MXPA97009955A

MXPA97009955A - Derivatives of the acid 5-pirazolilbenzo

Info

Publication number: MXPA97009955A
Application number: MXPA/A/1997/009955A
Authority: MX
Inventors: Misslitz Ulf; Klintz Ralf; Heistracher Elisabeth; Zagar Cyrill; Hamprecht Gerhard; Schafer Peter; Von Dem Christophsweder; Busschehunnefeld; Otto Wetphalen Karl
Original assignee: Basf Ag 67063 Ludwigshafen De
Priority date: 1995-07-06
Filing date: 1997-12-09
Publication date: 1998-10-15

Abstract

The present invention relates to: I derivatives of 5-pyrazolylbenzoic acid: wherein: R1 is H, C1-C4 alkyl, cyano-C1-C4 alkyl, halo-C1-C4 alkyl, R2 is C1-C4 alkoxy, alkyl -C1-C4-thio, haloalkoxy-C1-C4, or haloalkyl-C1-C4-thio, R3 is H, CN, NO2, halogen, R4 is halogen, R5 is CN, halogen, C1-C4 alkyl, haloalkyl- C1-C4, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy, R 6 is -O-R 7, -S-R 7, -N (R 8) -R 7 or -N (R 8) -O-R 7; R 7 is - XC (R9) = N-OR10, -XC (R9) = NOZ-R10; -XON = C (R11, R12), -X-SO2-R13 or hetercyclyl, unsubstituted or substituted, from 3 to 7 members, or heterocyclyl -alkyl-C1-C4, the heterocycle contains, in addition to methylene members, one to three ring members, selected from the group consisting of three aza bridges and two oxygen or sulfur bridges, and, if desired, it is possible, that one or two methylene groups of the heterocycle are replaced by -CO-, -CS- and / or -SO2-; R8 is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C5 alkenyl, haloalkenyl- C3-C5, C3-C5 alkynyl, C1-C4 alkylsulfonyl, R9 is H, CN, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio; R 10 is H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 cyanoalkyl, di (C 1 -C 4 alkyl) C4) amino-C1-C4 alkyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkyl-thio-C1-C4 alkyl, (C1-C4 alkyl) carbonyl, (C1-6 alkoxy) C4) carbonyl, di (C1-C4 alkyl) -aminocarbonyl, C1-C4 haloalkyl) carbonyl, C3-C5 alkenyl, C3-C5 haloalkenyl, di (C1-C4 alkyl) amino-C3-C5 alkenyl , C 1 -C 4 alkoxy-C 3 -C 5 alkenyl, C 1 -C 4 alkylthio-C 3 -C 5 alkenyl, C 3 -C 5 alkynyl, C 3 -C 5 haloalkynyl, C 3 -C 7 cycloalkyl, unsubstituted or substituted, phenyl , benzoyl or a 5-6 membered heteroaryl, having 1 to 3 heteroatoms, R 11, R 12, are H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 3 alkenyl -C5, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 haloalkynyl, C3-C7 cycloalkyl, unsubstituted or substituted, or phenyl, or R11 + R12 together with the carbon atom to which they are attached, form a saturated ring of 3 to 8 members, which, if desired, may also contain Methylene members, one or two oxygens, sulfur and / or aza ring members; R 13 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 cyanoalkyl, di (C 1 -C 4 alky) amino- ( C 1 -C 4 alkyl), C 1 -C 4 alkoxy-C 1 -C 4 alkyl), C 1 -C 4 alkylthio-C 1 -C 4 alkyl, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, di (C 1 -C 4 alkyl) C4) -C3-C5-alkenyl-alkyloxy-C1-C4-alkenyl-C3-C5 alkylthio-C1-C4-alkenyl-C3-C5), C3-C5 alkynyl, C3-C5 haloalkynyl, cycloalkyl- C3-C7, unsubstituted or substituted, phenyl or a 5-6 membered heteroaryl, having 1-3 heteroatoms; X, Z is a C1-C4 alkylene chain, unsubstituted or substituted, and its salts are used as herbicides; / defoliate plant

Description

ACID DERIVATIVES 5-PIRAZOLILBENZ01CO The present invention relates to novel 5-pyrazolylbenzoic acid derivatives of the formula I: where the variables have the following meanings: R 1 is hydrogen, C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, R 2 is C 1 -C 4 alkoxy, C 1 alkyl C4-thio, haloalkoxy-C? -C4, or haloalkyl-C? -C4thio; R3 is hydrogen, cyano, nitro, halogen; R4 is halogen; R 5 is cyano, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy; R6 is -0-R7, -S-R7, -N (R8) -R7 or -N (R8) -0-R7; R7 is -X-C (R9) = N-0-R10, -X-C (R9) = N-0-Z-R10; -X-0-N = C (R1: L, R12), -X-SO2-R13 or saturated heterocyclyl of 3 to 7 members, or heterocyclyl-C-C4 alkyl; where the heterocycium contains, in addition to methylene members, one to three ring members, selected from the group consisting of three aza bridges and two oxygen or sulfur atoms, and, if desired, one or two groups of methylene of the heterocycle are replaced by carbonyl, thiocarbonyl and / or sulfonyl, it is also possible that the heterocycle is unsubstituted or has attached thereto one to four substituents, each selected from the group consisting of halogen, C1-alkyl- C4, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkylcarbonyloxy Y (C 1 -C 4 alkylcarbonylamino; R 8 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, C 3 -C 5 alkynyl, C 1 -C 4 alkylsulfinyl; R 9 is hydrogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio; R10 is hydrogen, C1-C-alkyl, C1-C4 haloalkyl, C1-C-cyanoalkyl, di (C1-C4 alkyl) amino-C1-C-alkyl, C1-C4-alkoxy-C1-C-alkyl , C1-C-alkyl-thio-C1-C4 alkyl, (C1-C4 alkyl) carbonyl, (C1-C4 alkoxy) carbonyl, di (C1-C4 alkyl) -aminocarbonyl, C1-C haloalkyl) carbonyl, C3-C5 alkenyl, C3-C5 haloalkenyl, di (C1-C4 alkyl) C3-C5 aminoalkenyl, C1-C4 alkylthio-C3-C5 alkenyl, C3-C5 alkynyl, haloalkynyl- C3-C5, C3-C7 cycloalkyl, which, if desired, can be attached to one to three C alquilo-C3 alkyl radicals, or is phenyl, benzoyl, or 5- or 6-membered heteroaryl, which contains one to three heteroatoms, selected from the group consisting of three nitrogen and one oxygen or sulfur atoms, it being possible for the phenyl and heteroaryl rings to be unsubstituted or have attached to each substitutable ring member one of the following substituents: nitro, cyano, halogen, C 1 -C 4 alkyl, haloalkyl C 1 R 11, R 12, independently yes, they are hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 alkyloxy-C 3 -C 5 -alkyl, C 3 -C 5 -haloalkenyl, C 3 -C 5 alkynyl, C3-C5 haloalkynyl, C3-C7 cycloalkyl, which, if desired, can be attached to one or three C alquilo-C3 alkyl radicals, or they are phenyl, which, if desired, can be attached to each non-substitutable ring member one of the following substituents: nitro, cyano, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy, or R 11 and R 12 together with the carbon atom attached to the which they join, they form a saturated ring of 3 to 8 members, which, if desired, may also contain methylene members, one or two oxygens, sulfur and / or aza ring members, it being possible for the ring to be replace or have attached to it one to four C1-C4 alkyl radicals, * R 13 is C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 4 -C 4 -cyanoalkyl, di (C 1 -C 4 -alkyl) amino- (C 1 -C 4 -alkyl), C 2 -C 4 -alkoxy C 1 -C 4 alkyl), C 1 -C 4 alkylthio-C 1 -C 4 alkyl, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, di (C 1 -C 4 alkyl) amino-C 3 -C 5 alkenyl, alkoxy- C 1 -C 4 -C 3 -C 5 alkenyl, C 1 -C 4 -alkyl-C 3 -C 5 alkenyl, C 3 -C 5 alkynyl, C 3 -C 5 -haloalkynyl, C 3 -C 7 -cycloalkyl, which, if desired, can have linked to three C-C3-alkyl radicals, or is phenyl, or is 5- or 6-membered heteroaryl, which contains one to three heteroatoms, selected from the group consisting of three nitrogen atoms and one oxygen atom or of sulfur, it being possible that the phenyl and the heteroaryl ring are unsubstituted or have attached to each substitutable ring member one of the following substituents: nitro, cyano, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy; X and Z, independently of each other, are alkylene-cl ~ c4 'chains which may be unsubstituted or may have attached thereto one to four substituents, each selected from the group consisting of halogen, C-alkyl? ~ C4, haloalkyl-C? -C4 and alkoxy-C? ~ C4; and the salts useful in the agriculture of the compounds I. Also, the invention relates to the use of these compounds as herbicides, to the herbicidal compositions comprising the compounds I as active ingredients, to processes for the preparation of these herbicidal compositions and to methods for controlling undesirable vegetation with the use of the compounds I. The patents WO 92/06 962, EP-A 361 114 and EP-A 443 059, already describe 3-phenylpyrazoles of the type of compounds I having an ester, thioester or acid amide group on the phenyl ring in the meta position relative to the pyrazole radical. Likewise, Japanese patent JP-A 03/151 367 discloses that the compounds of formula II: lower alkyl wherein Ra is, inter alia, -C (Rb2CORc, -CH = CH-COTd or -C (COR * e) = CHRf and Rb is hydrogen or lower alkyl, Rc is hydroxyl, lower alkoxy or lower alkylthio, Rd is lower alkyl, lower alkoxy or lower alkenyloxy, Re is lower alkoxy or lower alkenyloxy and Rf is hydroxy or lower alkoxy, are herbicidally active Also, Japanese patent JP 06/199 805 also discloses that the compounds of the formula Illa: (halogen) hydrogen or lower alkyl where R9 is, inter alia, carboxyl, lower alkoxycarbonyl or lower alkyl-thiocarbonylalkoxycarbonyl, and European patent EP-A 447 055 discloses that the compounds of the formula Illb: IIIb They are suitable as herbicides. EP-A 619 946 discloses synergistic herbicidal compositions comprising 3-phenylpyrazole derivatives of the formula lile: I C ^ -Cg-alkyl where Rn is hydrogen, C 1 -Cg alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haoalkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl. EP-A 647 399 describes an aqueous, pesticidally active suspension of certain 3-phenylpyrazoles, compounds, among others, of the formula Illd: where R1 is Ci-Cg-alkyl, Ci-Cg-haloalkyl, C2-C6-alkenyl, or -CHIH / C ^ -alkyl-Ce-J-CO-JO / SJ-Rk, where Rk hydrogen, C-alkyl -Cg, haloalkyl-Ci-Cg, C2-Cg-alkenyl or C2-Cg alkynyl. Likewise, patent WO 92/02509 describes certain phenylpyrazoles as herbicidally active ingredients, which may have attached to them in the phenyl ring a group of ester, thioester or acid amide, among others, and in the pyrazole ring an alkyl group. C? -C5-sulfonyl or alkyl-C? ~ C5-sulfonyl substituted by halogen, among others. A suitable selection of substituents allows the precursors of these compounds to be constructed with alkylthio or haloalkylthio in the pyrazole ring and which belongs to the same type as the present compounds I. Finally, patent WO 95/30661 discloses phenylthiocarboxamidase, which can have attached to them in the phenyl ring in the ortho position in relation to the thiocarboxamide group, an ester, thioester or acid amide group, among others, and in the position for a pyrazol-3-yl ring, among others, for use as herbicides. An appropriate selection of substituents will give the corresponding cyanophenyl precursors of these compounds, which are of the same type as the 5-pyrazolylbenzoic acid derivatives I, where R5 = cyano. However, the herbicidal properties of the known herbicides are no longer always completely satisfactory in relation to weeds. Therefore, it is an object of the present invention to provide novel compounds, in particular herbicidally active compounds, with which objective control of the unwanted plants can be carried out, better than previously possible. Another object is to provide novel compounds that act as desiccants / defoliants.

