1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids and their use for controlling undesirable plant growth

Abstract

The present invention relates to novel substituted 1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids of general formula (I) having herbicidal activity, their derivatives or agriculturally acceptable salts, processes for their preparation, and their use for controlling broadleaf weeds and grass weeds in crops of useful plants and for generally controlling broadleaf weeds and grass weeds in areas where plant growth is problematic. The derivatives of the 1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids include, in particular, their esters, salts, and amides.

Description

[Technical field]

[0001] The present invention relates to novel substituted 1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids of general formula (I) and their derivatives or agriculturally acceptable salts thereof having herbicidal activity, to processes for their preparation and to 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 1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids include in particular the esters, salts and amides thereof. [Background technology]

[0003] The prior art discloses the biological effects of substituted 1,5-diphenylpyrazolyl-3-oxyacetic acids and substituted 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids as well as methods for preparing these compounds. DE 2828529A1 describes a method for preparing 1,5-diphenylpyrazolyl-3-oxyacetic acids and their lipid-reducing effect. CN 101284815 discloses 1,5-diphenylpyrazolyl-3-oxyacetic acid derivatives as bactericidal pesticides. Journal of Heterocyclic Chemistry (2012), 49(6), 1370-1375 describes further methods for the synthesis and fungicidal action of 1,5-diphenylpyrazolyl-3-oxyacetic acids. Methods for the synthesis of substituted 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids and their pharmaceutical action as FXR and LXR modulators are described in WO 2008 / 073825A1.

[0004] Substituted 1,5-diphenylpyrazolyl-3-oxyalkyl acids and substituted 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids have not been known to date as herbicides.

[0005] A feature of all 1,5-diphenylpyrazolyl-3-oxyalkyl acid derivatives and all 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acid derivatives in the above documents is that the 4-position of the pyrazole is not substituted.

[0006] In contrast, the common feature of the 1,5-diphenylpyrazolyl-3-oxyalkyl acids and the 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids according to the invention is an additional substituent at the 4-position of the pyrazole ring. Thus, the present invention relates to compounds which are exclusively substituted at the 4-position of the pyrazole (R 3 ≠ hydrogen) 1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids and derivatives thereof are provided.

[0007] WO 2008 / 083233A2 describes 1,5-diphenylpyrazolyl-3-oxyalkyl acids and their derivatives substituted at the 4-position of the pyrazole as substances suitable for disintegrating cell aggregates. Ethyl [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetate is specifically disclosed.

[0008] Furthermore, the synthesis of several 4-chloro-1,5-diphenylpyrazolyl-3-oxyacetic acids and their ethyl esters is specifically described in "European Journal of Organic Chemistry (2011), 2011 (27), 5323-5330": [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid Ethyl [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetate Ethyl {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetate Ethyl {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetate.

[0009] WO 2008 / 141154 discloses: 2-(4-chloro-1,5-diphenylpyrazol-3-yl)oxypropanoic acid and 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

[0010] The herbicidal activity of these compounds is not described.

[0011] The 1-phenyl-5-thienylpyrazolyl-3-oxyacetic acids or 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids and their derivatives encompassed by the present application are unknown to date. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] DE 2828529A1 [Patent Document 2] CN 101284815 [Patent Document 3] WO 2008 / 073825A1 [Patent Document 4] WO 2008 / 083233A2 [Patent Document 5] WO 2008 / 141154 [Non-patent literature]

[0013] [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 [Problem to be solved by the invention]

[0014] The object of the present invention is to provide novel pyrazole derivatives, namely 1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids and derivatives thereof, which have sufficient herbicidal action and a broad spectrum of activity against harmful plants and / or have a high degree of selectivity in useful plant crops and can be used as herbicides or plant growth regulators. [Means for solving the problem]

[0015] The object is achieved by substituted pyrazolyl-3-oxoalkyl acids, characterized by various substituents at the 4-position of the pyrazole ring, i.e. 4-substituted 1,5-diphenylpyrazolyl-3-oxyalkyl acid derivatives and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acid derivatives, which have very good herbicidal action and also very good selectivity.

[0016] 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.

[0017] Thus, the present invention relates to a compound of the general formula (I) [ka] [During the ceremony, A is A1-A3 [ka] selected from the group consisting of; R 1 teeth, OR 1a and · NR 9 R 10 ; wherein: R 1a teeth, Hydrogen; methyl, ethyl, which is unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C3-C6)-cycloalkyl, (C1-C4)-trialkylsilyl, (C1-C6)-alkoxy, cyano and nitro; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; (C2-C6)-Alkynyl; (C3-C6)-cycloalkyl, which is unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl; (C1-C4)-Alkyl-SO-(C1-C4)-Alkyl, (C1-C4)-Alkyl-SO2-(C1-C4)-Alkyl; heterocyclyl, heteroaryl and aryl, which are unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl; heterocyclyl-(C1-C4)-alkyl, heteroaryl-(C1-C4)-alkyl and aryl-(C1-C4)-alkyl, in which the heterocyclyl, heteroaryl and aryl are unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl; selected from the group consisting of; R 9 is hydrogen, (C1-C 12 )-alkyl; R 10 teeth, Hydrogen; aryl, heteroaryl, heterocyclyl, which is unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl; (C3-C7)-cycloalkyl-(C1-C4)-alkyl, heterocyclyl-(C1-C4)-alkyl, heteroaryl-(C1-C4)-alkyl, aryl-(C1-C4)-alkoxy, in which cycloalkyl, heterocyclyl, heteroaryl and aryl are unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl; (C1-C 12 )-Alkyl;(C3-C8)-Cycloalkyl, (C2-C 12 )-alkenyl, (C5-C8)-cycloalkenyl, (C2-C 12 )-alkynyl, wherein the above alkyl, cycloalkenyl, alkenyl, cycloalkenyl and alkynyl radicals are unsubstituted or substituted with cyano, nitro, OR 5 , S(O) n R 5 , SO2NR 6 R 7 , C(O)OR 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 radicals selected from the group consisting of: (C1-C 12 )-Haloalkyl; S(O) n R 5 , Cyano, Nitro, OR 5 , SO2NR 6 R 7 , CO2R 8 , C.O.R. 8 , N.R. 6 R 8 , N.R. 6 COR 8 , N.R. 6 CO2R 8 , N.R. 6 SO2R 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, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, OR 5 , S(O) n R 5 , CO2R 8 ,CONR 6 R 8 , C.O.R. 6 and C(R 6 )=NOR 8 and the ring may be substituted with 1 to 6 radicals selected from the group consisting of, in addition to the nitrogen atom, r carbon atoms, o oxygen atoms, p sulfur atoms, and NR7 , CO and NCOR 7 comprising q members selected from the group consisting of: R 5 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl or aryl; R 6 is hydrogen or R 5 and; 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 2a teeth, Hydrogen; Methyl; selected from the group consisting of; R 2b is hydrogen; R 3 teeth, · Halogens, cyano, isocyano, NO2; (C1-C6)-Alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Haloalkyl, (C1-C6)-Alkylcarbonyl, (C1-C6)-Haloalkylcarbonyl, (C1-C4)-Alkyloxycarbonyl; (C2-C3)-alkenyl, (C2-C3)-haloalkenyl; (C2-C3)-alkynyl, (C2-C3)-haloalkynyl; (C1-C2)-Alkyl-S(O) n and (C1-C2)-haloalkyl-S(O) n ; · CHO; NH2; selected from the group consisting of; R 4 is phenyl, wherein the phenyl radical is unsubstituted or · Halogens, cyano, isocyano, nitro; (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C3)-haloalkoxy; (C2-C3)-alkenyl, (C2-C3)-haloalkenyl, (C1-C6)-alkoxy; (C2-C3)-Alkynyl, (C2-C3)-Haloalkynyl, (C1-C4)-Alkyl-S(O) n ; CHO, (C1-C4)-alkyloxycarbonyl and NH2 and wherein the radicals are selected from the group consisting of: R 12 teeth, · Halogens, cyano, isocyano, NO2; (C1-C6)-Alkyl, (C1-C6)-Haloalkyl, (C1-C6)-Alkylcarbonyl, (C1-C6)-Haloalkylcarbonyl, (C1-C4)-Alkyloxycarbonyl, (C1-C6)-Alkoxy, (C1-C3)-Haloalkoxy, (C1-C4)-Alkyl-S(O) n ; (C2-C3)-alkenyl, (C2-C3)-haloalkenyl; (C2-C3)-alkynyl, (C2-C3)-haloalkynyl; NH2; selected from the group consisting of; and where the subscripts are as follows: 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; and s is 0, 1, 2, 3, 4 or 5. and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids represented by the formula: However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenylpyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

[0018] definition In the definitions of the symbols used in the above formulae, collective terms are used which generally represent the following substituents:

[0019] halogen fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, and more preferably fluorine or chlorine.

[0020] Alkyl: A linear or branched saturated hydrocarbon radical having 1 to 8 (preferably 1 to 6, and more preferably 1 to 4) carbon atoms, such as (but not limited to) C1-C6-alkyl, such as methyl, ethyl, propyl (n-propyl), 1-methylethyl (isopropyl), butyl (n-butyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylethyl, propyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 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, which are in particular C1-C4-alkyl groups, such as methyl, ethyl, propyl, 1-methylethyl (isopropyl), butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1,1-dimethylethyl (tert-butyl) groups. Unless otherwise defined, for example, with respect to alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, haloalkyl, or haloalkylsulfanyl, this definition also applies to alkyl as part of a composite substituent (eg, cycloalkylalkyl or hydroxyalkyl).

[0021] Alkenyl: A straight or branched unsaturated hydrocarbon group having 2 to 8 (preferably 2 to 6, and more preferably 2 to 4) carbon atoms and a double bond at any position, such as (but not limited to) C2-C6-alkenyl, such as vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, isopropenyl, homoallyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop- 1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl, ( Z)-1-methylbut-2-enyl, (E)-3-methylbut-1-enyl, (Z)-3-methylbut-1-enyl, (E)-2-methylbut-1-enyl, (Z)-2-methylbut-1-enyl, (E)-1-methylbut-1-enyl, (Z)-1-methylbut-1-enyl, 1,1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl, (E)-3,3-dimethylprop-1-enyl, (Z)-3,3-dimethylprop-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, 4-methylpent-4-enyl, 3-methylpent-4-enyl, 2-methylpent-4-enyl, 1-methylpent-4-enyl, 4-methylpent-3-enyl, (E)-3-methylpent-3-enyl, (Z)-3-methylpent-3-enyl, (E)-2-methylpent-3-enyl, (Z)-2-methylpent-3-enyl,(E)-1-methylpent-3-enyl, (Z)-1-methylpent-3-enyl, (E)-4-methylpent-2-enyl, (Z)-4-methylpent-2-enyl, (E)-3-methylpent-2-enyl, (Z)-3-methylpent-2-enyl, (E)-2-methylpent-2-enyl, (Z)-2-methylpent-2-enyl, (E)-1-methylpent-2-enyl, (Z)-1-methylpent-2-enyl, (E)-4-methylpent-1-enyl, (Z)-4-methylpenta -1-enyl, (E)-3-methylpent-1-enyl, (Z)-3-methylpent-1-enyl, (E)-2-methylpent-1-enyl, (Z)-2-methylpent-1-enyl, (E)-1-methylpent-1-enyl, (Z)-1-methylpent-1-enyl, 3-ethylbut-3-enyl, 2-ethylbut-3-enyl, 1-ethylbut-3-enyl, (E)-3-ethylbut-2-enyl, (Z)-3-ethylbut-2-enyl, (E)-2-ethylbut-2-enyl, (Z)- 2-Ethylbut-2-enyl, (E)-1-ethylbut-2-enyl, (Z)-1-ethylbut-2-enyl, (E)-3-ethylbut-1-enyl, (Z)-3-ethylbut-1-enyl, 2-ethylbut-1-enyl, (E)-1-ethylbut-1-enyl, (Z)-1-ethylbut-1-enyl, 2-propylprop-2-enyl, 1-propylprop-2-enyl, 2-isopropylprop-2-enyl, 1-isopropylprop-2-enyl, (E)-2-propylprop-1-enyl nyl, (Z)-2-propylprop-1-enyl, (E)-1-propylprop-1-enyl, (Z)-1-propylprop-1-enyl, (E)-2-isopropylprop-1-enyl, (Z)-2-isopropylprop-1-enyl, (E)-1-isopropylprop-1-enyl, (Z)-1-isopropylprop-1-enyl, 1-(1,1-dimethylethyl)ethenyl, buta-1,3-dienyl, penta-1,4-dienyl, hexa-1,5-dienyl or methylhexadienyl. This group is in particular vinyl or allyl. Unless otherwise defined, this definition also applies to alkenyl as part of a compound substituent (e.g. haloalkenyl).

