test plants in the greenhouse under optimal growing conditions for about 3 weeks, the activity of the preparations is visually assessed in comparison with untreated controls. For example, 100% activity = death of plants, 0% activity = same as control plants.

[0312] The efficacy / crop suitability against various harmful plants of selected compounds (see Table 39) at application rates equivalent to 80-320 g / ha, obtained by the test procedures specified below, is shown in Tables 41a and 41b below. [Table 12]

[0313] As shown by the results shown in Tables 41a and 41b, the compound of the present invention (I-01) exhibits significantly improved herbicidal activity against various harmful plants at application rates of up to 320 g / ha per hectare, compared to structurally similar compounds.

Claims

1. General formula (I) 【Chemistry 1】 [During the ceremony, A is A1, A2 and A3: 【Chemistry 2】 selected from the group consisting of: Q is Q1-Q16: 【Chemistry 3】 selected from the group consisting of: R １ is OR １ａ , N.R. ９ R １０ and R １ａ is hydrogen, or (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl [which are unsubstituted or, in any case, COOR ５ , halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-substituted independently with "m" groups selected from the group consisting of alkoxy, cyano, and nitro; or (C ２ -C ４ )-alkenyl, (C ２ -C ４ )-alkynyl, or (C １ -C ６ )-alkyl-SO-(C １ -C ６ )-alkyl-, (C １ -C ６ )-Alkyl-SO ２ - (C １ -C ６ )-alkyl- or heterocyclyl, heteroaryl, aryl, or Heterocyclyl-(C １ -C ４ )-alkyl-, heteroaryl-(C １ -C ４ )-alkyl-, aryl-(C １ -C ４ )-alkyl-[which are unsubstituted or, in each case, halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl; R ９ is hydrogen, (C １ -C １２ )-alkyl; R １０ is hydrogen, aryl, heteroaryl, heterocyclyl, (C １ -C １２ )-alkyl, (C ３ -C ８ )-cycloalkyl, (C ３ -C ８ )-cycloalkyl-(C １ -C ７ )-alkyl-, (C ２ -C １２ )-alkenyl, (C ５ -C ７ )-cycloalkenyl, (C ２ -C １２ )-alkynyl, S(O) ｎ R ５ , Cyano, OR ５ , S.O. ２ N.R. ６ R ７ , CO ２ R ８ , C.O.R. ８ [wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl groups are unsubstituted or optionally substituted with one or more substituted aryl, halogen, cyano, nitro, OR ５ , S(O) ｎ R ５ , S.O. ２ N.R. ６ R ７ , CO ２ R ８ , C.O.R. ６ R ８ , C.O.R. ６ , N.R. ６ R ８ , N.R. ６ C.O.R. ８ , N.R. ６ C.O.N.R. ８ R ８ , N.R. ６ CO ２ R ８ , N.R. ６ SO ２ R ８ , N.R. ６ SO ２ N.R. ６ R ８ , C(R ６ ) = NOR ８ each independently substituted with "m" groups selected from the group consisting of: Or, R ９ and R １０ together with the nitrogen atom to which they are attached form a saturated, partially unsaturated or fully unsaturated 5-, 6- or 7-membered ring, wherein the ring is selected from the group consisting of halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, OR ５ , S(O) ｎ R ５ , CO ２ R ８ , C.O.R. ６ R ８ , C.O.R. ６ and C(R ６ ) = NOR ８ and wherein the ring, in addition to the nitrogen atom, is optionally substituted with "m" groups selected from the group consisting of: ７ , CO and NCOR ７ containing as ring atoms "q" members selected from the group consisting of: R ５ (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl, aryl; R ６ is hydrogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl, aryl; R ７ is hydrogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C ３ -C ４ )-alkenyl, (C ３ -C ４ )-alkynyl; R ８ is hydrogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C ３ -C ４ )-alkenyl, (C １ -C ６ )-alkyl-COO(C １ -C ２ )-alkyl or (C ３ -C ４ )-alkynyl; R ２ is methoxy, ethoxy; R ３ is halogen, cyano, isocyano, NO ２ , (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl, (C ３ -C ６ )-halocycloalkyl, (C １ -C ６ )-alkylcarbonyl-, (C １ -C ６ )-haloalkylcarbonyl-, (C １ -C ６ )-alkyloxycarbonyl-, (C ２ -C ３ )-alkenyl, (C ２ -C ３ )-haloalkenyl, (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl, (C １ -C ６ )-alkyl-S(O) ｎ And (C １ -C ６ )-haloalkyl-S(O) ｎ , CHO and NH ２ and R １２ is halogen, cyano, NO ２ , (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl; R １３ is halogen, cyano, NO ２ , (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, (C １ -C ６ )-alkylcarbonyl, (C １ -C ６ )-haloalkylcarbonyl, (C １ -C ６ )-alkoxycarbonyl, (C １ -C ６ )-alkoxy, (C １ -C ６ )-haloalkoxy, (C １ -C ６ )-alkylS(O) ｎ , (C ２ -C ３ )-alkenyl, (C ２ -C ３ )-haloalkenyl, (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl; h is 0, 1 or 2; i is 0, 1, 2 or 3; k is 0, 1, 2, 3 or 4; m is 0, 1 or 2; n is 0, 1 or 2; o is 0, 1 or 2; p is 0 or 1; q is 0 or 1; r is 3, 4, 5 or 6; s is 0, 1, 2, 3, 4 or 5. and their agriculturally acceptable salts, N-oxides, hydrates, and hydrates of the salts and N-oxides.