Therefore, we have found that this object is achieved by the present 5-pyrazolylbenzoic acid derivatives of the formula I and their herbicidal action. It has also been found that the herbicidal compositions comprising the compounds I have a very good herbicidal action. Likewise, processes have been found for the preparation of these compositions and methods for controlling unwanted vegetation with the use of the compounds I. Likewise, it has been found that the compounds I are also suitable for the defoliation and desiccation of parts of the plants, suitable plants being crop plants, such as cotton, potatoes, oil and turnip seed, sunflower, soybeans or field grains, particularly cotton. In this regard, it has been found that the compositions for desiccating and / or defoling the plants, processes for the preparation of these compositions and methods for desiccating and / or defoling plants with the use of the compounds I. Depending on the substitution pattern, the compounds of formula I may contain one or more chiral centers, in which case they are present in the form of mixtures of enantiomers or diastereomers. The invention relates to pure enantiomers or diastereomers and also to mixtures thereof.

Suitable salts useful in agriculture are, in particular, the salts of sos cations or the acid addition salts of those acids whose cations, or anions, respectively, do not adversely affect the herbicidal action of the compounds I. Thus, particularly suitable cations are the alkali metal ions, preferably sodium and potassium, of alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion, which, if desired, it can be attached to one or all four C 1 -C 4 alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, triraethylbenzylammonium, also phosphonium ions, sulfonium ions, preferably the tri (C 1 -C 4 alkyl) sulfonium, and suloxonium ions, preferably tri (C 1 -C 4 alkyl) sulfoxonium. Anions of acid addition salts useful with mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogencarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of alkalic acid-C? C4, preferably the format, acetate, propionate and butyrate.