[0022] Alkynyl : A straight or branched chain hydrocarbon group having 2 to 8 (preferably 2 to 6, and more preferably 2 to 4) carbon atoms and a triple bond at any position, such as (but not limited to) C2-C6-alkynyl, such as ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methylprop-2-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, hex-1-ynyl, hex-2-ynyl, hex- 3-ynyl, hex-4-ynyl, hex-5-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-3-ynyl, 1-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1-methylpent-2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-ethylbut-3-ynyl, 1-ethylbut-3-ynyl, 1-ethylbut-2-ynyl, 1-propylprop-2-ynyl, 1-isopropylprop-2-ynyl, 2,2-dimethylbut-3-ynyl, 1,1-dimethylbut-3-ynyl, 1,1-dimethylbut-2-ynyl or 3,3-dimethylbut-1-ynyl. Said alkynyl group is in particular ethynyl, prop-1-ynyl or prop-2-ynyl. Unless otherwise defined, this definition also applies to alkynyl as part of a compound substituent (e.g. haloalkynyl).

[0023] Alkoxy: linear or branched saturated alkoxy radicals having 1 to 8 (preferably 1 to 6 and more preferably 1 to 4) carbon atoms, such as (but not limited to) 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, 1,1-dimethylpropoxy, alkoxy, 1,2-dimethylpropoxy, hexoxy, 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. Unless otherwise defined, this definition also applies to alkoxy as part of a compound substituent (e.g., haloalkoxy, alkynylalkoxy).

[0024] Alkoxycarbonyl An alkoxy group (as above) having 1 to 8 (preferably 1 to 6, and more preferably 1 to 4) carbon atoms attached to the backbone via a carbonyl group (-C(=O)-). Unless otherwise defined, this definition also applies to alkoxycarbonyl as part of a composite substituent (e.g., cycloalkylalkoxycarbonyl).

[0025] Cycloalkyl Monocyclic saturated hydrocarbyl groups having 3 to 10 (preferably 3 to 8, and more preferably 3 to 6) carbon ring members, such as (but not limited to) cyclopropyl, cyclopentyl, and cyclohexyl. Unless otherwise defined, this definition also applies to cycloalkyl as part of a composite substituent (e.g., cycloalkylalkyl).

[0026] Cycloalkenyl Monocyclic partially unsaturated hydrocarbyl groups having 3 to 10 (preferably 3 to 8, and more preferably 3 to 6) carbon ring members, such as (but not limited to) cyclopropenyl, cyclopentenyl, and cyclohexenyl. Unless otherwise defined, this definition also applies to cycloalkenyl as part of a compound substituent (e.g., cycloalkenylalkyl).

[0027] Cycloalkoxy Monocyclic saturated cycloalkyloxy radicals having 3 to 10 (preferably 3 to 8, and more preferably 3 to 6) carbon ring members, such as (but not limited to) cyclopropyloxy, cyclopentyloxy, and cyclohexyloxy. Unless otherwise defined, this definition also applies to cycloalkoxy as part of a composite substituent (e.g., cycloalkoxyalkyl).

[0028] Haloalkyl Straight or branched alkyl groups (as defined above) having 1 to 8 (preferably 1 to 6 and more preferably 1 to 4) carbon atoms, in which some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above, such as (but not limited to) C1-C3-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. Unless otherwise defined, this definition also applies to haloalkyl as part of a composite substituent (eg, haloalkylaminoalkyl).

[0029] Haloalkenyl and haloalkynyl are defined similarly to haloalkyl, except that an alkenyl group and alkynyl group, respectively, are present as part of the substituent instead of an alkyl group.

[0030] Haloalkoxy alkoxy groups having 1 to 8 (preferably 1 to 6, and more preferably 1 to 4) carbon atoms, straight or branched (as described above), in which some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above, such as (but not limited to) C1-C3-haloalkoxy, e.g., 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-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy. Unless otherwise defined, this definition also applies to haloalkoxy as part of a compound substituent (e.g., haloalkoxyalkyl).

[0031] Aryl : monocyclic, bicyclic or tricyclic aromatic or partially aromatic groups having 6 to 14 carbon atoms, such as (but not limited to) phenyl, naphthyl, tetrahydronaphthyl, indenyl and indanyl. The bond to the parent general structure can be via any desired suitable ring member of the aryl radical. Aryl is preferably selected from phenyl, 1-naphthyl and 2-naphthyl. Particularly preferred is phenyl.

[0032] Heteroaryl: a 5- or 6-membered cyclic aromatic group having at least one heteroatom or optionally 2, 3, 4 or 5 heteroatoms, each of which is independently selected from the group S, N and O, and wherein the group can also be part of a bicyclic or tricyclic system having up to 14 ring members, and wherein the ring system can be formed with one or two further cycloalkyl, cycloalkenyl, heterocyclyl, aryl and / or heteroaryl radicals, and wherein benzo-fused 5- or 6-membered heteroaryl groups are preferred. The bond to the parent general structure can be via any desired suitable ring member of the heteroaryl radical. a 5-membered heteroaryl group attached to the backbone through one of its carbon ring members; Examples of the aryl groups are fura-2-yl, fura-3-yl, thien-2-yl, thien-3-yl, pyrrol-2-yl, pyrrol-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazolyl ... and 1,3,4-triazol-2-yl, 1,3,4-triazol-2-yl, 1,3,4-triazol-4-yl, 1,3,4-triazol-5-yl, 1,2,4-triazol-2-yl, 1,3,4-triazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-triazol-2-yl, 1,3,4-triazol-2-yl, and 1,3,4-triazol-2-yl. A 5-membered heteroaryl group attached to the backbone via a nitrogen ring member Examples are pyrrol-1-yl, pyrazol-1-yl, 1,2,4-triazol-1-yl, imidazol-1-yl, 1,2,3-triazol-1-yl and 1,3,4-triazol-1-yl. 6-membered heteroaryl groupExamples are pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl. Benzo-fused 5-membered heteroaryl groups Examples of are indol-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-1-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran ... 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, 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, 1,3-benzoxazol-2-yl, 1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl and 1,3-benzoxazol-7-yl. Benzo-fused six-membered heteroaryl groupsExamples are quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl. Further examples of 5- or 6-membered heteroaryl radicals that are part of a bicyclic ring system are 1,2,3,4-tetrahydroquinolin-1-yl, 1,2,3,4-tetrahydroquinolin-2-yl, 1,2,3,4-tetrahydroquinolin-7-yl, 1,2,3,4-tetrahydroquinolin-8-yl, 1,2,3,4-tetrahydroisoquinolin-1-yl, 1,2,3,4-tetrahydroisoquinolin-2-yl, 1,2,3,4-tetrahydroisoquinolin-5-yl, 1,2,3,4-tetrahydroisoquinolin-6-yl and 1,2,3,4-tetrahydroisoquinolin-7-yl. Unless otherwise defined, this definition also applies to heteroaryl as part of a compound substituent (e.g., heteroarylalkyl).

[0033] Heterocyclyl A 3-7 membered saturated or partially unsaturated heterocyclic group, which may be benzo-fused, having at least one (optionally up to four) heteroatoms and / or heterogroups independently selected from the group consisting of N, O, S, S(=O), S(=O)2 and di-(C1-C4)alkylsilyl. The bond to the parent general structure may be via a ring carbon atom of the heterocyclic group or, where possible, via a ring nitrogen atom of the heterocyclic group. In the context of the present invention, Saturated Heterocyclic Groupsis, for example (but not limited to), oxiranyl, aziridinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, oxazolidin-2-yl, oxazolidin-4-yl, oxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-4-yl, thiazolidin-5-yl, imidazolidin-2-yl, imidazolidin-4-yl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-3-yl, Diazolidin-5-yl, 1,3,4-oxadiazolidin-2-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,3,4-thiadiazolidin-2-yl, 1,2,4-triazolidin-3-yl, 1,3,4-triazolidin-2-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-5-yl, tetrahydro Pyran-2-yl, tetrahydropyran-4-yl, tetrahydrothien-2-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-2-yl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl. Partially unsaturated heterocyclic groupis, for example, but not limited to, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, Xazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin- 5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5- dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl. Benzo-fused heterocyclic groupsExamples are indolin-1-yl, indolin-2-yl, indolin-3-yl, isoindolin-1-yl, isoindolin-2-yl, 2,3-dihydrobenzofuran-2-yl and 2,3-dihydrobenzofuran-3-yl. Unless otherwise defined, this definition also applies to heterocyclyl as part of a compound substituent (e.g., heterocyclylalkyl).

[0034] Combinations that are contrary to the laws of nature and therefore would be excluded by a person skilled in the art based on his or her own specialized knowledge are not included, for example ring structures having three or more adjacent oxygen atoms are excluded. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] Preferred is represented by the general formula (I) A is A1-A3 [ka] selected from the group consisting of; R 1 teeth, OR 1a and · NR 9 R 10 ; wherein: R 1a teeth, Hydrogen; methyl, ethyl, which is unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C3-C6)-cycloalkyl, (C1-C4)-trialkylsilyl, (C1-C4)-alkoxy, cyano and nitro; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; aryl-(C1-C4)-alkyl, in which the aryl is unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl; selected from the group consisting of; R 9 is selected from the group consisting of hydrogen, (C1-C6)-alkyl; R 10 teeth, Hydrogen; (C3-C7)-Cycloalkyl-(C1-C4)-alkyl, aryl-(C1-C4)-alkyl, aryl-(C1-C4)-alkoxy, in which the cycloalkyl and aryl are unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl; (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl; (C3-C8)-cycloalkyl, in which the above-mentioned alkyl, alkenyl, alkynyl and cycloalkenyl radicals are unsubstituted or substituted by cyano, C(O)OR 8 each independently substituted with m radicals selected from the group consisting of: (C1-C6)-Haloalkyl; selected from the group consisting of; R 8 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl; R 2a teeth, Hydrogen; Methyl; selected from the group consisting of; R 2b is hydrogen; R 3 teeth, · Fluorine, Chlorine, Bromine, Iodine, Cyano, Isocyano, NO2; (C1-C6)-Alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Haloalkyl, (C1-C4)-Alkyloxycarbonyl; (C2-C3)-alkynyl, (C2-C3)-haloalkynyl; selected from the group consisting of; R 4 is phenyl, wherein the phenyl radical is unsubstituted or · Fluorine, chlorine, bromine; Methyl, ethyl; · Methoxy, ethoxy; and wherein the radicals are selected from the group consisting of: R 12 teeth, · Halogens, cyano, nitro; (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C3)-haloalkoxy; (C1-C6)-alkoxy; selected from the group consisting of; and where the subscripts are as follows: m is 0, 1 or 2; and s is 0, 1, 2, or 3; and agriculturally acceptable salts thereof; However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenyl-pyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