2. A is A1-1, A1-2, A1-3, A1-4, A2-1, A3-1, A3-2, A3-3, A3-4 and A3-5 【Table 1】 and Q is Q1, Q2, Q9 and Q16 【Chemistry 4】 selected from the group consisting of: R １ is OR １ａ , N.R. ９ R １０ and R １ａ is hydrogen, or (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl [which are unsubstituted or, in any case, COOR ５ , halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-substituted independently with "m" groups selected from the group consisting of alkoxy, cyano, and nitro; or (C ２ -C ４ )-alkenyl, (C ２ -C ４ )-alkynyl, or (C １ -C ６ )-alkyl-SO-(C １ -C ６ )-alkyl-, (C １ -C ６ )-Alkyl-SO ２ - (C １ -C ６ )-alkyl-, aryl-(C １ -C ４ )-alkyl-[which are unsubstituted or, in each case, halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl; R ９ is hydrogen, (C １ -C ６ )-alkyl; R １０ is hydrogen, phenyl, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C ３ -C ６ )-cycloalkyl-(C １ -C ４ )-alkyl-, (C ２ -C ４ )-alkenyl, (C ５ -C ７ )-cycloalkenyl, (C ２ -C ４ )-alkynyl, S(O) ｎ R ５ , Cyano, OR ５ , S.O. ２ N.R. ６ R ７ , CO ２ R ８ , C.O.R. ８ [wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl groups are unsubstituted or may be singly or multiply substituted with phenyl, halogen, cyano, nitro, OR ５ , S(O) ｎ R ５ , S.O. ２ N.R. ６ R ７ , CO ２ R ８ , C.O.R. ６ R ８ , C.O.R. ６ , N.R. ６ R ８ , N.R. ６ C.O.R. ８ , N.R. ６ C.O.N.R. ８ R ８ , N.R. ６ CO ２ R ８ or R ９ and R １０ together with the nitrogen atom to which they are attached form a saturated, partially unsaturated or fully unsaturated 5-, 6- or 7-membered ring, wherein the ring is selected from the group consisting of halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, OR ５ , S(O) ｎ R ５ , CO ２ R ８ , C.O.R. ６ R ８ , C.O.R. ６ and C(R ６ ) = NOR ８ and wherein the ring, in addition to the nitrogen atom, is optionally substituted with "m" groups selected from the group consisting of: ７ , CO and NCOR ７ containing as ring atoms "q" members selected from the group consisting of: R ５ (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl or phenyl; R ６ is hydrogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl or phenyl; R ７ is hydrogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C ３ -C ４ )-alkenyl or (C ３ -C ４ )-alkynyl; R ８ is hydrogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C ３ -C ４ )-alkenyl or (C ３ -C ４ )-alkynyl; R ２ is methoxy, ethoxy; R ３ is halogen, cyano, isocyano, NO ２ , (C １ -C ４ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl, (C ３ -C ６ )-halocycloalkyl, (C ２ -C ３ )-alkenyl, (C ２ -C ３ )-haloalkenyl, (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl; R １３ is halogen, cyano, nitro, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, (C １ -C ６ )-alkoxy, (C １ -C ６ )-haloalkoxy, (C １ -C ６ )-alkylS(O) ｎ , (C ２ -C ３ )-alkenyl, (C ２ -C ３ )-haloalkenyl, (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl; i is 0, 1 or 2; k is 0, 1, 2, 3 or 4; m is 0, 1, 2; n is 0, 1, 2; o is 0, 1, 2; p is 0 or 1; q is 0 or 1; r is 3, 4, 5 or 6; s is 0, 1, 2, 4, 5; 2. A compound of formula (I) according to claim 1, or an agriculturally acceptable salt, N-oxide, hydrate or hydrate of said salt or N-oxide.