The organic parts mentioned for the substituents of R1 to R3, R5 and R7 to R13 or as radicals in alkylene chains, phenyl rings or heterocycles represent collective terms for individual enumerations of the members of individual groups. All carbon chains, ie, all alkyls, cyanoalkyls, haloalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylcarbonylamino, alkenyl, haloalkenyl, alkynyl, haloalkynyl and alkylsulfonyl, can be straight chain or branched Unless otherwise specified, halogenated substituents are preferably attached to one to five identical or different halogen atoms. The halogen, in each case, represents fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine. Additional examples of meanings are: C 1 -C 3 -alkyl: methyl, ethyl, n-propyl or 1-methylethyl, in particular methyl; • C 1 -C 4 alkyl and alkyl portions of (C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkylcarbonyloxy, C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxy alkyl) C 1 -C 4, C 1 -C 4 alkylthio-C 1 -C 4 alkyl, di (C 1 -C 4 alkyl) -aminocarbonyl, di (C 1 -C 4 alkyl) amino-C 1 -C 4 alkyl and di (C-alkyl) ? -C4) C3-C5 amino-alkenyl; methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl, in particular methyl or ethyl; • C 1 -C 4 alkylene: methylene, ethan-1, 2-diyl, propan-1,2-diyl, propan-1,3-diyl, butan-1, 2-diyl, butan-1,3-diyl, butan-1, 4-diyl or butan-2,3-diyl; • haloalkyl-C1-C4 and the haloalkyl part of (haloalkyl-C? -C4) carbonyl; a C 1 -C 4 alkyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluorophenyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoro- methyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 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, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2, 3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4- chlorobutyl, 4-bromobutyl or nonafluorobutyl, in particular trifluoromethyl or 1,2-dichloroethyl; • cyano-C 1 -C 4 -alkyl: cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanobut-1- ilo, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl, 1- (cyanomethyl) et-1-yl, 1- (cyanomethyl) -2-et-1-yl or 1- (cyanomethyl) -prop-1 -yl, preferably cyanomethyl or 2-cyanoethyl; • heterocyclyl-C-C 4 alkyl: heterocyclylmethyl, 1- (heterocyclyl) ethyl, 2- (heterocyclyl) ethyl, l- (heterocyclyl) -prop-1-yl, 2- (heterocyclyl) prop-1-yl, 3 - (heterocyclyl) -prop-1-yl, 1- (heterocyclyl) but-1-yl, 2- (heterocyclyl) -but-1-yl, 3- (heterocyclyl) but-1-yl, 4- (heterocyclyl) but-1-yl, l- (heterocyclyl) but-2-yl, 2- (heterocyclyl) but-2-yl, 3- (heterocyclyl) but-2-yl, 3- (heterocyclyl) but-2-yl, 4- (heterocyclyl) but-2-yl, 1- (heterocyclylmethyl) et-1-yl, 1- (heterocyclylmethyl) -1- (methyl) et-1-yl or 1- (heterocyclylmethyl) prop-1-yl, preferably (heterocyclyl) methyl or 2- (heterocyclyl) ethyl; C 1 -C 4 alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulphonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-Methylbutylsulfonyl, 3-methyl-butylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethyl-propylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, n-hexylsulfonyl, 1-methyl-pentylsulfonyl, 2-methylpentylsulfonyl, 3- methyl-pentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethyl-butylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethyl-butylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethyl-butylsulfonyl, 3,3-dimethylbutylsulfonyl, 3,3-dimethyl-butylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutyl-sulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropyl-sulfonyl, or 1-ethyl-2 -methylpropylsulfonyl, in particular methylsulfonyl or ethylsulfonyl; C 1 -C 4 alkoxy and the alkoxy portions of (C 1 -C 4) alkoxycarbonyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl and C 1 -C 4 -C 3 alkoxy alkenyl: methoxy , ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-raethylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, in particular methoxy, ethoxy, 1-methylethoxy or 1,1-dimethylethoxy: alkylthio-C? C4 and the alkylthio portions of C 1 -C 4 alkylthio-C 1 -C 4 alkyl and C 1 -C 4 alkylthio-C 3 -C 15 alkenyl: methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1 methylpropylthio, 2-methylpropylthio or 1,1-dimethylethylthio, in particular methylthio or ethylthio; haloalkoxy-C? ~ C4: alkoxy-C? ~ C4, as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy , dichlorofluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2-bromoethoxy, 2-iodoethoxy, 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, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2, 2 -difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 2- (fluoro- methyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably difluoromethoxy, trifluorometho xi or pentafluoroethoxy; haloalkylthio-C? -C4: alkylthio-C? -C4 as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromo-difluoromethylthio, 2-fluoroethylthio, -chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio , 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthiuo, 2-fluoro-propylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropyl, 2,2-difluoropropylthio, 2,3-difluoropropylthio , 2,3-dichloro-propylthio, 3, 3, 3-trifluoropropylthio, 3,3,3-trichloro-propylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoro-propylthio, 1- (fluoromethyl) -2 -fluoroethylthio, l- (chloro-methyl) -2-chloroethylthio, 1- (bromomethyl) -2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio or 4-bromobutylthio; C3-C6 alkenyl and the alkenyl portions of C 1 -C 4 alkoxy-C 3 -C 6 alkenyl, C 1 -C 6 alkylthio-C 4 -alkenyl and di (C 1 -C 4 alkyl) amino-C 3 -C 6 alkenyl, 1-en-l-yl, prop-2-en-l-yl, 1-methylenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3-yl, 1-methylpropyl l-en-l-yl, 2-methylprop-1-en-l-yl, l-methyl-prop-2-en-l-yl or 2-methylprop-2-en-l-yl, n-penten- l -yl, n-pentan-2-yl, n-penten-3-yl, n-penten-4-yl, l-methylbut-1-en-l-yl, 2-methylbut-l-en-l-yl, 3-methylbut-l-en-l-yl, 1-methylbut-2-en-l-yl, 2-methylbut-2-en-l-yl, 3- methy "I -but-2-en-l-yl, l-methylbut-3-en-l-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-l-yl, 1, l-dimethylprop-2-en-l-yl, 1,2-dimethylprop-l-en-l-yl, l, 2-dimethylprop-2-en-1-yl, l-ethylprop-l-enyl 2-yl, l-ethylprop-2-en-l-yl, n-hex-1-en-l-yl, n-hex-2-en-l-yl, n-hex-3-en-l- ilo, n-hex-4-en-l-yl, n-hex-5-en-l-yl, 1-methylpent-l-en-l-yl, 2-methylpent-l-en-l-yl, 3-methylpent-lnl-yl, 4-methylpent-1-en-l-yl, l-methylpent-2-en-l-yl-2-methyl-pent-2-en-l-yl, 3-methyl- pent-2-en-l-yl, 4-methylpent-2-en-l-yl, l-methylpent-3-en-l-yl, 2-methylpent-3-en-l-yl, 3-methylpent- 3-en-l-yl, 4-methylpent-3-en-l-yl, 1-methylpent-4-en-l-yl, 2-methyl-pent-4-en-l-yl, 3-methyl- pent-4-en-l-yl, 4-methylpent-4-en-l-yl, 1,1-dimethyl-but-2-en-l-yl, 1, l-dimethylbut-3-en-l- ilo, 1, 2-dimethyl-but-1-en-l-yl, 1, 2-dimethylbut-2-en-l-yl, 1,2-dimethyl-but-3-en-l-yl, 1, 3-dimethylbut-l-en-l-yl, 1,3-dimethyl-b ut-2-en-l-yl, 1,3-dimethylbut-3-en-l-yl, 2,2-dimethyl-but-3-en-l-yl, 2,3-dimethylbut-l-enyl l -yl, 2,3-dimethyl-but-2-en-l-yl, 2,3-dimethylbut-3-en-l-yl, 3,3-dimethyl-but-1-en-l-yl, 3,3-dimethylbut-2-en-l-yl, 1-ethylbut-l-en-l-yl, l-ethylbut-2-en-l-yl, l-ethylbut-3-en-l-yl, 2-ethylbut-l-en-l-yl, 2-ethylbut-2-en-l-yl, 2-ethylbut-3-en-l-yl, l, l, 2-trimethylprop-2-en-l- ilo, 1-ethyl-l-me 1 'lprop-2-en-l-yl, l-ethyl-2-methylprop-l-en-l-yl or l-ethyl-2-methylprop-2-en-l -ilo; C3-Cg alkynyl: prop-1-yn-l-yl, prop-2-yn-l-yl, but-1-yn-l-yl, but-l-yn-3-yl, but-l-in 4-yl, but-2-yn-l-yl, pent-1-yn-l-yl, n-pent-l-in-3-yl, n-pent-1-yn-4-yl, 4 -pent-l-in-5-yl, n-pent-2-yn-l-yl, n-pent-2-yn-4-yl, 4-pent-2-yn-5-yl, 3-methylbut -l-in-3-yl, 3-methylbut-l-in-4-yl, n-hex-1-yn-l-yl, n-hex-l-in-3-yl, n-hex-l -in-4-yl, n-hex-l-in-5-yl, n-hex-l-in-6-yl, n-hex-2-yn-l-yl, n-hex-2-in -4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-yl, n-hex-3-yn-2 -yl, 3-methylpent-l-in-l-ynyl, 3-methylpent-l-in-3-yl, 3-methylpent-l-in-4-yl, 3-methylpent-l-in-5 -yl, 4-methylpent-1-yn-l-yl, 4-methylpent-2-yn-4-yl or 4-methylpent-2-yn-5-yl; C3-Cg haloalkenyl: C3-C6 alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 2-chloroallyl, 3-chloroallyl, 3,3-dichloroallyl or pentafluoroalyl, in particular C3 or C4 haloalkenyl. . haloalkynyl-C3-Cg: C3-Cg alkynyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 4-chlorobut-2-yn-1-yl; • C3-C7 cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, in particular C3-C6 cycloalkyl; • saturated heterocyclic of 3 to 7 members and the heterocyclyl part of heterocyclyl-C-C4-alkyl: for example oxiranyl, tiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3 -yl, oxetane-2-yl, oxetan-3-yl, thiettan-2-yl, tietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl , tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, , 3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl, l , 3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, l, 3-oxazolidin-5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, l , 2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl , pyrrolidin-5-yl, tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetra-hydropyran-3-yl, tetrahydropyran-4-yl, tetrahydro -thiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydro-pyran-4-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, 1,3-dioxan -2-yl, l, 3-dioxan-4-yl, l, 3-dioxan-5-yl, 1,4-dioxan-2-yl, l, 3-oxatian-2-yl, 1,3-oxatian -4-yl, l, 3-oxathian-5-yl, l, 3-oxathian-6-yl, 1,4-oxathia-2-yl, 1,4-oxathiane-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyridazin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidine -4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, hexahydro-l, 3,5-triazin-1-yl, hexahydro-l, 3-5 -triazin-2-yl, oxepan-2-yl, oxepan-3-yl, oxepan-4-yl, tiepan-2-yl, tiepan-3-yl, tiepan-4-yl, 1,3-dioxepan-2 -yl, l, 3-dioxepan-4-yl, 1,3-dioxepan-5-yl, l, 3-dioxepan-6-yl, l, 3-dithiepan-2-yl, 1,3-dithiepan-2 -yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan-7-yl, hexahydroazepin-1-yl, hexahydroazepin -2-yl, hexa-hydroazepin-3-yl, hexahydroazepin-4-yl, hexahydro-1,3-diazepin-1-yl, hexahydro-l, 3-diazepin-2-yl, hexahydro-l, 3-diazepin -4-yl, hexahydro-l, 4-diazepin-1-yl or hexahydro-l, 4-diazepin-2-yl; 5- or 6-membered heteroaryl, in particular furyl, such as 2-furyl and 3-furyl, thienyl, such as 2-thienyl and 3-thienyl, pyrrolyl, such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl, such as -isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl, such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl, such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl, such as 2-oxazolyl , 4-oxazolyl and 5-oxazolyl, thiazolyl, such as 2-thiazolyl, 4-thiaz < oyl and 5-thiazolyl, imidazolyl, such as 2-imidazolyl and 4-imidazolyl, xadiazolyl, such as l, 2,4-oxadiazol-3-yl, l, 2,4-oxadiazol-5-yl yl, 3,4 -oxadiazol-2-yl, thiadiazolyl, such as 1,2,4-thiadiazol-3-yl, l, 2,4-thiadiazol-5-yl and 1,3,4-thiadiazol-2-yl, triazolyl, such as 1,2,4-triazol-1-yl, 1, 2,4-triazol-3-yl and 1, 2,4-triazol-4-yl, pyridinyl, such as 2-pyridinyl, 3-pyridinyl and 4- pyridinyl, pyridazinyl, such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl, such as 2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl, likewise 2-pyrazinyl, 1, 3,5-triazin-2-yl and 1, 2 , 4-triazin-3-yl, in particular pyridyl, pyrimidyl, furanyl and thienyl.

All phenyl rings and heterocyclic rings are preferably unsubstituted or have a halogen, methyl, trifluoromethyl or methoxy substituent attached thereto. With respect to the use of the derivatives I of 5-pyrazolylbenzoic acid as herbicides, preferred compounds are those in which the substituents have the following meanings, in each case alone or in combination: R1 is hydrogen or C1-C4alkyl, in particular C-alkyl ? ~ C4 ,; methyl is particularly preferred; R2 is haloalkoxy-C? ~ C4, in particular difluoromethoxy; R3 is hydrogen or halogen, in particular halogen; chlorine is particularly preferred; R5 is halogen or haloalkyl-C? -C4, in particular halogen; chlorine is particularly preferred; R6 is _o-R7 or -N (R8) -R7; R7 is -XC (R9) = N-0-Z-R10 -X-0-N = C (R ?: L, R12) / -X-S02-R13 or saturated heterocyclyl or heterocyclyl-C1-C4 alkyl, from 3 to 6 members, the heterocycle also contains methylene members, one to three ring members selected from the group consisting of three aza bridges and two oxygen or sulfur atoms, and it is possible, if desired, that one or two methylene groups of the heterocycle are replaced by carbonyl, thiocarbonyl and / or sulfonyl, it is also possible that the heterocycle is unsubstituted or has one or four substituents, each selected from the group consisting of halogen, alkyl-C? -C4 , C 1 -C 4 alkoxy, (C 1 -C 4 alkoxy) carbonyl, (C 1 -C 4) alkylcarbonyl, (C 1 -C 4 alkyl) carbonyloxy and (C 1 -C 4 alkyl) carbonylamino; in particular -X-C (R9) = N-0-Z-R10 or -X-0-N = C (R?: L, R12); R 8 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl; R 9 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl; R 0 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy-C 1 -C 4 alky, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, C 3 alkynyl -C5, haloalkynyl-C3-C5, cycloalkyl-C3-C7, which, if desired, can have one to three C-C3-alkyl radicals, or is phenyl, benzoyl or heteroaryl of 5 or 6 members, which contains one to three heteroatoms, selected from the group consisting of three nitrogen atoms and one oxygen or sulfur atom, it being possible for the phenyl and heteroaryl rings to be unsubstituted or have a substitutable ring member attached to each one of the following substituents: nitro, cyano, halogen, C 1 -C 4 alkyl, C 1 -C haloalkyl, C 1 -C 4 alkoxy, in particular hydrogen, C 1 -C 4 alkyl, C 1 -C haloalkyl, C 2 alkenyl -C5, C3-C5 alkynyl, phenyl, benzoyl or 5- or 6-membered heteroaryl, which contains one to three heteroatoms selected from the group consisting of three hydrogen atoms and one oxygen or sulfur atom, being It is clear that the phenyl and heteroaryl rings are unsubstituted or have attached to each substitutable ring member one of the following substituents: nitro, cyano, halogen or C 1 -C 4 alkyl; R 11, R 12, independently of one another, are hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,. C3-C5-alkenyl, C3-C5-alkynyl, C3-C7-cycloalkyl or phenyl, which, if desired, can have attached to each substitutable ring member one of the following substituents: nitro, cyano, halogen and alkyl- C? ~ C4, in particular C 1 -C 4 alkyl, or R 11 and R 12, together with the arbon atom to which they bind, form a saturated carbocyclic ring of 5 or 6 members; R13 is C1-C-alkyl, C1-C-haloalkyl, C1-C4-alkyl, C3-C5-alkenyl, C3-C5-haloalkenyl, C3-C5-alkynyl, 5- or 6-membered phenyl or heteroaryl, each having one to three heteroatoms, selected from the group consisting of three nitrogen and one oxygen or sulfur atoms, it being possible for the phenyl and heteroaryl ring to be unsubstituted or have a halogen or a halo substituent attached to each substitutable ring member; C 1 -C 4 alkyl, in particular C 1 -C 4 alkyl or phenyl; X and Z, independently of one another, are alkylene-4-chain chains which may be unsubstituted or have one or four heterologous substituents and / or C-C4-alkyl, in particular methylene, ethane-1 linked thereto. , 2-diyl or propane-l, 3-diyl.