[0036] Particularly preferred is represented by the general formula (I) A is A1 [ka] and; R 1 teeth, OR 1a and · NR 9 R 10 ; wherein: R 1a teeth, Hydrogen; Methyl, ethyl, trimethylsilylmethyl; 1-propenyl, 2-propenyl; benzyl, 1-phenylethyl, 2-phenylethyl [wherein the phenyl radical in each of the three groups named is unsubstituted or substituted with a halogen]; selected from the group consisting of; R 9 is hydrogen; R 10 teeth, Hydrogen; Cyclopropylmethyl; benzyl, 1-phenylethyl, 2-phenylethyl, benzyloxy [wherein the phenyl radical in each of the four groups named is unsubstituted or substituted by halogen]; 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, wherein the radicals are unsubstituted or C(O)OR 8 each independently being monosubstituted with a radical]; Cyclopropyl, cyclobutyl, cyclopentyl [where the three radicals mentioned are unsubstituted or C(O)OR 8 each independently being monosubstituted with a radical]; 1-propenyl, 2-propenyl, 2-methyl-2-propenyl, prop-2-yn-1-yl, but-2-yn-1-yl; selected from the group consisting of; R 8is hydrogen, methyl, ethyl; R 2a teeth, Hydrogen; Methyl; selected from the group consisting of; R 2b is hydrogen; R 3 teeth, · Fluorine, Chlorine, Bromine, Iodine, Cyano, NO2; Trifluoromethyl; · Ethynyl; C(O)Omethyl; selected from the group consisting of; R 4 is phenyl, wherein the phenyl radical is unsubstituted or · Fluorine, chlorine, bromine; Methyl, ethyl; · Methoxy, ethoxy; and wherein the radicals are selected from the group consisting of: R 12 teeth, · Fluorine, Chlorine, NO2; · Trifluoromethyl, methoxy, ethoxy; selected from the group consisting of; and where the subscripts are as follows: and s is 1, 2, or 3; and agriculturally acceptable salts thereof; However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenyl-pyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

[0037] Very particularly preferred is represented by the general formula (I) A is A1 [ka] and; R 1 teeth, OR 1a and · NR 9 R 10 ; wherein: R 1a teeth, Hydrogen; Methyl, ethyl; 2-Propenyl; selected from the group consisting of; R 9 is hydrogen; R 10 teeth, · C(O)OR 8 Cyclopentyl monosubstituted with; Cyclopropylmethyl; · CH2C(O)OR 8 , CH2CH2C(O)OR 8 ; 2-Propenyl, prop-2-yn-1-yl; selected from the group consisting of; R 8 is hydrogen, methyl, ethyl; R 2a teeth, Hydrogen; Methyl; selected from the group consisting of; R 2b is hydrogen; R 3 teeth, · Chlorine, Bromine, Iodine, Cyano, NO2; selected from the group consisting of; R 4 is phenyl, wherein the phenyl radical is unsubstituted or · Fluorine, chlorine; and wherein the radicals are selected from the group consisting of: R 12 teeth, · Fluorine, chlorine; selected from the group consisting of; and where the subscripts are as follows: and s is 1 or 2] and agriculturally acceptable salts thereof; However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, ethyl, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenyl-pyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

[0038] 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] According to the rules of Cahn, Ingold and Prelog (CIP rules), this carbon atom can have either the (R) or the (S) configuration.

[0039] 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 possesses the The present invention is intended to include compounds represented by the following formula:

[0040] Further within the scope of the present invention are: (3) Any mixture of a compound represented by general formula (I) having an (R) configuration (a compound represented by general formula (I-(R)) and a compound represented by general formula (I) having an (S) configuration (a compound represented by general formula (I-(S))): The present invention also encompasses a racemic mixture of a compound represented by general formula (I) having an (R) configuration and a compound represented by general formula (I) having an (S) configuration.

[0041] However, in the context of the present invention, preference is given to compounds of the general formula (I) having the (R) configuration which exhibit a selectivity of 60-100% (preferably 80-100%, in particular 90-100%, very particularly 95-100%), where the particular (R)-compound is present with an enantioselectivity of more than 50% ee in each case (preferably an enantioselectivity of 60-100% ee, in particular an enantioselectivity of 80-100% ee, very particularly an enantioselectivity of 90-100% ee, most preferably an enantioselectivity of 95-100% ee), based on the total content of the (R)-compounds.

[0042] The present invention therefore relates in particular to compounds of the general formula (I * ) [In the formula, ( * ) is present in a stereochemical purity of 60 to 100% (R) (preferably 80 to 100% (R), in particular 90 to 100% (R), and very particularly 95 to 100% (R)).

[0043] Furthermore, depending on the selected individual radicals, further stereoelements may be present in the compounds of general formula (I) according to the invention.

[0044] Preference is given to the compounds listed in the table below. Compounds of general formula (I) having the (R) configuration are correspondingly represented by the radical R 2a A check mark is placed in the column in which the value is written. For example, R 2a = alkyl, the ( *The preferred stereochemical configuration at the carbon atom to which is attached is the (R) configuration.

[0045] Considering the rules of Cahn, Ingold and Prelog, ( * At the carbon atom to which is attached (), due to the priority of the substituents, * There may be situations where the (S) configuration is preferred at the carbon atom to which R is attached. 2a This is the case when the radical corresponds to a (C1-C6)-alkoxy radical.

[0046] Thus, in the context of the present invention, preference is given, in particular with regard to their spatial arrangement, to compounds of the general formula (I), 2a is methyl having the (R) configuration with a selectivity of 60% to 100% (preferably 80% to 100%, in particular 90% to 100%, very particularly 95% to 100%), in which the individual (R) analogues are present with an enantioselectivity of more than 50% ee in each case (preferably 60% to 100% ee, in particular 80% to 100% ee, very particularly 90% to 100% ee, most preferably 95% to 100% ee), based on the total content of the (R) analogues.

[0047] Thus, the present invention relates in particular to a compound represented by the formula ( * The present invention relates to compounds of general formula (I) in which the stereochemical configuration at the carbon atom to which is attached (R or R analogue) is present in a stereochemical purity of 60% to 100% (R or R analogue), preferably 80% to 100% (R or R analogue), in particular 90% to 100% (R or R analogue), very particularly 95% to 100% (R or R analogue).

[0048] Table I: Esters [ka] [Table 1] TIFF0007631346000009.tif250166TIFF0007631346000010.tif251167TIFF0007631346000011.tif250167TIFF0007631346000012.tif182167

[0049] Table II: Salts [ka] [Table 2]

[0050] Table III: Amides [ka] [Table 3] TIFF0007631346000017.tif238160

[0051] A further aspect of the invention relates to the preparation of the compounds of general formula (I) according to the invention.The compounds according to the invention can be prepared in various ways.

[0052] The compounds according to the invention can be prepared, for example, from substituted 1,5-diphenyl-1H-pyrazol-3-ol or 1-phenyl-5-thienyl-1H-pyrazol-3-ol (II) by the synthetic method shown in Scheme 1 below. [ka] Scheme 1 Scheme 1 illustrates the reaction of a substituted pyrazole represented by general formula (IV) with an electrophilic halogenating reagent represented by general formula V, such as N-chlorosuccinimide (V, R 3 =Cl), N-bromosuccinimide (V, R 3=Br) or N-iodosuccinimide (V, R 3 =I)) to give a compound of the general formula (Ia, R 3 = Cl, Br, I) are described. In a similar manner, other electrophiles, such as electrophilic nitration reagents (e.g., nitrating acid, nitronium tetrafluoroborate, or ammonium nitrate / trifluoroacetic acid) (R 3 = NO2) or electrophilic fluorination reagents (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) within the temperature range of 0°C to 120°C.

[0053] General formula (Ib;R 3 The compound represented by formula (Ia;R =CN) can be, for example, 3 = Cl, Br, I, preferably R 3=Br, I) in a suitable solvent, by reacting with a metal cyanide M-CN(VI) with a suitable amount of a transition metal catalyst, in particular a palladium catalyst (e.g., palladium(0) tetrakis(triphenylphosphine) or palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride) or a nickel catalyst (e.g., nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride), preferably at elevated temperature in an organic solvent (e.g., 1,2-dimethoxyethane or N,N-dimethylformamide). The "M" radical represents, for example, magnesium, zinc, lithium 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. Belier, 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.

[0054] The compound of general formula (IV) can be prepared by alkylating 3-hydroxypyrazole of general formula (II) with halide of general formula (III) in the presence of a base, or by or in analogy to methods known to those skilled in the art. Preferably, the base is an alkali metal carbonate selected from the group consisting of lithium, sodium, potassium and cesium. 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 J. Med. Chem. 2011, 54(16), 5820-5835 and WO2010 / 010154. The "X" radical represents, for example, chlorine, bromine or iodine.

[0055] 3-Hydroxypyrazoles (II) can be prepared, for example, in two steps from substituted 3-phenyl- or thienylpropionic acid derivatives of general formula (VII) in analogy to methods known from the literature (Scheme 2; see, for example, Adv. Synth. Catal. 2014, 356, 3135-3147). [ka] Scheme 2 In the first step (Scheme 2), compounds of general formula (IX) are synthesized via amide coupling of substituted propionic acids of general formula (VII) with arylhydrazines of general formula (VIII) in the presence of amide coupling reagents such as propanephosphonic anhydride (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 2). For T3P peptide coupling conditions, see Organic Process Research & Development 2009, 13, 900-906.

[0056] In the second step (Scheme 2), the compound of general formula (IX) is cyclized in the presence of a copper halide (e.g., copper(I) iodide, copper(I) bromide) or a base (e.g., sodium methoxide) or an acid (e.g., methanesulfonic acid) to give a 3-hydroxypyrazole of general formula (II). The reaction is preferably carried out in a suitable solvent (e.g., 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, n-propanol, n-butanol or ethyl acetate) at a temperature range of 0° C. to 120° C.

[0057] 3-Hydroxypyrazole (II) can also be prepared, for example, from a protected 3-hydroxypyrazole of the general formula (X), in which the protecting group R is preferably a benzyl group or a trialkylsilyl group. [ka] Scheme 3 In the first step of scheme 3, a compound of general formula (XII) is prepared by N-arylation of a protected 3-hydroxypyrazole of general formula (X) with an aryl halide of general formula (XI) in the presence of a copper halide (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 or cesium carbonate) at a temperature range of 0°C to 120°C. Compounds of general formula (XII) can be prepared according to similar methods known to those skilled in the art (see, for example, Chem. Med. Chem. 2015, 10, 1184-1199). The "X" radical in compounds of general formula (XI) is, for example, chlorine, bromine or iodine.

[0058] In the second step, 5-iodopyrazole of general formula (XIII) is prepared from compound of general formula (XII). The reaction is carried out in the presence of a strong base (e.g., n-butyllithium or 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.

[0059] The compound of formula (XV) can be prepared, for example, by reacting the compound of formula (XIII) with the compound MA (XIV) in a suitable solvent, preferably at elevated temperature in an organic solvent (for example 1,2-dimethoxyethane), by adding a suitable amount of a transition metal catalyst, in particular a palladium catalyst (for example palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride) or a nickel catalyst (for example nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride). The "M" radical can be, for example, B(OR b )(OR c ), where R b and R c The radicals are independently, for example, hydrogen or (C1-C4)-alkyl or the radical R b and R c are linked together to form ethylene or propylene. Compounds of formula (XV) are deprotected by standard methods well known to those skilled in the art to finally obtain 3-hydroxypyrazoles of general formula (II), which can be further transformed into compounds according to the invention, for example as described in Scheme 1.