3. A is A1-1, A1-2, A1-3, A1-4, A2-1, A3-1, A3-2, A3-3, A3-4 and A3-5 【Table 2】 and Q is Q1, Q2, Q9 and Q16 【Chemistry 5】 selected from the group consisting of: R １ is OR １ａ , N.R. ９ R １０ and R １ａ is hydrogen, or (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl [which are unsubstituted or, in any case, COOR ５ , halogen, (C １ -C ４ )-alkyl, (C １ -C ４ )-haloalkyl; or Aryl-(C １ -C ４ )-alkyl-[which is unsubstituted or, in each case, halogen, (C １ -C ４ )-alkyl, (C １ -C ４ )-haloalkyl; R ９ is hydrogen; R １０ (C １ -C ４ )-alkyl, S(O) ｎ R ５ , S.O. ２ N.R. ６ R ７ , CO ２ R ８ wherein the above groups are unsubstituted or substituted, such as phenyl, S(O) ｎ R ５ , S.O. ２ N.R. ６ R ７ , CO ２ R ８ , N.R. ６ CO ２ R ８ each independently substituted with "m" groups selected from the group consisting of: R ５ is ethyl, methyl, CF ３ or CH ２ CF ３ and R ６ is hydrogen; R ７ is hydrogen, methyl or ethyl; R ８ is methyl or ethyl; R ２ is methoxy, ethoxy; R ３ is halogen, cyano, nitro, (C １ -C ４ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ４ )-haloalkyl, (C ３ -C ６ )-halocycloalkyl; R １３ is fluorine, chlorine, bromine, cyano, methyl, ethyl, methoxy, ethoxy, CF ３ , O.C.F. ３ and i is 0, 1 or 2; k is 0, 1 or 2; m is 0, 1 or 2; n is 0, 1 or 2; s is 0, 1 or 2; 3. A compound of formula (I) according to claim 1 or 2, or an agriculturally acceptable salt, N-oxide, hydrate or hydrate of said salt or N-oxide.

4. A is A1-1, A1-2, A1-3, A1-4, A2-1, A3-1, A3-2, A3-3, A3-4 and A3-5 【Table 3】 and Q is Q1, Q9 and Q16 【Chemistry 6】 selected from the group consisting of: R １ is OR １ａ and R １ａ is hydrogen, ethyl, methyl, -CH ２ CH (CH ３ ) COOmethyl, -CH ２ CH ２ COOmethyl; R ２ is ethoxy, methoxy; R ３ is chlorine, bromine, iodine, cyano, cyclopropyl, CF ２ CF ３ , C.H.F. ２ Or CF ３ and R １３ is fluorine, chlorine, methyl, MeS(O), MeS or CF ３ and i is 0, 1 or 2; k is 0, 1 or 2; s is 0, 1 or 2; 2. A compound of formula (I) according to claim 1, or an agriculturally acceptable salt, N-oxide, hydrate or hydrate of said salt or N-oxide.

5. A method for preparing a compound of formula (Ic) or an agriculturally acceptable salt thereof according to claim 1, comprising converting a compound of general formula (III) and a compound of general formula (IV) in the presence of a sulfurizing reagent (e.g., phosphorus pentasulfide or Lawesson's reagent). 【Chemistry 7】 [Here, R ２ , R １ａ , R ３ , A and Q have the definitions given above, and X is chlorine, bromine or iodine.

6. A method for preparing a compound of formula (Ia) or an agriculturally acceptable salt thereof according to claim 1, said method being carried out by converting a compound of general formula (Ic) in the presence of a base or a Lewis acid. 【Chemistry 8】 [In the formula, R ２ , R １ａ , R ３ , A and Q have the definitions given above.

7. A method for preparing a compound of formula (Ib) or an agriculturally acceptable salt thereof according to claim 1, by converting a compound of general formula (Ia) and a compound of general formula (II) in the presence of an amide coupling reagent. 【Chemistry 9】 [In the formula, R ９ , R １０ , R ２ , R １ａ , R ３ , A and Q have the definitions given above.

8. 1. An agrochemical composition comprising (a) at least one compound of formula (I) as defined in claim 1 or a pesticidally acceptable salt thereof, and (b) adjuvants and additives customary in crop protection.

9. 1. A pesticide composition comprising: (a) at least one compound of formula (I) as defined in claim 1 or a pesticidally acceptable salt thereof; (b) one or more pesticidal active ingredients other than component (a); and, optionally, (c) adjuvants and additives customary in crop protection; The pesticide composition comprising:

10. 1. A method for controlling undesirable plants or for regulating the growth of plants, which comprises applying an effective amount of at least one compound of formula (I) as defined in claim 1 or an agronomically acceptable salt thereof to the plants, to the seeds or to the area in which the plants are growing.

11. 2. Use of a compound of formula (I) as defined in claim 1 or an agriculturally acceptable salt thereof as a herbicide or plant growth regulator.

12. 12. Use according to claim 11, wherein the compounds of formula (I) or their pesticidally acceptable salts are used for controlling harmful plants or for regulating the growth in crop plants.

13. The use according to claim 12, wherein the crop plant is a transgenic crop plant or a non-transgenic crop plant.

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