Very particularly preferred are the compounds listed in the following Table I (where R 1 = methyl, R 2 = difluoromethoxy, R 3, R 4 and R 5 = chlorine): Table 1 Likewise, the 5- pyrazolylbenzoic acid derivatives of the formula Ib are particularly preferred, in particular the compounds Ib.001-Ib.481, which differ only from the corresponding compounds la.001 - la.481 in that R4 is fluorine .

The 5-pyrazolylbenzoic acid derivatives of the formula I can be obtained by several routes, in particular by one of the following methods: A) A derivative of β-ketocarboxylic acid IV is reacted with hydrazine or a hydrazine derivative in an inert solvent (for example, see JP-A 04/225 937 and JP-A 03/072 460) and Product V of the process is rented: + L1- (C? -C4 -alkyl) + L1- (C1-C-haloalkyl) is a customary leaving group, such as halogen, -0-S02CH3, -0-S02CF3, -0-S02C4F9 and -0-S02 (p-CH3-C6H4); R 14 is preferably halogen, C 1 -C 4 alkoxy (C 1 -C 4 alkyl) -carbonyloxy; .15 is hydrogen, nitro, amino, halogen, alkyl, haloalkyl, -CH2-R6, formyl, carboxyl, alkoxycarbonyl or -CO-R6.

The solvent can be aprotic or protic. Examples of suitable solvents are organic acids, such as acetic acid, hydrocarbons, halogenated hydrocarbons, ethers, such as ethylene glycol dimethyl ether, alcohols, such as methanol and ethanol, and sulfoxides. However, the process can also be carried out in the presence of a solvent. The reaction temperature is predetermined mainly by the melting point of the solvent or compound IV and the boiling point of the reaction mixture. The process is preferably carried out at a temperature of about 60 to 120SC. In general, approximately 0.95 to 5 times the molar amount, preferably 1 to 1.4 times the amount, of hydrazine or a hydrazine derivative, based on the IV derivative of β-ketocarboxylic acid is used. The amount of the alkylating agent, L ^ -alkyl-C2-C4) or L1- (haloalkyl-C1-C4) is also conventionally from 0.95 to 5 times the molar amount, based on the intermediate product V. With respect to the Preferred radicals R1 in the 3-phenylpyrazoles I, particularly preferred hydrazine derivatives are those having an alkyl group attached. The alkylation is conventionally carried out using the halide, preferably the chlorine or the bromine, or using the sulfate of an alkane or haloalkane, if desired, in the presence of an organic base, for example a trialkylamine, or pyridine, or of an inorganic bse, such as an alkali metal carbonate. The alkylation is conveniently carried out in an inert organic solvent, for example in an aliphatic or cyclic ether, such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aliphatic ketone, such as acetone, in an amide, such such as dimethylformamide, in a sulfoxide, such as dimethyl sulfide, or in a mixture of one of these solvents and water. The reaction is generally carried out at a temperature of 02C to the boiling point of the reaction mixture, preferably of about 20 to 80 ° C.

B) Compounds VI, where R3 = hydrogen, are halogenated: VI (R3 = H) VI (R3 = halogen) The reaction can be carried out in an inert solvent / diluent or in the absence of a solvent. Examples of suitable solvents are organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers, sulphides, sulfoxides and sulfones. Suitable halogenating agents are, for example, chlorine, bromine, N-bromosuccinimide, N-chlorosuccinimide or sulfuryl chloride. Depending on the starting compound and the halogenating agent, an addition of a free radical initiator, for example an organic peroxide, such as dibenzoyl peroxide or an azo compound, such as azo-bis-isobutyronitrile, or irradiation with light, it can have an advantageous effect in the course of the reaction. The amount of the halogenating agent is not critical.

Both sub-stoichiometric and large excess amounts of the halogenating agent are possible, based on the compound VI to be halogenated, where R3 = hydrogen. If a free radical initiator is used, a catalytic amount will generally suffice. The reaction temperature is usually from -100dC to 2002C, more preferred from 10 to 100 ° C, or the boiling point of the reaction mixture.

C) The 3- (3-methylphenyl) pyrazoles VI (R15 = CH3) are halogenated and a) the products of the process are subjected to a nucleophilic substitution, followed by oxidation, or b) the products of the process are hydrolyzed: SAW . { R15 = CH3} SAW . { R15 CH2 (halogen) 2 -CH (halogen) 2, -C (halogen) 3.}.

SAW. { R15 = _CH2- nucleophilic halogen J VI. { R ^ = -CH2-OR7 - * + - -CH2-N (R8) -R7, substitution \ -CH2-N (R8) -OR7} oxidation *. { R "- -OR7, -N (R8) -R7, -N (R8) -OR7} hydrolysis t VI. { R15 - VI (Rl 5 = CHO) + VI (R 5 = COOH) -CH2 (halogen) 2, f -CH (halogen) 3.}. oxidation With respect to the solvents, the amounts used and the reaction conditions for halogenation, reference is made to the information given in method B). In halogenated compounds VI, where R15 = halomethyl, the halogen atom can be subjected to nucleophilic substitution with an alcohol (-0-R7) or an amine radical (-N (R8) -R7 or -N (R8) - 0-R7). The nucleophiles used are any of the corresponding alcohols or amines, in which case the process is preferably carried out in the presence of a base (eg, an alkali metal hydroxide, an alkaline earth metal hydroxide, a carbonate of an alkali metal or an alkaline earth metal carbonate), or the alkali metal salts of these compounds are also used, which are obtained by the reaction of the alcohols or amines with a base (for example an alkali metal hydride). Suitable solvents are, in particular, aprotic organic solvents, for example tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or hydrocarbons, such as toluene and hexane. The reaction is carried out between the melting point and the boiling point of the reaction mixture, preferably between 0 and 100dC. The substitution products can be converted into the corresponding derivatives I of the 5-pyrazolylbenzoic acid (R6 = -0-R7, -N (R8) -R7 or -N (R8) -o-R7) by oxidation in a manner of per se known (see, for example, Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Vol. E5, Georg, Thieme Verlag, Stuttgart 1985, pp. 935 et seq .: SJ Angyal, K. James, Carbohydr Res 12, 147 (1970), PF Schuda, MB-Cichowicz, MR Heimann, Tetrahedron Lett 24, 3829 (1983), ibid 24 4267 (1983)). Oxidanets suitable for this purpose are preferably the transition metal compounds, for example chromium, rhodium or ruthenium oxides, preferably in a catalytic or stoichiometric amount, based on the compound VI to be oxidized. When catalytic amounts are used, additional oxidants, for example oxygen, amine N-oxides or alkali metal per-iodates, are required in stoichiometric amounts, or also in excess, for example, to achieve particularly high conversion rates. Suitable solvents are, in addition to customary organic solvents, organic acids. The oxidation can also be carried out in a two-phase aqueous organic system, preferably in the presence of a phase transfer catalyst.