[0060] The compounds according to the invention can also be prepared from substituted 5-amino-1-phenyl-1H-pyrazol-3-ols of general formula (XVI), for example, by the synthetic method depicted in Scheme 4 below. [ka] Scheme 4 Scheme 4 describes the synthesis of compounds of formula (Ia) by methods known to those skilled in the art or by methods analogous to those known to those skilled in the art, by reacting a compound of general formula (XIX), in which Hal is preferably bromine or iodine, more preferably iodine, with a compound MA (XX) in the presence of a suitable amount of a transition metal catalyst, in particular a palladium catalyst (e.g. palladium diacetate or bis(triphenylphosphine)palladium(II)dichloride) or a nickel catalyst (e.g. nickel(II)acetylacetonate or bis(triphenylphosphine)nickel(II)chloride), preferably at elevated temperature in an organic solvent (e.g. 1,2-dimethoxyethane or dioxane). The "M" radical is, for example, Mg-Hal, Zn-Hal, Sn((C1-C4)-alkyl), lithium, copper or B(OR b )(OR c ), where R b and R c The radicals are independently, for example, hydrogen, (C1-C4)-alkyl or the radical R b and R c When linked to each other, they together form ethylene or propylene.

[0061] Compounds of general formula (XIX) can be prepared by diazotization followed by reaction of 5-aminopyrazoles of general formula (XVIII) with conventional organic and inorganic nitrites (e.g., 1,1-dimethylethyl nitrite, tert-butyl nitrite or isoamyl nitrite) in the presence of available reagents (e.g., copper(I) and copper(II) bromide / chloride mixtures, iodine or diiodomethane) (Scheme 4). The reaction is preferably carried out in a suitable solvent (e.g., dichloromethane, acetonitrile or N,N-dimethylformamide) at a temperature range of 0°C to 120°C.

[0062] Compounds of general formula (XVIII) can be prepared by reacting a substituted pyrazole of general formula (XVII) with an electrophilic reagent, such as an electrophilic halogenating reagent, e.g., N-chlorosuccinimide (R 3 =Cl), N-bromosuccinimide (R 3 =Br), N-iodosuccinimide (R 3 = I)] or electrophilic nitration reagents [e.g., nitrating acid, nitronium tetrafluoroborate, ammonium nitrate / trifluoroacetic acid] (R 3 = NO2) or electrophilic fluorination reagents (e.g., DAST, Selectfluor, N-fluorobenzenesulfonimide) (R 3 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. The compound of the general formula (XVIII; where R 3 The compound represented by formula (XVIII; where R 3 = halogen, preferably R 3=Br, I) in a suitable solvent, by reacting with a metal cyanide (e.g. zinc cyanide) with the addition of a suitable amount of a transition metal catalyst, in particular a palladium catalyst (e.g. palladium(0) tetrakis(triphenylphosphine) or palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride) or a nickel catalyst (e.g. nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride), preferably at elevated temperature in an organic solvent (e.g. 1,2-dimethoxyethane or N,N-dimethylformamide). 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. Belier, 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.

[0063] The compounds of general formula (XVII) can be synthesized by alkylating substituted 5-amino-1-phenyl-1H-pyrazol-3-ols of general formula (XVI) with halides of general formula (III) in the presence of a base (see scheme 4), by methods known to those skilled in the art or similar to those known to those skilled in the art. The base can be a carbonate of an alkali metal (e.g., lithium, sodium, potassium or cesium). 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. The "X" radical in the compounds of general formula (III) is, for example, chlorine, bromine or iodine. The compounds of general formula (XVI) are commercially available or known from the literature.

[0064] The compound of formula (Ia) may be used to prepare a compound of formula (Ic), 1a =H] and general formula (Id) [wherein R 1 =NR 9 R 10 The compound of the present invention represented by the formula (I) can be prepared by the method of the present invention. [ka] Scheme 5 As shown in scheme 5, acids of general formula (Ic) can be prepared by hydrolysis of esters of general formula (Ia) by methods known to those skilled in the art or by methods similar to those known to those skilled in the art. 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.

[0065] The compounds of the present invention represented by general formula (Id) are synthesized via amide coupling of acids represented by general formula (Ic) with amines represented by general formula (XXI) in the presence of amide coupling reagents such as propanephosphonic anhydride (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, 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] The compounds of the invention can be selective among useful plant crops and can also be used as non-selective herbicides.

[0073] 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.

[0074] Preferably, the compounds of formula (I) or salts thereof are used in economically important transgenic crops of useful and ornamental plants.

[0075] 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.

[0076] 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").

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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).

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] The combination partner that can be used for the compound of the present invention in a mixed formulation or in a tank mix is, for example, a known active ingredient 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, etc., known from, for example, "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 documents cited therein. The known herbicides or plant growth regulators that can be combined with the compound of the present invention are, for example, the following, where the active ingredient is indicated by "common name" according to the International Organization for Standardization (ISO), or indicated by chemical name, or indicated by code number: They always include all use forms, such as acids, salts, esters, etc., even if not explicitly mentioned, as well as all isomeric forms, such as stereoisomers and optical isomers.

[0092] Examples of such herbicidal admixture partners are: Acetochlor, Acifluorfen, Acifluorfen-sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-sodium, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, Aminocyclopyrachlor, Aminocyclopyrachlor-potassium, Aminocyclopyrachlor-methyl, Aminopyralid, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Atto azithromycin, azafenidine, azimsulfuron, beflubutamide, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazon, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanaphos, bilanaphos-sodium, bispyribac, bispyribac-sodium, bixlozone, bromacil, bromobutide, bromofenoxime, bromoxynil, bromoxynil-butyrate, potassium, heptanoate and octanoate, busoxynone (busoxinone), butachlor, butafenacil, butamiphos, butenachlor, butralin, butroxydim, butyrate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, 1-{2-chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6-(trifluoromethyl)phenyl}piperidin-2-one, 4-{2-chloro-3-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-4-( methylsulfonyl)benzoyl}-1,3-dimethyl-1H-pyrazole-5-yl-1,3-dimethyl-1H-pyrazole-4-carboxylate, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, 2-[2-chloro-4-(methylsulfonyl)-3-(morpholin-4-ylmethyl)benzoyl]-3-hydroxycyclohex-2-en-1-one, 4-{2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzoyl}-1-ethyl-1H-pyrazol-5-yl 1,3-dimethyl-1H-pyrazole-4-carboxylate, chlorophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, 3-[5-chloro-4-(trifluoromethyl)pyridin-2-yl]-4-hydroxy-1-methylimidazolidin-2-one, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clasifos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam , cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamine, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropanolammonium and -trolazine trolamine, 2,4-DB, 2,4-DB-butyl, dimethylammonium, isooctyl, potassium and sodium, daimuron, dymron, dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufe Nikan, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, 3-(2,6-dimethylphenyl)-6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1-methylquinazoline-2,4(1H,3H)-dione, 1,3-dimethyl-4-[2-(methylsulfonyl)-4-(trifluoromethyl)benzoyl]-1H-pyrazol-5-yl 1,3-Dimethyl-1H-pyrazole-4-carboxylate, dimetrasulfuron, dinitramine, dinoterb, diphenamide, diquat, diquat dibromide, dithiopyr, diuron, DMPA, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyphene, ethoxyphene-ethyl, ethoxysulfuron, etobenzanide, [(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)phenyl]phenyl] ethyl acetate, F-9960, F-5231, i.e., N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]-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, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, florpyrauxifen, florpyrauxifen-benzyl, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, -dimethyl Ammonium and -methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium and -trimesium, H-9201, i.e., O-(2,4-dimethyl-6-nitrophenyl) O-Ethyl isopropyl phosphoramidothioate, haloxifene, haloxifene-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e., 1-(dimethoxyphosphoryl)ethyl (2,4-Dichlorophenoxy)acetate, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, (5-hydroxy-1-methyl-1H-pyrazol-4-yl)(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophen-5-yl)methanone, 6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1,5-dimethyl-3-(2-methylphenyl)quinazoline-2,4(1H,3H)-dione, imazamethabenz, imazamethabenz-methyl, imazamox, imazamo ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-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, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, Mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozoline, 2-({2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)pyridin-3-yl}carbonyl)cyclohexane-1,3-dione, methyl isothiocyanate, 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, metobromuron, metolachlor, S-metolachlor, metoslam, methoxron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, i.e., N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methylpentanamide, NGGC-011, napropamide, NC-310, i.e., 4-(2,4-Dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, nebulon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxotrione (lancotrione), oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsura , pentachlorophenol, pentoxazone, petroleum, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, propoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prop, Rosulfocarb, 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, Pyroxas Lufon, Piroxisulam, Quinclorac, Quinmelac, Quinoclamine, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, QYM-201, QYR-301, Rimsulfuron, Saflufenacil, Sethoxydim, Siduron, Simazine, Simetryne, Sulcotrione, Sulfentrazone, Sulfometuron, Sulfometuron-methyl, Sulfosulfuron, SYN-523, 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 (trifluoroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, tetflupyrolimet, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, thiaphena Sil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, ZJ-0862, i.e., 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline.

[0093] Examples of plant growth regulators as possible mixing partners are: Acibenzolar, Acibenzolar-S-methyl, 5-Aminolevulinic acid, Ancymidol, 6-Benzylaminopurine, Brassinolide, Catechol, Chlormequat-chloride, Cloprop, Cyclanilide, 3-(Cycloprop-1-enyl)propionic acid, Daminozide, Dazomet, n-Decanol, Dikegulac, Dikegulac-sodium, Endothal, Endothal-dipotassium, -disodium and Mono(N,N-dimethylalkylammonium), Ethephon, Flumetralin, Flurenol, Flurenol-butyl, Flurprimidol, Forchlorfenuron, Gibberellic acid, Inabenfide, Indole-3-acetic acid (IAA), 4-Indol-3-yl Butyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic acid methyl ester, maleic hydrazide, mepiquat chloride, 1-methylcyclopropene, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixture, 4-oxo-4-[(2-phenylethyl)amino]butyric acid, paclobutrazol, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P.

[0094] Safeners which can be used in combination with the compounds of the invention of formula (I) and, optionally, with further active compounds (e.g. the fungicides, herbicides, acaricides, insecticides mentioned above) are preferably selected from the group consisting of:

[0095] (S1) Equation (S1) [ka] 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; RA 1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl; W A is an unsubstituted or substituted divalent heterocyclic radical 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 are present in the ring, preferably (W A 1 )~(W A 4 ) [ka] is a radical 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 A 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 consisting of O and S, which is linked to the carbonyl group in (S1) via a nitrogen atom and which is unsubstituted or substituted with a radical 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 radical of the formula N(CH3)2, in particular of the formula OR A 3 is a radical represented by: R A 3is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, 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 8 are 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.

[0096] (S2) Formula (S2) [ka] wherein the symbols and indices have the following meanings: R A 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 B 2 OR B 3 , S.R. B 3 Or NR B 3 R B 4or 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 linked to the carbonyl group in (S2) via a nitrogen atom and which is unsubstituted or substituted with a radical 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 radical of the formula N(CH3)2, in particular of the formula OR B 3 is a radical represented by: R B 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, 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 radicals 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 (5-chloro-8-quinolinoxy)acetate 1-methylhexyl ("cloquintocet-mexyl") (S2-1), (5-chloro-8-quinolinoxy)acetate (1,3-dimethyl-but-1-yl) (S2-2), (5-chloro-8-quinolinoxy)acetate 4-allyloxybutyl (S2-3), (5-chloro-8-quinolinoxy)acetate 1-allyloxyprop-2-yl (S2-4), (5-chloro-8-quinolinoxy)acetate ethyl (S2-5), (5-chloro-8-quinolinoxy)acetate methyl (S2-6), (5-chloro-8-quinolinoxy)acetate allyl (S2-7), (5-chloro-8-quinolinoxy)acetate 2-(2-propyl) (5-chloro-8-quinolinoxy)acetic acid 2-oxoprop-1-yl (S2-8), (5-chloro-8-quinolinoxy)acetic acid 2-oxoprop-1-yl (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.

[0097] (S3) Equation (S3) [ka] wherein the symbols and indices are defined as follows: R C 1is (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 compounds of the dichloroacetamide type, which are often used as pre-emergence safeners (soil-acting safeners), such as, for example, "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).