As a rule, the reaction temperature is between the melting point and the boiling point of the reaction mixture, preferably at 0 to 100 ° C. Compounds VI, where R 15 = dihalo- or trihalo-methyl, are preferably hydrolyzed under acidic conditions, for example in the absence of a solvent in hydrochloric acid, acetic acid, formic acid or sulfuric acid, or else in aqueous solutions thereof . As a rule, hydrolysis is carried out between the melting point and the boiling point of the reaction mixture, preferably at 0 to 10 s The hydrolysis products VI, where R15 = formyl can be oxidized in a manner known per se to give the corresponding carboxylic acids (see, in this context, in particular pages 179 to 181 of AH-Haines , in "Methods of the Oxidation of Organic Compounds", Academic Press, 1988). D) The "Sandmeyer" reaction of the anilines VI (R15 = NH2) in a manner known per se (see, for example, Houben-Weyl, in "Methoden der Organischen Chemie" [Methods in Organic Chemistry], Vol. 5/4, Georg Thieme Verlag, Stuttgart 1960, pp. 438 et seq.): VI (Rl5 - NH2) VI (Rl5 = Cl, Br, I) In general, the diazonium salt is obtained in a manner known per se, by the reaction of the aniline VI (R15-H2) with a nitrite, such as sodium nitrite or potassium nitrite, in an aqueous solution of an acid, for example in hydrochloric acid, hydrobromic acid or sulfuric acid. However, it is also possible to carry out the process under anhydrous conditions, for example in glacial acetic acid containing hydrogen chloride, in absolute ethanol or in dioxane or tetrahydrofuran, in acetonitrile or in acetone, in this case, the aniline VI ( R15 = NH2) is treated with a nitrous ester, such as tertiary butyl nitrite and isopentyl nitrite. Particularly preferred, the resulting diazonium salt is converted to the halogen compound VI, where R15 = chlorine, bromine, or iodine, by its reaction with a solution or suspension of a copper (I) salt, such as copper chloride (I), copper bromide (I) and copper iodide (I), or with a solution of an alkali metal salt. This reaction of the diazonium salt can be carried out, for example, in water, in hydrochloric acid or aqueous hydrobromic acid or in a ketone, such as acetone, diethyl ketone and methyl ethyl ketone, in a nitrile, such as acetonitrile, in an ether, such as dioxane and tetrahydrofuran, or in an alcohol, such as methanol and ethanol. The reaction temperature is usually -30 to + 505C. Preferably, all reagents are used in approximately stoichiometric amounts, but an excess of one or another component may be advantageous. Anilines VI, where R15 = amino, can be obtained by reducing the corresponding nitro compounds VI, where R15 = nitro: VI (R5 - nitro) VI (Rl5 = amino) The reduction is carried out with a metal, such as iron, zinc or tin, under acetic reaction conditions, or with a complex hydride, such as lithium hydride. aluminum and sodium borohydride, suitable solvents - depending on the selected reducing agent - are, for example, water, alcohols, such as methanol, ethanol and isopropanol, or ethers, such as diethyl ether, methyl-t-butyl -teter, dioxane, tetrahydrofuran and ethylene glycol dimethyl-ether. When the reduction is carried out with a metal, the process is preferably carried out in the absence of a solvent, in an inorganic acid, in particular in concentrated or dilute hydrochloric acid, or in an organic acid, such as acetic acid . However, it is also possible to mix an inert solvent, for example one of those mentioned above, with the acid. The starting compound VI (R15 = N02) and the reducing agent are conveniently used in approximately equimolar amounts; however, to optimize the course of the reaction, one of the two components can advantageously be used in an excess, approximately up to 10 times the molar amount. The amount of the acid is not critical. In order to reduce the starting compound as completely as possible, it is convenient to use at least an equivalent amount of the acid. The reaction temperature is generally from -30 to + 2000C, preferably from 0 to 80QC. For working up, the reaction mixture is usually diluted with water and the product is isolated by filtration, crystallization or extraction with a solvent, which is largely immiscible with water, for example with ethyl acetate, diethyl ether or methylene chloride . If desired, the product can subsequently be purified in the usual manner. The nitro group of nitrophenylpyrazoles VI (R15 = nitro) can also be subjected to catalytic hydrogenation by means of hydrogen. Catalysts which are suitable for this purpose are, for example, Raney nickel, palladium on carbon, palladium oxide, platinum and platinum oxide, an amount of 0.05 to 10.0 mol% of the catalyst based on the compound to be reduce, will generally be enough. The process is carried out either in the absence of a solvent or in an inert solvent or diluent, for example in acetic acid, in a mixture of acetic acid and water, ethyl acetate, ethanol or in toluene.

After the catalyst has been removed, the reaction solution can be worked up in a usual manner to give the product. The hydrogenation can be carried out under atmospheric pressure or under elevated pressure. The nitro compounds VI, where R15 = nitro, are, in turn, preferably accessible by nitrating the phenylpyrazoles VI, where R15 = H2.

VI (Rl5 - H) VI (Rl5 = N02) Suitable nitrating reagents are, for example, nitric acid in various concentrations, or also concentrated and smoking nitric acid, mixtures of sulfuric acid and nitric acid, acetyl nitrates and alkyl nitrates. The reaction can be carried out or in the absence of a solvent in an excess of the nitrating reagent or in an inert solvent or diluent, suitable solvents or diluents are, for example, water, mineral acids, organic acids, chlorohydrocarbons, such as methylene chloride, anhydrides, such as acetic anhydride, and mixtures thereof. The starting compound VI (R15-H) and the nitrating reagent are conveniently used in quasi-equimolar amounts; however, to optimize the rate of conversion of the compound to be nitrated, it may be advantageous to use the nitration reagent in an excess, approximately up to 10 times, the molar amount. If the reaction is carried out in the absence of a solvent in the nitrating reagent, the latter will be present in an even greater excess. The reaction temperature is usually from -100 to + 200 ° C, preferably from -30 to + 50 ° C. E) Synthesis of esters, amides, thioesters and hydroxamic esters of the carboxylic acids VI, where R15 = COOH, in a manner known per se: VI (Rl5 = COOH) VI (Rl5 = COCÍ) yls _o-, -S-, -N (R8) -, -N (R8) -0; and 2 is _S_f -N (R8) -, -N (R8) -0-; X1 is a radical X, as defined, with the exception of methylene and substituted methylene; L2 and L3 are customary leaving groups, such as halogen, -O-SO2CH3, -0-S02-CF3, -O-SO2C4F9 or -0-S02"(4-methylphenyl) .The reactions are carried out in a manner in itself known {see, for example, Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag, Stuttgart, Vol. 8, 4ß Edition 1952, page 471 et seq., page 655) and following and pages 686 and following, Vol. 9, 1955, pp. 753 et seq., and pp. 745 et seq., Vol. E5, 1985, pp. 941 et seq.), For example, the carboxylic acids VI where R15 = COOH can be converted to their acid chlorides VII, of which the derivatives I of 5-pyrazolylbenzoic acid and the compounds VIII are accessible by reaction with suitable alcohols, amines, thiols or alkoxy-amines. carboxylic acids VI (R15 = COOH) can also be reacted directly with alcohols, amines, thiols or alkoxyamines, in this context, the presence of a reagent of activation, for example N, N'-dicyclohexylcarbodiimide or carbonyldi idazolide, may be advantageous. Finally, it is also possible to rent the carboxylic acids VI (R15 = COOH) with compounds R7-L3 to give the corresponding esters I (R6 = -0-R7). The 3-phenylpyrazoles VIII can subsequently be converted to compounds I in a manner known per se. For example, compounds VIII where R16 = -Y1 -? - CO-R9 react with hydroxylamines H2N-0-Z-R10 to give oximes I (R6 = Y1-XC (R9) = N-0-Z-R10 ), (see, for example, Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag, Stuttgart 1968, Vol. 10/4, p.10 et seq. and Vol. E14b, Stuttgart 1990, p. 290 and following). The oximes, thiols, thioacids, acid amides and hydroxamic acids VIII (R16 = -Y1-XC (= N-OH) -R9, -S-X'-SH and Y2-H) can be converted into compounds I by means of of alkylation (see, for example, Houben-Weyl, Methoden der Organiechen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag, Vol. E5 Stuttgart 1985, pp. 934 et seq. and pp. 1148 et seq., and Vol. 9, 4th Edition 1955, p. 749 et seq.) And thiols VII (R16 = -S-Y3-SH) can be converted to thioethers VIII (R16 _ -S-X'-SZ-R13), and these can be oxidized to give the sulfones I (R6 = -SX, -S? 2 ~ Z-R13) (see, in this context, for example, Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag, Stuttgart Vol. 9, 4th Edition 1955 , p.103 et seq. and p.227 et seq. Likewise, sulfones I (R6 = -Y1-XS? 2 ~ Z-R13) are accessible by the reaction of compounds VIII (R16 = -C0-yi-X) -L2) with thiols, SH-Z-R1 'followed by oxidation The carboxylic acids VI, where R15 _ COOH in turn, are preferably accessible by carboxylation of the halogen compounds VI, where R15 = chlorine, bromine or iodine , in a manner known per se (see, for example, JP-A 06/073 015): VI (R15 = Cl, Br, I) VI (R "= COOH) It is convenient to carry out the process in the presence of catalytic amounts of a complex of a transition metal, preferably a palladium phosphine complex, under a carbon monoxide pressure of about 1 to 100 bar. As a rule, the reaction is carried out in an inert organic solvent, which is miscible with water, for example in acetonitrile or in tetrahydrofuran. Normally, water and an organic or inorganic base, such as, in particular, sodium carbonate, are used in approximately equivalent amounts or in an excess of about up to 10 times the molar amount, based on the amount of compound VI starting (where R15 = chlorine, bromine or iodine). The reaction temperature is usually from the melting point of the reaction mixture to about 200 ° c.