[0098] (S4) Equation (S4) [ka] wherein the symbols and indices are defined as follows: A D is SO2-NR D 3 -CO or CO-NRD 3 -SO2; X D is CH or N; R D 1 is CO-NR D 5 R D 6 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. Dcontaining 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 radical; 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 Dis 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] [During the ceremony, R D 7 is (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] For example, in the above formula, R D 5 = cyclopropyl, and (R D 4 ) = 2-OMe ("cyprosulfamide", S4-1); R D 5 = cyclopropyl, and (RD 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 D 4 ) = 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] [During the ceremony, R D 8 and R D 9 represents 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] 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.

[0099] (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).

[0100] (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).

[0101] (S7) Formula (S7) (which is described in WO-A-1998 / 38856) [ka] 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 3are 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).

[0102] (S8) Formula (S8) (which is described in WO-A-98 / 27049) [ka] [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 radicals 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 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 radicals selected from the group consisting of halogen and alkoxy; A compound or a salt thereof.

[0103] (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.

[0104] (S10) Formula (S10 a ) or formula (S10 b ) (these are described in WO-A-2007 / 0237190 and WO-A-2007 / 023764) [ka] [During the ceremony, R G 1is 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:

[0105] (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.

[0106] (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).

[0107] (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).

[0108] (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.

[0109] (S15) Formula (S15) (which is described in WO-A-2008 / 131861 and WO-A-2008 / 131860) [ka] [During the ceremony, R H 1is a (C1-C6)-haloalkyl radical; 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 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 one side of the ring to a 4-6-membered saturated or unsaturated carbocyclic ring, in which the last four radicals mentioned are each unsubstituted or substituted by one or more radicals 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 4is hydrogen or (C1-C4)-alkyl; or R H 3 and R H 4 represents, together with the nitrogen atom to which it is directly attached, a 4-8 membered heterocyclic ring which, in addition to the nitrogen atom, may 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 radicals 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.

[0110] (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 (lactidichlor-ethyl).

[0111] Particularly preferred safeners are mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl, dichlormid and metcamifen.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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).

[0116] 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.

[0117] 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.

[0118] 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 solid inert materials.

[0119] For the preparation of bread granules, fluid bed granules, extrusion granules and spray granules, reference is made, for example, to the methods described in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; "Agglomeration", J.E. Browning, Chemical and Engineering 1967, pages 147 ff.; and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

[0120] For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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".

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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 recombinant DNA techniques. They can be cultivars, varieties, biotypes and genotypes.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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).

[0164] 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.

[0165] 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).

[0166] 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.

[0167] 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.

[0168] 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).

[0169] 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).

[0170] 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).

[0171] 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.

[0172] 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.

[0173] - Extension of application: A reference to an earlier application in which an extension in scope or duration is being sought.

[0174] - Company: the name of the person submitting the application.

[0175] - Restricted item: the plant species in question.

[0176] - Transgenic phenotype: The trait conferred to a plant by a transformation event.

[0177] - 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.

[0178] - APHIS Documents: Various documents that are relevant to the application and have been published by APHIS or are available from APHIS upon request.

[0179] 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).

[0180] The following examples illustrate the invention. EXAMPLES

[0181] Working Example The present invention will be described in detail by the following examples, which are not intended to limit the present invention in any way.

[0182] A. Synthesis Examples (2R)-2-{[4-bromo-1-(2,5-difluorophenyl)-5-(3,4-difluorophenyl)-1H-pyrazol-3-yl]oxy}propanoic acid methyl ester (I-182)0.40 g (1.01 mmol) of methyl (2R)-2-{[1-(2,5-difluorophenyl)-5-(3,4-difluorophenyl)-1H-pyrazol-3-yl]oxy}propanoate in 14 mL of DMF was added with 0.22 g (1.22 mmol) of N-bromosuccinimide and the mixture was stirred at 65° C. for 1 h. The solvent was removed under reduced pressure, the residue was taken up in water and repeatedly extracted with methylene chloride, the organic phases were combined, dried over sodium sulfate and the solvent was removed under reduced pressure. After purification by silica gel column chromatography with a heptane / ethyl acetate gradient (starting with heptane / ethyl acetate=95:5 and up to heptane / ethyl acetate=50:50 within 20 min), m / z (%)=473 (50) [M + ], 475(50)[M + 0.36 g (71%) of product was obtained with 5,4-dichlorophenyl ether] and specific rotation [α]=+20°.

[0183] 1 H-NMR (400 MHz, CDCl3): δ = 1,57 (d, 3H), 3,69 (s, 3H), 5,15 (q, 1H), 7,18 (m, 1H), 7,36 (m, 2H), 7,50 (m, 3H).

[0184] Synthesis of starting compounds: (a) (2R)-2-{[1-(2,5-difluorophenyl)-5-(3,4-difluorophenyl)-1H-pyrazol-3-yl]oxy}propanoic acid methyl ester0.50 g (1.54 mmol) of 1-(2,5-difluorophenyl)-5-(3,4-difluorophenyl)-1H-pyrazol-3-ol in 31 g of dimethylformamide was added with 0.75 g (2.31 mmol) of cesium carbonate, the mixture was stirred at room temperature for 10 min, 0.23 g (1.85 mmol) of methyl (2S)-2-chloropropanoate was added and the mixture was stirred at 80° C. for another 1 h. The solvent was removed under reduced pressure, the residue was taken up in water and repeatedly extracted with methylene chloride, the organic phases were combined, dried over sodium sulfate and the solvent was removed under reduced pressure. After purification by silica gel column chromatography with heptane / ethyl acetate (starting with heptane / ethyl acetate=95:5 and up to heptane / ethyl acetate=50:50 within 12 min), m / z=395 [M + 0.46 g (72%) of product was obtained with 5,3'-dihydro-1,2'-triazol-2-yl] and specific rotation [α]=+40°.

[0185] 1 H-NMR (400 MHz, CDCl3): δ = 1,63 (d, 3H), 3,78 (s, 3H), 5,18 (q, 1H), 6,03 (s, 1H), 6,91 (m, 1H), 7,08 (m, 4H), 7,16 (m, 1H).

[0186] (b) 1-(2,5-difluorophenyl)-5-(3,4-difluorophenyl)-1H-pyrazol-3-ol To a solution of 4.95 g (9.64 mmol) of N'-(2,5-difluorophenyl)-3-(3,4-difluorophenyl)prop-2-inhydrazide in 10 mL of DMF, 0.15 g (0.77 mmol) of copper(I) iodide was added, and the mixture was stirred at 80° C. for 1 h. After purification by silica gel column chromatography using heptane / ethyl acetate (starting with heptane / ethyl acetate=95:5 and increasing to heptane / ethyl acetate=20:80 within 15 min), m / z=309 [M + 1.06 g (28%) of product having the formula:

[0187] 1 H-NMR (400 MHz, d6 -DMSO): δ = 6,09 (s, 1H), 7,02 (m, 1H), 7,40 (m, 4H), 7,50 (m, 1H), 10,41 (s, 1H).

[0188] (c) N'-(2,5-difluorophenyl)-3-(3,4-difluorophenyl)prop-2-inhydrazide 1.86 g (12.92 mmol) of (2,5-difluorophenyl)hydrazine and 5.94 g (58.75 mmol) of triethylamine were added successively to a solution of 2.14 g (11.75 mmol) of 3-(3,4-difluorophenyl)prop-2-ynoic acid in 20 mL of tetrahydrofuran. 11.22 g (17.62 mmol) of propanephosphonic anhydride (T3P, 50% solution in tetrahydrofuran) were added dropwise and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into water, repeatedly extracted with methyl acetate, the combined organic phases were dried over magnesium sulfate and the solvent was removed under reduced pressure to give 4.97 g (80%) of an oily product (HPLC / MS purity=80%, m / z=309 [M + ]) was obtained, which was further transformed without purification.

[0189] (d) 3-(3,4-difluorophenyl)prop-2-ynoic acid To 5.00 g (20.83 mmol) of 1,2-difluoro-4-iodobenzene in 30 mL of dry tetrahydrofuran under an argon atmosphere were added successively: 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 was stirred at room temperature for 2 hours, the reaction mixture was added to water, 15.00 mL of 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. After purification by silica gel column chromatography using heptane / ethyl acetate (starting with heptane / ethyl acetate = 95:5 and increasing to heptane / ethyl acetate = 40:60 within 15 min), m / z = 183 [M + 2.89 g (76%) of product having the formula:

[0190] 1 H-NMR (400 MHz, d6- DMSO ): δ = 7,56 (m, 2H), 7,86 (m, 1H), 13,95 (bs, 1H).

[0191] (2R)-2-{[4-cyano-1-(2,5-difluorophenyl)-5-(3,4-difluorophenyl)-1H-pyrazol-3-yl]oxy}propanoic acid methyl ester (I-185) A mixture of 0.18 g (0.37 mmol) of methyl (2R)-2-{[4-bromo-1-(2,5-difluorophenyl)-5-(3,4-difluorophenyl)-1H-pyrazol-3-yl]oxy}propanoate (I-182), 0.04 g (0.35 mmol) of zinc cyanide and 0.04 g (0.04 mmol) of tetrakis(triphenylphosphine)palladium in 5 mL of dimethylacetamide was heated to 180° C. for 40 min under argon in a microwave oven. The solvent was removed under reduced pressure, the residue was taken up in water / methylene chloride, the aqueous phase was repeatedly extracted with methylene chloride, 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 a heptane / ethyl acetate gradient (starting with heptane / ethyl acetate = 95:5 and increasing to heptane / ethyl acetate = 60:40 within 15 min), m / z = 420 [M + 0.11 g (67%) of product was obtained with 5,3'-dihydro-1,3'-trimethylsilyl 2,4'-dihydro-1,5 ...

[0192] 1 H-NMR (400 MHz, CDCl3): δ = 1,68 (d, 3H), 3,78 (s, 3H), 5,18 (q, 1H), 7,12 (m, 6H).

[0193] Methyl 2-{[4-chloro-5-(3,5-difluorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}propanoate (I-165): A reaction mixture consisting of 150.0 mg (0.35 mmol) of methyl 2-[(4-chloro-5-iodo-1-phenyl-1H-pyrazol-3-yl)oxy]propanoate, 83.0 mg (0.53 mmol) of (3,5-difluorophenyl)boronic acid, 12.3 mg (0.02 mmol) of bis(triphenylphosphine)palladium(II) dichloride, 228.4 mg (0.70 mmol) of cesium carbonate (2.5 molar in water) and 4.4 mL of 1,2-dimethoxyethane was heated to 80° C. for 3 h. The solvent was removed under reduced pressure, the residue was taken up in water / ethyl acetate, the aqueous phase was repeatedly extracted with ethyl acetate, 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, m / z (%)=393 (76) [M + ], 395(24)[M + 0.11 g (67%) of product having the formula:

[0194] 1 H-NMR (400 MHz, CDCl3): δ = 1,69 (d, 3H), 3,79 (s, 3H), 5,24 (q, 1H), 6,82 (m, 3H), 7,12 (m, 2H), 7,29 (m, 3H).

[0195] Synthesis of starting compounds : (a) Methyl 2-[(4-chloro-5-iodo-1-phenyl-1H-pyrazol-3-yl)oxy]propanoate 10.14 g (37.87 mmol) of diiodomethane and 2.22 g (18.94 mmol) of isopentyl nitrite were added successively to a solution of 2.80 g (9.47 mmol) of methyl 2-[(5-amino-4-chloro-1-phenyl-1H-pyrazol-3-yl)oxy]propanoate in 56 mL of acetonitrile, and the mixture was heated to 50° C. for 30 min. The solvent was removed under reduced pressure, the residue was taken up in water / ethyl acetate, the aqueous phase was repeatedly extracted with ethyl acetate, 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, m / z (%)=407 (76) [M +], 409(24)[M + 2.59 g (64%) of a yellowish solid was obtained having the formula:

[0196] 1 H-NMR (400 MHz, CDCl3): δ = 1,65 (d, 3H), 3,75 (s, 3H), 5,17 (q, 1H), 7,41 (m, 2H), 7,45 (m, 3H).