Unless otherwise specified, the reactions, described above, are conveniently carried out under atmospheric pressure or under the inherent pressure of the reaction mixture in question. As a rule, the reaction mixtures are prepared by methods known per se, for example, by diluting the reaction solution with water, followed by the isolation of the product by means of filtration, crystallization or solvent extraction, or by removing the solvent , dividing the waste into a mixture of water and a suitable organic solvent and elaborating the organic phase to obtain the product. During their preparation, the derivatives I of 5-pyrazolylbenzoic acid can be obtained in the form of isomeric mixtures, but, if desired, they can be separated by methods customary for this purpose, such as crystallization or chromatography, for example. , in an optically active adsorbate, to give the pure isomers. Optically active pure isomers can be advantageously prepared from the corresponding optically active starting materials. Useful salts in agriculture of the compounds I can be formed by their reaction with a base of the corresponding cation, preferably a hydroxide or hydride of an alkali metal, or by its reaction with a corresponding anion acid, preferably hydrochloric acid, hydrobromic acid , sulfuric acid, phosphoric acid or nitric acid. The salts of the compounds I whose metal ion is not an alkali metal can also be prepared by subjecting the alkali metal salt corresponding to double decomposition in the customary manner, and also the salts of ammonium, phosphonium, sulfonium and sulfoxonium by means of the ammonia and phosphonium, sulfonium or sulfoxonium hydroxides. The compounds I and their salts useful in agriculture are suitable for use as herbicides, or in the form of a mixture of isomers or in the form of pure isomers. The herbicidal compositions comprising the compounds I perform a very efficient control of the vegetation in non-harvest areas, in particular at high application rates. They act against broad-leaved weeds and grass weeds in crops, such as wheat, rice, corn, soybeans and cotton, without harming the harvest plants to a significant extent. This effect is particularly pronounced at low application regimes. Depending on the method of application in question, the compounds I or the herbicidal compositions comprising them, may also be employed in a further number of harvest plants to eliminate unwanted plants. The following are examples of suitable crops: Allium cepa, Ananas comosus, Arachis hypogasa, Asparagus officinalls, Beta vulgaris ssp. altissima, Beta vulgaris ssp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. sylvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus lemon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycin max, Gossypium hirsutum, (Gossypium arboreaum, Gossypium herbacem, Gossypium vitifolim), Helianthus annus, Hevea brsiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus ssp. , Manihot esculenta, Medicago sativa, Musa ssp. , Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phasaeolus lunatus, Phaseolus vulgaris, Picea abies, Pinus ssp. , Pisum, sativum, Prunus avium, Prunus pérsica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum Sécale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobromo cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba , Vitis v ini fer and Zea maye. Also, compounds I can be used in crops which tolerate the action of herbicides, as a result of breeding, which include genetic engineering methods. Likewise, the 5-pyrazolylbenzoic acid derivatives I are also suitable for the desiccation and / or defoliation of the plants. As desiccants, they are particularly suitable for drying the aerial parts of crop plants, such as potatoes, turnip, sunflower and soybean oil. This allows the completely mechanical harvest of these important harvest plants. Also of economic interest is to facilitate the harvest, which is made possible by the concentration, in n period of time, dehiscence, or reduce the adhesion to the trees, in citrus fruits, olives and other species and variants of pome fruits, fruits and nuts of bone. The same mechanism, for example the promotion of tissue separation between fruits or leaves and shoots of plants, is also important for the easily controllable defoliation of useful plants, in particular cotton. Also, the reduction of the period within which the individual cotton plants mature, results in an improved quality of the fiber after harvest. The compounds I, or the compositions comprising them, can be used, for example, in the form of aqueous solutions ready for spraying, powders, suspensions, also suspensions or aqueous dispersions oily or other high percentage, emulsions, oil dispersions , powdered pastes, materials for spreading or granules, by means of spraying, atomization, dusting, dispersion or emptying. The forms of use depend on the intended object; in any case, they must guarantee the finest possible distribution of the active ingredients, according to the invention. Inert auxiliaries suitable for the preparation of solutions ready for spraying, emulsions, pastes or oil dispersions are mainly: fractions of mineral oils from medium boiling point to high, such as, kerosene and diesel oil, as well as tar oils of coal and oils of vegetable and animal origin. aliphatic, cyclic and aromatic hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols, such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones, such as cyclohexanone, strongly polar solvents , for example amines, such as N-methylpyrrolidine, and water. Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or granules dispersible in water, by the addition of water. To prepare emulsions, pastes or oil dispersions, the substances either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, adhesion agent, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates comprising the active ingredient, wetting agent, adhesion agent, dispersant or emulsifier and, if desired, a solvent or oil, which are suitable for dilution with water. Suitable surface-active agents (aants) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example ligno-, phenol-, naphthalene- and dibutylnaphthalene sulfonic acid, or of fatty acids, alkyl- and alkylaryl sulphonates, alkyl and lauryl ether and sulfates of fatty alcohols, and salts of sulfated hexa-, hepta and octa-decanoates, and also glycol ethers of fatty alcohols, condensates of naphthalene sulphonated and their derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-octylphenol-ether, isooctyl-, octyl- or nonylphenol ethoxylated, alkylphenyl-polyglycol ether, tributylphenyl-polyglycol ether, alkylaryl-polyether alcohols, isotridecyl alcohol, condensates of fatty alcohol / ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ether or poloxipropylene alkyl ethers, polyglycol ether ethyl alcohol laur Lico, sorbitol esters, lignosulfite waste liquors or methylcellulose. Powders, materials for dispersion and sprinkling can be prepared by mixing or grinding the active ingredients together with a solid carrier. Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by ligating the active ingredients to the solid carriers. Solid carriers are mineral soils, such as silicas, silicate gels, silicates, talc, kaolin, limestone, lime, clay, clay earth, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, oxide magnesium, synthetic milled materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal flour, tree bark flour, wood flour and husk meal of nuts, cellulose powders, or other solid carriers. The concentrations of the active ingredients I in ready-to-use preparations may vary within wide limits. In general, the formulations comprise about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90 to 100%, preferably 95 to 100% (according to the nuclear magnetic resonance spectrum [NMR]). The formulation examples that follow illustrate the production of such preparations: I. 20 parts by weight of compound No. 0.003 were dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct from 8 to 120 moles of ethylene oxide to 1 mole of the N-monoethanolaramide of oleic acid, 5 parts by weight of the calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. The solution was poured into 100,000 parts by weight of water and finely distributed to give an aqueous dispersion comprising 0.02% by weight of the active ingredient. II. 20 parts by weight of compound No. 00.00 were dissolved in a mixture composed of 40 parts by weight of the cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of the isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. The solution was poured into 100,000 parts of water by weight and finely distributed to give an aqueous dispersion comprising 0.02% by weight of the active ingredient.

III. 20 parts by weight of compound No. 0.006 were dissolved in a mixture composed of 25 parts by weight of the cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210-280P-C and 10 parts by weight. Adduct weight of 40 moles of ethylene oxide to 1 mole of castor oil. The solution was poured into 100,000 parts of water by weight and finely distributed to give an aqueous dispersion comprising 0.02% by weight of the active ingredient. IV. 20 parts by weight of compound No. 007 were dissolved in a mixture composed of 3 parts by weight of the sodium diisobutyl naphthalene-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a waste liquor. of sulfite, and 60 parts by weight of powdered silica gel, and the mixture was milled in a hammer mill. The fine distribution of the mixture in 20,000 parts by weight of water gave a spray mixture comprising 0.1% by weight of the active ingredient. V. 3 parts by weight of active ingredient No. 0.008 were mixed with 97 parts by weight of finely divided kaolin. This gave a powder comprising 3% by weight of the active ingredient. SAW. 20 parts by weight of compound No. 00.00 were intimately mixed with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol condensate. urea / formaldehyde and 68 parts by weight of a paraffinic mineral oil. This gave a stable oily dispersion. VII. 1 part by weight of compound No. 0,010 was dissolved in a mixture composed of 70 parts by weight of the cyclohexanone, 20 parts by weight of the ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gave a stable emulsion concentrate.

VIII. 1 part by weight of compound No.,022 was dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM31 (= non-ionic emulsifier based on ethoxylated castor oil). This gave a stable emulsion concentrate. The active ingredients I, or the herbicidal compositions, can be applied before or after the emergence of the weeds. If the active ingredients are tolerated less well by certain crop plants, the application techniques can be used in which the herbicidal compositions are sprayed, with the help of the spray equipment, in such a way that they can come into contact as little as possible. possible with the leaves of sensitive crop plants, while the active ingredients reach the leaves of the unwanted plants that grow under these harvest plants, or to the soil surface alone (subsequently placed). Depending on the intended object, the season, the target plants and the growth stage, the application regimes of the active ingredient I are from 0.001 to 3.0, preferably from 0.01 to 1.0 kg of the active ingredient (i. A.) Per hectare (ha). To broaden the spectrum of action and to achieve synergistic effects, the 5-pyrazolylbenzoic acid derivatives I can be mixed with a large number of representatives of other groups of herbicides or ingredients that regulate growth and then applied concomitantly. Suitable components for the mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anuides, aryloxy / hetaryloxyalkane acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2- (hetacroyl / aroyl) -l, 3-cyclohexanediones, hetaryl-aryl-ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexan-1 derivatives , 3-dione, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy and hetaryloxy-phenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridine-carboxylic acid and its derivatives, pyrimidyl-ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils. It may also be advantageous to apply the compounds I, alone or in combination with other herbicides, together with additional crop protection agents, for example with pesticides or agents for the control of phytopathogenic fungi or bacteria. Equally of interest is the miscibildiad with the solutions of mineral salts, which are used to treat and deficiencies of trace elements and nutrients. Non-phytotoxic oils and oil concentrates can also be added.

Preparation Examples Example 1 Synthesis of the 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzoic acid precursor: Step 1: 5- (2,4-Dichloro-5-methylphenyl) -1,2-dihydro-2-methyl-3H-pyrazol-3-one 13.5 g (292 mmol) of the methylhydrazine were added slowly to 80.4 g (292 mmol) ) of ethyl 2,4-dichloro-5-methylbenzoylacetate in 300 ml of diethylene glycol dimethyl ether. After 4 hours at 100 ° C, the solution was stirred in 1 liter of ice-water. The precipitate formed was separated by filtration, washed with a small amount of methylene chloride and dried. Yield: 38.8 g. * H NMR (270 MHz, in d6-dimethyl sulfoxide): d (ppm) = 2.32 (s, 3H), 3.60 (s, 3H), 5.89 (s, 1H), 7.58 (s, 1H), 7.76 ( s, 1H), 11.12 (s, 1H).

Step 2: 3- (2,4-dichloro-5-methylphenyl) -5-difluoro. methoxy-1-methyl-1H-pyrazole 28.8 g (720 mmol) of sodium hydroxide, dissolved in 240 ml of water, were added to a solution of 37 g (144 mmol) of the 5- (2,4-dichloro- 5-methylphenyl) -1,2-dihydro-2-methyl-3H-pyrazol-3-one in 390 ml of dioxane. The chlorodifluoromethane was subsequently passed at 60-65 ° C, over the course of 4 hours, after which the reaction solution was stirred in 1 liter of water. It was then extracted using methyl-t-butyl ether. The organic phase was dried over magnesium sulfate, filtered and then concentrated. The crude product was purified by means of column chromatography on silica gel (eluent: diethyl ether). Yield: 35.1 g. iH NMR (270 MHz, in CDC13): d (ppm) = 2.39 (s, 3H), 3.84 (s, 3H), 6.45 (S, 1H), 6.59 (t, 1H), 7.46 (s, 1H), 7.70 (s, 1H).