[0197] (b) 2-[(5-amino-4-chloro-1-phenyl-1H-pyrazol-3-yl)oxy]propanoic acid methyl ester 0.80 g (2.76 mmol) of methyl 2-[(5-amino-1-phenyl-1H-pyrazol-3-yl)oxy]propanoate in 5.0 mL of dimethylformamide was added with 0.44 g (3.31 mmol) of N-chlorosuccinimide and the mixture was stirred at room temperature for 30 min. The solvent was removed under reduced pressure, the residue was taken up in water / methylene chloride, the aqueous phase was repeatedly extracted with methylene chloride, 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, m / z(%)=296(76)[M + ], 298(24)[M + 0.50 g (59%) of a colorless solid was obtained having the formula:

[0198] 1 H-NMR (400 MHz, CDCl3): δ = 1,64 (d, 3H), 3,76 (s, 3H), 3,91 (bs, 2H), 5,20 (q, 1H), 7,30 (m, 1H), 7,45 (m, 4H).

[0199] (c) 2-[(5-amino-1-phenyl-1H-pyrazol-3-yl)oxy]propanoic acid methyl ester0.20 g (1.09 mmol) of 5-amino-1-phenyl-1H-pyrazol-3-ol was dissolved in 5.0 mL of dimethylformamide, to which was added 0.53 g (1.63 mmol) of cesium carbonate, the mixture was stirred at room temperature for 10 min, 0.22 g (1.30 mmol) of methyl 2-bromopropanoate was added, and the mixture was stirred at room temperature for 2 h. The mixture was filtered, the filtrate was concentrated under reduced pressure, and the residue was stirred with dimethyl ether. This gave m / z=262 [M + 0.19 g (64%) of crystalline product was obtained having the formula:

[0200] 1 H-NMR (400 MHz, CDCl3): δ = 1,59 (d, 3H), 3,77 (s, 3H), 3,80 (bs, 2H), 5,16 (q, 1H), 5,20 (s, 1H), 7,26 (m, 1H), 7,45 (m, 2H), 7,49 (m, 2H).

[0201] Methyl {[4-chloro-1-(2-fluorophenyl)-5-(5-fluoro-2-thienyl)-1H-pyrazol-3-yl]oxy}acetate (I-094): 42.0 mg (0.32 mmol) of N-chlorosuccinimide was added in portions to a solution of 85.0 mg (0.24 mmol) of methyl {[1-(2-fluorophenyl)-5-(5-fluoro-2-thienyl)-1H-pyrazol-3-yl]oxy}acetate in 3.2 mL of dimethylformamide, and the mixture was stirred at room temperature for 14 h. The solvent was removed under reduced pressure, the residue was taken up in water / methylene chloride, the organic phase was washed with saturated aqueous sodium bicarbonate and water, the combined aqueous phases were repeatedly extracted with methylene chloride, the combined organic phases were dried over sodium sulfate, and the solvent was removed under reduced pressure. This gave m / z(%)=385(76)[M + ], 387(24)[M + 78 g (67%) of product having the formula:

[0202] 1H-NMR (400 MHz, CDCl3): δ = 3,79 (s, 3H), 4,90 (s, 2H), 6,38 (d, 2H), 6,72 (d, 2H), 7,16 (t, 1H), 7,24 (m, 1H), 7,41 (m, 2H).

[0203] Synthesis of starting compounds : (a) {[1-(2-fluorophenyl)-5-(5-fluoro-2-thienyl)-1H-pyrazol-3-yl]oxy}acetate methyl Under argon, 0.40 g (1.06 mmol) of methyl {[1-(2-fluorophenyl)-5-iodo-1H-pyrazol-3-yl]oxy}acetate was dissolved in 6.1 mL of dioxane, to which was successively added: 37.0 mg (0.05 mmol) of bis(triphenylphosphine)palladium(II) dichloride, 0.24 g (1.06 mmol) of 2-(5-fluoro-2-thienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 0.44 g (3.19 mmol) of potassium carbonate, and 0.4 mL of water. The mixture was heated at reflux for 6 h. The solvent was removed under reduced pressure, the residue was taken up in water / methylene chloride, the aqueous phase was repeatedly extracted with methylene chloride, the combined organic phases were dried over sodium sulfate, and the solvent was removed under reduced pressure. After purification by silica gel column chromatography using heptane / ethyl acetate, m / z(%)=351[M + 0.18 g (38%) of product having the formula:

[0204] 1 H-NMR (400 MHz, CDCl3): δ = 3,80 (s, 3H), 4,84 (s, 2H), 6,06 (s, 1H), 6,31 (d, 2H), 6,45 (d, 2H), 7,18 (t, 1H), 7,28 (m, 1H), 7,44 (m, 2H).

[0205] (b) Methyl {[1-(2-fluorophenyl)-5-iodo-1H-pyrazol-3-yl]oxy}acetate3.67 g (26.54 mmol) of potassium carbonate was added to a solution of 2.69 g (8.85 mmol) of 1-(2-fluorophenyl)-5-iodo-1H-pyrazol-3-ol in 197 mL of acetonitrile, the mixture was stirred at room temperature for 10 min, 1.35 g (8.85 mmol) of methyl bromoacetate was added and the mixture was stirred at reflux for 8 h. The mixture was filtered, the filtrate was concentrated under reduced pressure, the residue was taken up in water / methylene chloride, the aqueous phase was repeatedly extracted with methylene chloride, the combined organic phases were dried over sodium sulfate and the solvent was removed under reduced pressure. After purification by silica gel column chromatography using heptane / ethyl acetate, m / z (%)=377 [M + 1.81 g (54%) of product having the formula:

[0206] 1 H-NMR (400 MHz, CDCl3): δ = 3,78 (s, 3H), 4,80 (s, 2H), 6,18 (s, 1H), 7,22 (m, 2H), 7,39 (m, 1H), 7,45 (m, 1H).

[0207] (c) 1-(2-fluorophenyl)-5-iodo-1H-pyrazol-3-ol 3.82 g (14.61 mmol) of tetra-n-butylammonium fluoride was added to a solution of 4.70 g (11.24 mmol) of 3-{[tert-butyl(dimethyl)silyl]oxy}-1-(2-fluorophenyl)-5-iodo-1H-pyrazole in 105 mL of tetrahydrofuran, and the mixture was stirred at room temperature for 4 h. The solvent was removed under reduced pressure, the residue was taken up in water / ethyl acetate, the aqueous phase was repeatedly extracted with ethyl acetate, 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, m / z (%) = 305 [M + 2.37 g (69%) of product having the formula:

[0208] 1H-NMR (400 MHz, CDCl3): δ = 6,01 (s, 1H), 7,30 (m, 2H), 7,42 (m, 1H), 7,48 (m, 1H), 10,56 (bs, 1H).

[0209] (d) 3-{[tert-butyl(dimethyl)silyl]oxy}-1-(2-fluorophenyl)-5-iodo-1H-pyrazole : Under argon, a solution of 6.00 g (20.52 mmol) of 3-{[tert-butyl(dimethyl)silyl]oxy}-1-(2-fluorophenyl)-1H-pyrazole in 98 mL of tetrahydrofuran was added to a mixture of 1.71 g (26.67 mmol) of n-butyllithium and 2.70 g (26.67 mmol) of diisopropylamine in 98 mL of tetrahydrofuran, and the mixture was stirred at −78° C. for 1 h. A solution of 6.77 g (26.67 mmol) of iodine in 98 mL of tetrahydrofuran was added dropwise, and the mixture was stirred at −78° C. for another 1 h. The mixture was allowed to warm to room temperature, water was added, and repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, and the solvent was removed under reduced pressure. After purification by silica gel column chromatography using heptane / ethyl acetate, m / z (%)=419 [M + 4.72 g (55%) of product having the formula:

[0210] 1 H-NMR (400 MHz, CDCl3): δ = 0,26 (s, 6H), 0,98 (s, 9H), 6,02 (s, 1H), 7,23 (m, 2H), 7,40 (m, 2H).

[0211] (e) 3-{[tert-butyl(dimethyl)silyl]oxy}-1-(2-fluorophenyl)-1H-pyrazole 20.00 g (112.26 mmol) of 1-(2-fluorophenyl)-1H-pyrazol-3-ol was dissolved in 900 mL of dichloromethane, to which 21.05 g (208.1 mmol) of triethylamine and 15.32 g (101.64 mmol) of tert-butyl(chloro)dimethylsilane were added in sequence, and the mixture was stirred at room temperature for 4 hours. The solvent was removed under reduced pressure to give m / z=293 [M +29.60 g (quantitative) of product with 4-aminopropyl ether was obtained, which was further transformed without purification.

[0212] 1 H-NMR (400 MHz, CDCl3): δ = 0,31 (s, 6H), 1,00 (s, 9H), 5,85 (d, 1H), 7,17 (m, 3H), 7,84 (m, 2H).

[0213] Methyl 2-{[4-bromo-5-(4-fluorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}propanoate (I-132) 0.57 g (3.20 mmol) of N-bromosuccinimide was added to a solution of 1.10 g (2.91 mmol) of methyl 2-{[5-(4-fluorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}propanoate in 16 mL of DMF, and the mixture was stirred at 70° C. for 3 h. The solvent was removed under reduced pressure, the residue was taken up in water and repeatedly extracted with methylene chloride, 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, m / z (%)=419 (50) [M + ], 421(50)[M + 1.04 g (81%) of product having the formula:

[0214] 1 H-NMR (400 MHz, CDCl3): δ = 1,69 (d, 3H), 3,79 (s, 3H), 5,26 (q, 1H), 7,07 (m, 4H), 7,22 (m, 5H).

[0215] Synthesis of starting compounds The starting compound was synthesized as described in Example No. I-182.

[0216] 2-{[4-bromo-5-(4-fluorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}propanoic acid (I-138) A mixture of 1.00 g (2.27 mmol) of methyl 2-{[4-bromo-5-(4-fluorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}propanoate (I-132), 0.73 g (18.25 mmol) of 2N sodium hydroxide solution, and 5 mL of tetrahydrofuran was stirred at room temperature for 3 h. The solvent was removed under reduced pressure, and the remaining organic phase was adjusted to pH 2 with 2N HCl. The precipitated solid was dried under reduced pressure at 40° C. to give m / z (%)=405 (50) [M + ], 407(50)[M + 0.90 g (93%) of a colorless solid was obtained having the formula:

[0217] 1 H-NMR (400 MHz, CDCl3): δ = 1,71 (d, 3H), 5,27 (q, 1H), 7,08 (m, 4H), 7,25 (m, 5H).

[0218] Methyl N-(2-{[4-bromo-5-(4-fluorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}propanoyl)glycinate (III-056) Under argon, 0.15 g (0.35 mmol) of 2-{[4-bromo-5-(4-fluorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}propanoic acid (I-138) in 4 mL of tetrahydrofuran was successively added: 2.13 g (1.68 mmol) of 2-methoxy-2-oxoethanaminium chloride, 1.71 g (1.68 mmol) of propanephosphonic anhydride (T3P, 50% solution in tetrahydrofuran), and 0.34 g (3.36 mmol) of triethylamine. The mixture was stirred at 50° C. for 6 h. The solvent was removed under reduced pressure, the residue was taken up in water and repeatedly extracted with methylene chloride, the combined organic phases were dried over sodium sulfate, and the solvent was removed under reduced pressure. After purification by silica gel column chromatography using heptane / ethyl acetate, m / z(%)=478(50)[M + ], 476(50)[M + 0.14 g (79%) of a colorless oil having the formula:

[0219] 1H-NMR (400 MHz, CDCl3): δ = 1,71 (d, 3H), 3,77 (s, 3H), 4,12 (m, 2H), 5,35 (q, 1H), 7,08 (m, 2H), 7,15 (m, 3H), 7,26 (m, 5H).

[0220] NMR Data for Selected Examples : Selected examples of compounds of formula (I) 1 1 H NMR data can be analyzed in two different ways: (a) by conventional evaluation and interpretation of NMR, or (b) by the methods described further below. 1 The results are shown in the form of a H NMR peak list.

[0221] (a) Conventional interpretation of NMR I-094: 1 H-NMR (400 MHz, CDCl3): δ = 3,79 (s, 3H), 4,90 (s, 2H), 6,38 (d, 2H), 6,72 (d, 2H), 7,16 (t, 1H), 7,24 (m, 1H), 7,41 (m, 2H). I-125: 1 H-NMR (400 MHz, CDCl3): δ = 1,70 (d, 3H), 3,79 (s, 3H), 5,23 (q, 1H), 6,88 (m, 1H), 7,0 (m, 3H), 7,17 (m, 2H), 7,27 (m, 1H), 7,40 (m, 1H). I-132: 1 H-NMR (400 MHz, CDCl3): δ = 1,69 (d, 3H), 3,79 (s, 3H), 5,26 (q, 1H), 7,07 (m, 4H), 7,22 (m, 5H). I-138: 1 H-NMR (400 MHz, CDCl3): δ = 1,71 (d, 3H), 5,27 (q, 1H), 7,08 (m, 4H), 7,25 (m, 5H). I-143: 1 H-NMR (400 MHz, CDCl3): δ = 1,28 (t, 3H), 4,27 (q, 2H), 4,98 (s, 2H), 7,11 (m, 5H), 7,33 (t, 1H), 7,40 (m, 1H). I-145: 1 H-NMR (400 MHz, CDCl3): δ = 1,69 (d, 3H), 3,79 (s, 3H), 5,26 (q, 1H), 7,08 (m, 4H), 7,25 (m, 5H). I-165: 1 H-NMR (400 MHz, CDCl3): δ = 1,69 (d, 3H), 3,79 (s, 3H), 5,24 (q, 1H), 6,82 (m, 3H), 7,12 (m, 2H), 7,29 (m, 3H). I-181: 1 H-NMR (400 MHz, CDCl3): δ = 3,81 (s, 3H), 4,91 (s, 2H), 7,00 (m, 3H), 7,13 (m, 3H). I-182: 1 H-NMR (400 MHz, CDCl3): δ = 1,57 (d, 3H), 3,69 (s, 3H), 5,15 (q, 1H), 7,18 (m, 1H), 7,36 (m, 2H), 7,50 (m, 3H). I-183: 1 H-NMR (400 MHz, CDCl3): δ = 3,81 (s, 3H), 4,91 (s, 2H), 7,07 (m, 1H), 7,13 (m, 3H), 7,21 (m, 2H). I-184: 1 H-NMR (400 MHz, CDCl3): δ = 1,67 (d, 3H), 3,77 (s, 3H), 5,22 (q, 1H), 6,98 (m, 1H), 7,02 (m, 1H), 7,12 (m, 2H), 7,17 (t, 1H), 7,32 (m, 2H). I-185: 1 H-NMR (400 MHz, CDCl3): δ = 1,68 (d, 3H), 3,78 (s, 3H), 5,18 (q, 1H), 7,12 (m, 6H). III-056: 1 H-NMR (400 MHz, CDCl3): δ = 1,71 (d, 3H), 3,77 (s, 3H), 4,12 (m, 2H), 5,35 (q, 1H), 7,08 (m, 2H), 7,15 (m, 3H), 7,26 (m, 5H).

[0222] (b) NMR peak list method Selected Examples 1 H NMR data is 1 It may also be shown in the form of a H-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.

[0223] Thus, the peak list for one example takes the following form: δ1(Intensity 1);δ2(Intensity 2);...;δ i (strength i );...;δ n (strength n ).

[0224] 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.

[0225] 1 To calibrate the chemical shifts of the H-NMR spectra, tetramethylsilane is used and / or, especially if the spectrum is measured in DMSO, the chemical shifts of the solvent are used, and thus, in the NMR peak list, the tetramethylsilane peaks can be, but do not have to be, present.

[0226] 1 The list of H NMR peaks is given in the conventional 1 It resembles a 1 H NMR printout and therefore contains all the peaks that would normally be described in a conventional NMR interpretation.

[0227] Furthermore, they are 1 Like the 1 H NMR printout, signals of the solvent, signals of stereoisomers of the target compound (which are likewise provided by the present invention) and / or signals of impurity peaks may also be shown.

[0228] In recording compound signals within the delta range of the solvent and / or water, 1 Our list of H NMR peaks shows standard solvent peaks, e.g., DMSO peaks in DMSO-D6, and water peaks, which usually have high intensity on average.

[0229] 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%).

[0230] 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 methods in terms of "by-product fingerprints".

[0231] 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.

[0232] 1 Further details regarding the 1 H NMR peak list can be found in Research Disclosure Database Number 564025.

[0233] [Table 4] TIFF0007631346000037.tif239165TIFF0007631346000038.tif236165TIFF0007631346000039.tif241166TIFF0007631346000040.tif231166TIFF0007631346000041.tif242166TIFF0007631346000042.tif234165TIFF0007631346000043.tif237165TIFF0007631346000044.tif240165TIFF0007631346000045.tif238167TIFF0007631346000046.tif241166TIFF0007631346000047.tif241165TIFF0007631346000048.tif237165TIFF0007631346000049.tif232166TIFF0007631346000050.tif228166TIFF0007631346000051.tif237165TIFF0007631346000052.tif237165TIFF0007631346000053.tif240166TIFF0007631346000054.tif237165TIFF0007631346000055.tif239165TIFF0007631346000056.tif240164TIFF0007631346000057.tif236165TIFF0007631346000058.tif229165TIFF0007631346000059.tif238166TIFF0007631346000060.tif230166TIFF0007631346000061.tif229166

[0234]

Table 5

[0235] [Table 6] TIFF0007631346000068.tif241163TIFF0007631346000069.tif231164TIFF0007631346000070.tif241165TIFF0007631346000071.tif239166TIFF000 7631346000072.tif234163TIFF0007631346000073.tif240164TIFF0007631346000074.tif229164TIFF0007631346000075.tif237163TIFF0007631346 000076.tif236164TIFF0007631346000077.tif239163TIFF0007631346000078.tif239164TIFF0007631346000079.tif241163TIFF0007631346000080. tif235163TIFF0007631346000081.tif238164TIFF0007631346000082.tif234165TIFF0007631346000083.tif227164TIFF0007631346000084.tif19161

[0236] 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.

[0237] (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.

[0238] (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.

[0239] (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.

[0240] (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.

[0241] (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.

[0242] C. Biological Examples 1. Pre-emergence herbicidal activity and crop plant compatibility Seeds of monocotyledonous and dicotyledonous weed plants are placed in sandy loam in plastic pots (one type of monocotyledonous or dicotyledonous weed plant is sown twice per pot) and covered with soil. The surface of the covered soil is then 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 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.

[0243] In Tables 4.1-4.15 and 5.1-5.16 below, the following abbreviations are used: [Table 7]

[0244] The following Tables 4.1 to 4.15 show the effects of selected compounds of general formula (I) as described in Tables 1 to 3 against various harmful plants at application rates equivalent to 1280 g / ha or 320 g / ha, obtained by the above experimental method.

[0245] [Table 8]

[0246]

Table 9

[0247]

Table 10

[0248]

Table 11

[0249]

Table 12

[0250]

Table 13

[0251]

Table 14

[0252]

Table 15

[0253]

Table 16

[0254]

Table 17

[0255]

Table 18

[0256]

Table 19

[0257]

Table 20

[0258]

Table 21

[0259]

Table 22

[0260] As shown by the above results, the compounds of the present invention, e.g., compound Nos. I-002, I-003, I-008, I-021, I-022, I-056, I-057, I-061, I-067, I-069, I-070, I-072, I-121, I-125, I-138, I-139, II-013, III-003, III-022, III-027, III-053, III-069 and other compounds in Tables 4.1-4.15, show good herbicidal activity against harmful plants when applied pre-emergence. For example, compounds Nos. I-008, I-056, I-057, I-061, I-067, I-070 and I-072 applied by the pre-emergence method show very good activity (80% to 100% herbicidal activity) against harmful plants such as Alopecurus myosuroides, Amaranthus retroflexus, Matricaria inodora, Polygonum convolvulus, Setaria viridis and Stellaria media at application rates of up to 1.28 kg of active substance per hectare.

[0261] 2. Post-emergence herbicidal activity and crop plant compatibility Seeds of monocotyledonous and dicotyledonous weed plants are placed in sandy loam in plastic pots (one pair of monocotyledonous or dicotyledonous weed plants per pot), 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 equivalent to 600 L / ha. 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.

[0262] Tables 5.1 to 5.16 below show the effects of selected compounds of general formula (I) as described in Tables 1 to 3 against various harmful plants at application rates equivalent to 1280 g / ha or 320 g / ha, obtained by the above experimental method.

[0263] [Table 23]

[0264] [Table 24]

[0265] [Table 25] TIFF0007631346000113.tif34156

[0266] [Table 26]

[0267] [Table 27] TIFF0007631346000116.tif39155

[0268] [Table 28] TIFF0007631346000118.tif253153TIFF0007631346000119.tif116155

[0269] [Table 29]

[0270] [Table 30] TIFF0007631346000122.tif253154TIFF0007631346000123.tif40153

[0271]

Table 31

[0272]

Table 32

[0273]

Table 33

[0274]

Table 34

[0275]

Table 35

[0276]

Table 36

[0277]

Table 37

[0278]

Table 38

[0279] As shown by the results in Tables 5.1-5.16, the compounds of the present invention exhibit good post-emergence herbicidal activity against a wide range of grass and weed species.

[0280] As shown by the above results, the compounds of the present invention, e.g., Compound Nos. I-002, I-003, I-006, I-014, I-021, I-054, I-072, II-04, III-058 and other compounds in Tables 5.1-5.16, show very good herbicidal activity against harmful plants when applied post-emergence. For example, compounds Nos. I-002, I-006, I-022, I-056 and I-072 applied by the post-emergence method show very good activity (80% to 100% herbicidal activity) against harmful plants such as Alopecurus myosuroides, Amaranthus retroflexus, Matricaria inodora, Setaria viridis, Pharbitis purpurea and Stellaria media at application rates of up to 1.28 kg of active substance per hectare.