Step 3: 4-Chloro-3- (2,4-dichloro-5-methylphenyl) -5-difluoro-methoxy-1-methyl-1H-pyrazole 16.9 g (125 mmol) of sulfuryl chloride were added, dropwise, to a 35 g solution (114 mmol) of 3- (2,4-dichloro-5-methylphenyl) -5-difluoromethoxy-1-methyl-1H-pyrazole in 120 ml of tetrachloromethane. After the reaction mixture had been stirred for 2 hours, it was washed with water, a saturated aqueous sodium hydrogen carbonate solution and an aqueous saturated sodium chloride solution, and then dried over magnesium sulfate, filtered and concentrated. Yield: 30.8 g. H NMR (270 MHz, in CDC13: d (ppm) = 2.39 (s, 3H), 3.85 (s, 3H), 6.74 (t, 1H), 7.30 (s, 1H), 7.49 (s, 1H).

Step 4: 3- (5-Dibromomethyl-2,4-dichlorophenyl) -4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole 99.3 g (560 mmol) of the N-bromosuccinimide were added to a solution of 28 g (82 mmol) of 4-chloro-3- (2,4-dichloro-5-methylphenyl) -5-difluoromethoxy-1-methyl-1H-pyrazole in 1.5 liters of tetrachloromethane. The reaction mixture was then irradiated for 2 hours, using a UV lamp and a 150 W high pressure mercury vapor lamp. The solids content was subsequently removed by filtration, then the filtrate was concentrated. Performance: quantitative. H NMR (270 MHz, in CDC13: d (ppm) = 3.88 (s, 3H), 6.75 (t, 1H), 7.05 (s, 1H), 7.50 (S, 1H), 8.08 (s, 1H).

Step 5: 5- (4-Chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzaldehyde 45.5 g (91 mmol) of 3- (5-dibromomethyl-2,4-dichlorophenyl) 4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole was added, a little at a time, to 65 ml of concentrated sulfuric acid at 852C, during the process the mixture was slowly heated to 95ce The reaction mixture was The mixture was subsequently stirred for an additional 5 minutes, then stirred in 600 ml of ice-water. The product was extracted using dichloromethane. The organic phase was washed with the use of a saturated solution of sodium chloride, dried over magnesium sulfate, filtered and finally concentrated. The crude product was purified by dissolving in hexane / ethyl acetate (1: 1) and the solution was filtered through a pad of silica gel. Yield after concentration: 20 g. H NMR (270 MHz, in CDC13: d (ppm) = 3.87 (s, 3H), 6.77 (t, 1H), 7.65 (s, 1H), 8.02 (s, 1H), 10.4 (s, 1H).

Step 6: 5- (4-Chloro-5-difluoromethoxy-1-methoxy-1H-pyrazol-3-yl) -2,4-dichlorobenzoic acid A solution of 2.5 g (16 mmol) of sodium dihydrogen phosphate dihydrate in 25 g. ml of water, was added, dropwise, at 10-15 ° C, to a solution of 21.3 g (60 mmol) of 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2.4 -dichlorobenzaldehyde in 120 ml of acetonitrile. 6 ml of a 30% by weight hydrogen peroxide solution and then, in the course of two hours, a solution of 8.7 g (96 mmol) of sodium chlorite in 80 ml of water were added in drops to this mixture . The reaction mixture was stirred for a further hour and then acidified with 3N hydrochloric acid. The solids content was separated from the resulting suspension and dried. Yield: 13.7 g; melting point of 159-1602C.

Example 2 2- (4-Chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichloro-benzoate of 2- (ethoxyimino) ethyl (# la. 003) A solution of 1.9 g (5 mmoles) of 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-di-chlorobenzoic acid, 0.9 g (6.5 mmol) of potassium carbonate (milled) ) and 0.6 g (5 mmoles) of the 0-ethyl-chloroacetaldehyde oxime in 50 ml of dimethylformamide was stirred for 3 hours at 50-60 ° C, then concentrated. The residue was taken up in ethyl acetate and water. The aqueous phase was subsequently removed and again briefly mixed with ethyl acetate. The combined organic phases were dried over magnesium sulfate and then filtered and concentrated. The crude product was purified by column chromatography on silica gel (eluent: hexane / ethyl acetate = 4: 1). Yield: 1.6 g. iH NMR (250 MHz, in CDC13: d (ppm) = 1.26 (m, 3H), 3.85 (s, 3H), 4.10-4.23 (m, 2H), 4.90 and 5.12 (2d, together 2H), 6.71 (t, 1H), 6.88 and 7.54 (2t, together 1H), 7.62 (m, 1H), 8.02 (m, 1H).

EXAMPLE 3 2- (2-pyrrolidon-1-yl) ethyl 2- (2-pyrrolidon-1-yl) -2,4-dichlorobenzoate 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzoate (No. ) A solution of 1 g (2.6 mmol) of 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzoyl chloride and 0.5 g (3.8 mmol) of the 2- (2-pyrrolidon-1-yl) ethanol in 20 ml of pyridine, was stirred for approximately hours, then the reaction mixture was concentrated. The residue was treated with 10 ml of water and 20 ml of ethyl acetate. The organic phase was then separated, dried over magnesium sulfate and concentrated. The crude product was purified by column chromatography on solid gel (eluent: initially hexane / ethyl acetate = 1: 1, then ethyl acetate). Yield: 0.8 g.

Precursor 5- (4-chloro-5-difluoromethoxy-l-methyl-lH-pyrazol-3-yl) -2,4-dichlorobenzoyl chloride 20.5 g (160 mmol) of the oxalyl chloride were added dropwise to a solution of 7.7 g (20 mmol) of 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzoic acid in 300 ml of toluene. After stirring for 6 hours at reflux temperature, the reaction mixture was concentrated. Performance: quantitative. iH NMR (250 MHz on CDC13): d (ppm) = 3.97 (s, 3H), 6.72 (t, 1H), 7.66 (s, 1H), 8.21 (s, 1H).

Example 4 5- (4-Chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichloro-benzoic acid 2- (allyloxyimino) ethyl ester (# 005) A solution of 2 g (5 mmoles) of 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzoyl chloride and 0.6 g (5 mmol) of 0-allyl oxime glycollaldehyde in 40 ml of pyridine, heated for 5 hours at 50-60 ° C, then the mixture was concentrated. The residue was taken in ethyl acetate. The obtained solution was washed using 2N hydrochloric acid and a saturated solution of sodium chloride, dried over magnesium sulfate, filtered and then concentrated. The crude product was purified by column chromatography on silica gel (eluent: hexane / ethyl acetate = 1: 1). Yield: 1.2 g. iH NMR (250 MHz, in CDC13): d (ppm) = 3.84 (s, 3H), 4.55-4.66 (m, 2H), 4.91 and 5.12 (2d, together 2H), 5.20 and 5.37 (m, 2H), 5.88-6.08 (m, 1H), 6.71 (t, 1H), 6.92 and 7.60 (2t, together 1H), 7.64 (m, 1H), 8.00 (m, 1H).

Example 5 N- [2- (1, 3-dioxolan-2-yl) ethyl] -N-methyl-5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2 , 4-dichloro-benzamide (No. I? 459) After stirring for 1 hour a solution of 1 g (2.7 mmol) of 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole- 3-yl) -2,4-dichlorobenzoic acid and 0.66 g (4.1 mmol) of 1,1-carbonyldiimidazole, in 20 ml of tetrahydrofuran, 0.55 g (4.1 mmol) of the N- [2- (1-, 3- dioxolan-2-yl) ethyl] -N-methylamine. The mixture was subsequently stirred for a further 16 hours at about 202c. The reaction mixture was then concentrated. The crude product was purified by chromatography on silica gel (eluent: hexane / ethyl acetate = 1: 1). Yield: 0.4 g. In addition to the compounds described above, the following Tables 2 and 3 show more I-derivatives of 5-pyrazolylbenzoic acid, which were prepared or can be prepared as follows: Table 2 Examples of use (herbicidal activity) The herbicidal action of the derivatives I of 5-pyrazolylbenzoic acid was demonstrated by the following greenhouse experiments: The culture vessels used were plastic pots containing marl black earth with approximately 3.0% humus as the substrate The seeds of the test plants were sown in kind per species. In the case of pre-emergence treatment, the active ingredients that were suspended or emulsified in water, were applied directly after sowing by means of fine distribution nozzles. The containers were then covered with transparent plastic caps until the plants had roots. This cover limits the uniform germination of the test plants, unless adversely affected by the active ingredients. For the purposes of post-emergence treatment, the test plants first grew to a plant height of 3 to 15 cm, depending on the form of the rearing, and only then were treated with the active ingredients, which were suspended or emulsified in water. . For this purpose, the test plants were seeded directly and recited in the same containers or they first grew separately as seedlings and were then transplanted into the test vessels a few days before treatment. The application regime for the post-emergency treatment was 0.0156 or 0.0078 kg of i.a. (active ingredient) per ha (hectare). Depending on the species, the plants were kept at a temperature of 10 to 25 C or 20 to 352 C. The trial period was extended over 2 to 4 weeks. During this time, the plants were treated and their responses to individual treatments evaluated. A scale from 0 to 100 was used for the evaluation. 100 means no emergence of the plants or complete destruction of at least the aerial parts, and 0 means that there was no damage or normal growth. The plants used in greenhouse experiments were composed of the following species: At application rates of 0.0156 and 0.0078 kg of i.a. per ha, compound No. IA.003 had a very good action against the aforementioned plants, when applied after emergence.