Claims

1. General formula (I) 【Chemistry 1】 [During the ceremony, A is A1-A3 【Chemistry 2】 selected from the group consisting of: R １ teeth, ・OR １ａ and ・NR ９ R １０ ; wherein: R １ａ teeth, hydrogen; Methyl, ethyl [which is unsubstituted or substituted with halogen, (C ３ -C ６ )-cycloalkyl, (C １ -C ４ )-trialkylsilyl, (C １ -C ６ )-substituted with one or more substituents selected from the group consisting of alkoxy, cyano and nitro; ・ (C ２ -C ６ )-alkenyl, (C ２ -C ６ )-haloalkenyl; ・ (C ２ -C ６ )-alkynyl; ・ (C ３ -C ６ )-cycloalkyl [which is unsubstituted or substituted with halogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl; ・ (C １ -C ４ )-alkyl-SO-(C １ -C ４ )-alkyl, (C １ -C ４ )-Alkyl-SO ２ - (C １ -C ４ )-alkyl; Heterocyclyl, heteroaryl and aryl, which are unsubstituted or substituted with halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl; Heterocyclyl (C １ -C ４ )-alkyl, heteroaryl-(C １ -C ４ )-alkyl and aryl-(C １ -C ４ )-alkyl, wherein the heterocyclyl, heteroaryl and aryl are unsubstituted or substituted with halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl; selected from the group consisting of: R ９ is hydrogen, (C １ -C １２ )-alkyl; R １０ teeth, hydrogen; Aryl, heteroaryl, heterocyclyl [which is unsubstituted or is selected from the group consisting of halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl; ・ (C ３ -C ７ )-cycloalkyl-(C １ -C ４ )-alkyl, heterocyclyl-(C １ -C ４ )-alkyl, heteroaryl-(C １ -C ４ )-alkyl, aryl-(C １ -C ４ )-alkyl, aryl-(C １ -C ４ )-alkoxy, wherein the cycloalkyl, heterocyclyl, heteroaryl and aryl are unsubstituted or substituted with halogen, (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl; ・ (C １ -C １２ )-alkyl; (C ３ -C ８ )-cycloalkyl, (C ２ -C １２ )-alkenyl, (C ５ -C ８ )-cycloalkenyl, (C ２ -C １２ )-alkynyl, wherein the alkyl, cycloalkenyl, alkenyl, cycloalkenyl and alkynyl radicals are unsubstituted or substituted with cyano, nitro, OR ５ , S(O) ｎ R ５ , S.O. ２ N.R. ６ R ７ , C(O)OR 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 radicals selected from the group consisting of: ・ (C １ -C １２ )-haloalkyl; ・ S (O) ｎ R ５ , cyano, nitro, OR ５ , S.O. ２ N.R. ６ R ７ , CO ２ R ８ , C.O.R. ８ , N.R. ６ R ８ , N.R. ６ C.O.R. ８ , N.R. ６ CO ２ R ８ , N.R. ６ SO 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 not further substituted by halogen, (C １ -C ６ )-alkyl, halo-(C １ -C ６ )-alkyl, 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 the ring may be substituted with 1 to 6 radicals selected from the group consisting of, in addition to the nitrogen atom, r carbon atoms, o oxygen atoms, p sulfur atoms, and NR ７ , CO and NCOR ７ comprising 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 aryl; R ６ is hydrogen or R ５ and 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 ２ａ teeth, hydrogen; methyl; selected from the group consisting of: R ２ｂ is hydrogen; R ３ teeth, ・Halogen, cyano, isocyano, NO ２ ; ・ (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl, (C １ -C ６ )-alkylcarbonyl, (C １ -C ６ )-haloalkylcarbonyl, (C １ -C ４ )-alkyloxycarbonyl; ・ (C ２ -C ３ )-alkenyl, (C ２ -C ３ )-haloalkenyl; ・ (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl; ・ (C １ -C ２ )-alkyl-S(O) ｎ And (C １ -C ２ )-haloalkyl-S(O) ｎ ; CHO; ・ NH ２ ; selected from the group consisting of: R ４ is phenyl, wherein the phenyl radical is unsubstituted or - halogen, cyano, isocyano, nitro; ・ (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, (C １ -C ３ )-haloalkoxy; ・ (C ２ -C ３ )-alkenyl, (C ２ -C ３ )-haloalkenyl, (C １ -C ６ )-alkoxy; ・ (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl, (C １ -C ４ )-alkyl-S(O) ｎ ; ・ CHO, (C １ -C ４ )-alkyloxycarbonyl and NH ２ and wherein the radicals are selected from the group consisting of: R １２ teeth, ・Halogen, cyano, isocyano, 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 ４ )-alkyloxycarbonyl, (C １ -C ６ )-alkoxy, (C １ -C ３ )-haloalkoxy, (C １ -C ４ )-alkyl-S(O) ｎ ; ・ (C ２ -C ３ )-alkenyl, (C ２ -C ３ )-haloalkenyl; ・ (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl; ・ NH ２ ; selected from the group consisting of: and where the subscripts are as follows: 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; and s is 0, 1, 2, 3, 4 or 5. or an agriculturally acceptable salt thereof; However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenyl-pyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

2. A is A1-A3 【Chemistry 3】 selected from the group consisting of: R １ teeth, ・OR １ａ and ・NR ９ R １０ ; wherein: R １ａ teeth, hydrogen; Methyl, ethyl [which is unsubstituted or substituted with halogen, (C ３ -C ６ )-cycloalkyl, (C １ -C ４ )-trialkylsilyl, (C １ -C ４ )-substituted with one or more substituents selected from the group consisting of alkoxy, cyano and nitro; ・ (C ２ -C ６ )-alkenyl, (C ２ -C ６ )-haloalkenyl; Aryl-(C １ -C ４ )-alkyl, wherein the aryl is unsubstituted or is selected from the group consisting of halogen, (C １ -C ４ )-alkyl, (C １ -C ４ )-haloalkyl; selected from the group consisting of: R ９ is hydrogen, (C １ -C ６ )-alkyl; R １０ teeth, hydrogen; ・ (C ３ -C ７ )-cycloalkyl-(C １ -C ４ )-alkyl, aryl-(C １ -C ４ )-alkyl, aryl-(C １ -C ４ )-alkoxy, wherein the cycloalkyl and aryl are unsubstituted or substituted with halogen, (C １ -C ４ )-alkyl, (C １ -C ４ )-haloalkyl; ・ (C １ -C ６ )-alkyl, (C ２ -C ６ )-alkenyl, (C ２ -C ６ )-alkynyl; (C ３ -C ８ )-cycloalkyl, wherein the alkyl, alkenyl, alkynyl and cycloalkenyl radicals are unsubstituted or substituted with cyano, C(O)OR ８ each independently substituted with m radicals selected from the group consisting of: ・ (C １ -C ６ )-haloalkyl; selected from the group consisting of: R ８ is hydrogen, (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl; R ２ａ teeth, hydrogen; methyl; selected from the group consisting of: R ２ｂ is hydrogen; R ３ teeth, ・ Fluorine, chlorine, bromine, iodine, cyano, isocyano, NO ２ ; ・ (C １ -C ６ )-alkyl, (C ３ -C ６ )-cycloalkyl, (C １ -C ６ )-haloalkyl, (C １ -C ４ )-alkyloxycarbonyl; ・ (C ２ -C ３ )-alkynyl, (C ２ -C ３ )-haloalkynyl; selected from the group consisting of: R ４ is phenyl, wherein the phenyl radical is unsubstituted or Fluorine, chlorine, bromine; methyl, ethyl; - methoxy, ethoxy; and wherein the radicals are selected from the group consisting of: R １２ teeth, - halogen, cyano, nitro; ・ (C １ -C ６ )-alkyl, (C １ -C ６ )-haloalkyl, (C １ -C ３ )-haloalkoxy; ・ (C １ -C ６ )-alkoxy; selected from the group consisting of: and where the subscripts are as follows: m is 0, 1 or 2; s is 0, 1, 2, 3; 2. A compound of formula (I) according to claim 1 or an agriculturally acceptable salt thereof; However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenyl-pyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

3. A is A1 【Chemistry 4】 and R １ teeth, ・OR １ａ and ・NR ９ R １０ ; wherein: R １ａ teeth, hydrogen; methyl, ethyl, trimethylsilylmethyl; 1-propenyl, 2-propenyl; benzyl, 1-phenylethyl, 2-phenylethyl, where the phenyl radical in each of the three groups named is unsubstituted or substituted with a halogen; selected from the group consisting of: R ９ is hydrogen; R １０ teeth, hydrogen; cyclopropylmethyl; benzyl, 1-phenylethyl, 2-phenylethyl, benzyloxy, in which the phenyl radical in each of the four groups named is unsubstituted or substituted with a halogen; 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, wherein the radicals are unsubstituted or C(O)OR ８ each independently being monosubstituted with a radical; Cyclopropyl, cyclobutyl, cyclopentyl, where the three radicals mentioned are unsubstituted or C(O)OR ８ each independently being monosubstituted with a radical; 1-propenyl, 2-propenyl, 2-methyl-2-propenyl, prop-2-yn-1-yl, but-2-yn-1-yl; selected from the group consisting of: R ８ is hydrogen, methyl, ethyl; R ２ａ teeth, hydrogen; methyl; selected from the group consisting of: R ２ｂ is hydrogen; R ３ teeth, ・ Fluorine, chlorine, bromine, iodine, cyano, NO ２ ; trifluoromethyl; ethynyl; C(O)Omethyl; selected from the group consisting of: R ４ is phenyl, wherein the phenyl radical is unsubstituted or Fluorine, chlorine, bromine; methyl, ethyl; - methoxy, ethoxy; and wherein the radicals are selected from the group consisting of: R １２ teeth, Fluorine, chlorine, NO ２ ; - trifluoromethyl, methoxy, ethoxy; selected from the group consisting of: and where the subscripts are as follows: s is 1, 2, 3; 3. A compound of formula (I) according to claim 1 or 2 or an agriculturally acceptable salt thereof; However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenyl-pyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

4. A is A1 【Chemistry 5】 and R １ teeth, ・OR １ａ and ・NR ９ R １０ ; wherein: R １ａ teeth, hydrogen; methyl, ethyl; 2-propenyl; selected from the group consisting of: R ９ is hydrogen; R １０ teeth, ・ C(O)OR ８ cyclopentyl monosubstituted with; cyclopropylmethyl; ・ CH ２ C(O)OR ８ 、CH ２ CH ２ C(O)OR ８ ; 2-propenyl, prop-2-yn-1-yl; selected from the group consisting of: R ８ is hydrogen, methyl, ethyl; R ２ａ teeth, hydrogen; methyl; selected from the group consisting of: R ２ｂ is hydrogen; R ３ teeth, Chlorine, bromine, iodine, cyano, NO ２ ; selected from the group consisting of: R ４ is phenyl, wherein the phenyl radical is unsubstituted or fluorine, chlorine; and wherein the radicals are selected from the group consisting of: R １２ teeth, fluorine, chlorine; selected from the group consisting of: and where the subscripts are as follows: s is 1, 2; A compound of formula (I) according to any one of claims 1 to 3 or an agriculturally acceptable salt thereof; However, the following compounds are excluded: [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]acetic acid, {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, [(4-chloro-1,5-diphenyl-1H-pyrazol-3-yl)oxy]ethyl acetate {[4-chloro-5-(4-methylphenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}acetic acid, ethyl, {[4-chloro-5-(3-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl]oxy}ethyl acetate, 2-(4-chloro-1,5-diphenyl-pyrazol-3-yl)oxypropanoic acid, 2-(4-bromo-1,5-diphenylpyrazol-3-yl)oxypropanoic acid.

5. A method for preparing a compound of general formula (Ia) or an agrochemically acceptable salt thereof according to any one of claims 1 to 4, comprising reacting a compound of general formula (II) with a compound of general formula (III) to produce a compound of general formula (IV), which is then reacted with a compound of general formula (V) to produce a compound of formula (Ia): 【Chemistry 6】 【change】 Here, R ４ , R ２ａ , R ２ｂ , R １ａ , R ３ and A has the definition given above, and X is chlorine, bromine or iodine.

6. A method for preparing a compound of formula (Ib) or an agriculturally acceptable salt thereof according to any one of claims 1 to 4, comprising reacting a compound of general formula (Ia) ４ , R ２ａ , R ２ｂ , R １ａ , R ３ and A has the definition given above] with a compound of formula (VI) to give a compound of formula (Ib): 【Chemistry 7】

7. 1. An agrochemical composition comprising (a) at least one compound of formula (I) as defined in one or more of claims 1 to 4 or a pesticidally acceptable salt thereof, and (b) adjuvants and additives customary in crop protection.

8. 1. A pesticide composition comprising: (a) at least one compound of formula (I) as defined in one or more of claims 1 to 4 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:

9. 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 one or more of claims 1 to 4 or an agronomically acceptable salt thereof to the plants, to the seeds or to the area in which the plants are growing.

10. Use of a compound of formula (I) as defined in one or more of claims 1 to 4 or an agriculturally acceptable salt thereof as a herbicide or plant growth regulator.

11. 11. Use according to claim 10, wherein the compounds of formula (I) or their agriculturally acceptable salts are used for controlling harmful plants or for regulating the growth in crop plants.

12. The use according to claim 11, wherein the crop plant is a transgenic crop plant or a non-transgenic crop plant.

Images