Examples of use (drying / defoliant activity) The test plants used were young cotton plants with 4 leaves (without cotyledons) that grew under greenhouse conditions (relative atmospheric humidity of 50 to 70%, day / night temperature = 27 / 202C). The young cotton plants were subjected to the foliar treatment at the drop point with the aqueous preparations of the active ingredients (with an addition of 0.15% by weight, based on the dewdrops, of the Plurafec LF® 700 fatty alcohol alkoxylate, which acts as a surfactant agent). The amount of water applied was 1000 liters / hectare (converted). After 13 days, the number of scattered fallen leaves and the degree of defoliation as a percentage were determined. No leaf fell on the untreated control plants.

Claims

1. A 5-pyrazolylbenzoic acid derivative of the formula: where the substituents the following meanings: R 1 is hydrogen, C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, halo C 1 -C 4 alkyl. R 2 is C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkoxy, or C 1 -C 4 haloalkyl thio; R3 is hydrogen, cyano, nitro,. halogen; R4 is halogen; R 5 is cyano, halogen, C 1 -C 4 alkyl, C 1 -C haloalkyl, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy; R6 is -0-R7, -S-R7, -N (R8) -R7 or -N (R8) -0-R7; R7 is -X-C (R9) = N-0-R10, -X-C (R9) = N-0-Z-R10 '-X-0-N = C (R1; L, R12), -X-SO2- 13 or saturated heterocyclyl of 3 to 7 members, or heterocyclyl-C-C4 alkyl; where the heterocycle contains, in addition to methylene members, one to three ring members, selected from the group consisting of three aza bridges and two oxygen or sulfur atoms, and, if desired, one or two groups of methylene of the heterocycle are replaced by carbonyl, thiocarbonyl and / or sulfonyl, it is also possible that the heterocycle is unsubstituted or has attached thereto one to four substituents, each selected from the group consisting of halogen, C-alkyl? ~ C4, alkoxy-C? ~ C4, (C1-C4 alkoxy) carbonyl, (C 1 -C 4 alkyl) carbonyl, (C 1 -C 4 alkyl) carbonyloxy and (C 1 -C 4 alkyl) carbonylamino; R 8 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, C 3 -C 5 alkynyl, C 1 -C 4 alkyl sulphinyl; R 9 is hydrogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio; R! 0 is hydrogen, C1-C-alkyl, C1-C4 haloalkyl, C1-C-cyanoalkyl, di (C1-C4 alkyl) amino-C1-C4 alkyl, C1-C4 alkoxy-C1-alkyl -C4, alkyl-C1-C-thio-C1-C4 alkyl, (C1-C alkyl) carbonyl, (C1-C4 alkoxy) -carbonyl, di (C1-C4 alkyl) -aminocarbonyl, haloalkyl- C1 -C4) carbonyl, C3-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 di (C 1 -C 4 alkyl) amino alkenyl, C 1 -C 4 alkyl-thio-C 3 -C 5 alkenyl, C 3 -C 3 alkynyl C5, C3-C5 haloalkynyl, C3-C7 cycloalkyl, which, if desired, can be attached to one to three alkyloxy radicals, or is phenyl, benzoyl, or 5- or 6-membered heteroaryl, which contains one to three heteroatoms, selected from the group consisting of three nitrogen and one oxygen or sulfur atoms, it being possible for the phenyl and heteroaryl rings to be unsubstituted or have attached to each substitutable ring member one of the following substituents: nitro, cyano, halogen, C1-C4-alkyl, haloalkyl-Ci- C4 or alco-C-C4; R 11, R 12, independently of one another, are hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 4 -C 4 -alkyl-C 1 -C 4 alkenyl-C 3 -C 5 alkenyl, C 3 -C 5 -haloalkenyl, C3-C5 alkynyl, C3-C5 haloalkynyl, C3-C7 cycloalkyl, which, if desired, can be attached to one or three C-C3-alkyl radicals, or are phenyl, which, if desired , each non-substitutable ring member can be attached to one of the following substituents: nitro, cyano, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy, or R 11 and R 12 together with the atom of carbon attached to which they join, form a saturated ring of 3 to 8 members, which, if desired, may also contain methylene members, one or two oxygens, sulfur and / or aza ring members, being possible to the ring is unsubstituted or has one to four C-C4 alkyl radicals attached thereto; R 13 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 4 -C 4 cyanoalkyl, di (C 1 -C 4 alkyl) amino- (C 1 -C 4 alkyl), C 1 -C 4 alkylamino -C1-C), C 1 -C 4 -alkylthio-C 1 -C-alkyl, C 3 -C 5 -alkenyl, C 3 -C 5 -haloalkenyl, di (C 1 -C 4 -alkyl) -3-C5-alkenyl-alkenyl, alkoxy -C1-C4-C3-C5-alkenyl, C, -C4-C3-C3-alkenyl, C3-C5-alkynyl, C3-C5-haloalkynyl, C3-C7-cycloalkyl, which, if desired, can have linked to three C-C3-alkyl radicals, or is phenyl, or is 5- or 6-membered heteroaryl, which contains one to three heteroatoms, selected from the group consisting of three nitrogen atoms and one oxygen atom or of sulfur, it being possible for the phenyl and the heteroaryl ring to be unsubstituted or have attached to each substitutable ring member one of the following substituents: nitro, cyano, halogen, C 1 -C 4 alkyl, haloalkyl-Cι C 4 or alkoxy C1-C4; X and Z, independently of each other, are alkylene-cycloalkyl chains which may be unsubstituted or may have attached thereto one to four substituents, each selected from the group consisting of halogen, C-alkyl? ~ C4, haloalkyl-C? -C4 and alkoxy-C1-C4; and the salts useful in the agriculture of the compounds I.

2. The use of the derivatives I of 5-pyrazolylbenzoic acid, and its salts useful in agriculture, as claimed in claim 1, as herbicides or for desiccation / defoliation of plants.

3. A herbicidal composition, comprising a herbicidally active amount of at least one 5-pyrazolylbenzoic acid derivative of the formula I, or at least one useful agricultural salt of I, as claimed in claim 1, and at least one inert carrier, liquid and / or solid and, if desired, at least one surfactant.

4. A composition for drying and / or defoling plants, comprising an amount of at least one derivative of 5-pyrazolylbenzoic acid, of formula I, or at least one salt useful in agriculture of I, as claimed in claim 1, which acts as a desiccant and / or defoliant, and at least one inert carrier, liquid and / or solid and, if desired, at least one surfactant.

5. A process for the preparation of herbicidally active compositions, which comprises mixing a herbicidally active amount of at least one 5-pyrazolylbenzoic acid derivative of the formula I, or at least one useful agricultural salt of I, as claimed in Claim 1, and at least one inert carrier, liquid and / or solid and, if desired, at least one surfactant.

6. A process for the preparation of compositions that act as desiccants and / or defoliants, which comprises mixing an amount of at least one 5-pyrazolylbenzoic acid derivative of the formula I, or at least one useful salt in agriculture of I, as claimed in claim 1, which acts as a desiccant and / or defoliant, and at least one inert carrier, liquid and / or solid and, if desired, at least one surfactant.

7. A method for controlling unwanted vegetation, which comprises allowing a quantity, herbicidally active, of at least one derivative of 5-pyrazolylbenzoic acid, of formula I, or at least one useful salt in agriculture of I, as claim in claim 1, act on the plants, their environment or their seeds.

8. A method for drying and / or defoling plants, which comprises allowing an amount of at least one derivative of 5-pyrazolylbenzoic acid, of formula I, or at least one useful salt in agriculture of I, as claimed in the reivindicacióh 1, act as a desiccant and / or defoliant on plants. SUMMARY OF THE INVENTION Derivatives I of 5-pyrazolylbenzoic acid: wherein: R1 is H, C1-C4 alkyl, cyano-C1-C4 alkyl, halo-C1-C4 alkyl; R 2 is C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkoxy, or C 1 -C 4 haloalkyl thio; R3 is H, CN, N0, halogen; R4 is halogen; R 5 is CN, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy, R 6 is -0-R 7, -S-R 7, -N (R 8) -R7 or -N (R8) -0-R7; R7 is -X-C (R9) = N-0-R10, R12), -X-S02-Ri3 or heterocyclyl, unsubstituted or substituted, from 3 to 7 members, or heterocyclyl-C-C4-alkyl; the heterocycle contains, in addition to methylene members, one to three ring members, selected from the group consisting of three aza bridges and two oxygen or sulfur atoms, and, if desired, one or two groups of methylene of the heterocycle are replaced by -CO-, -CS- and / or -S02-; R 8 is H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, C 3 -C 5 alkynyl, C 1 -C 4 alkylsulfonyl; R 9 is H, CN, C 1 -C a alkyl, 3100x1-02-04 ° C 1 -C 4 alkylthio; R 10 is H, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, cyanoalkyl-cl 4 ', di (C 1 -C 4 alkyl) amino-C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 1 alkoxy C4, C 1 -C 4 alkylthio-C 1 -C 4 alkyl, (C 1 -C 4 alkyl) carbonyl, (C 1 -C 4 alkoxy) carbonyl, di (C 1 -C 4 alkyl) aminocarbonyl, haloalkyl C ? ~ C4) carbonyl, C3-C5 alkenyl, C3-C5 haloalkenyl, di (C 1 -C 4 alkyl) amino-C 3 -C 5 alkenyl, C 1 -C 4 alkoxy-C 3 -C 5 alkenyl, C 1 -C 8 alkenyl C4-thio-C3-C5-alkenyl, C3-C5-alkynyl, C3-C5-haloalkynyl, C3-C7-cycloalkyl, unsubstituted or substituted, phenyl, benzoyl or a 5- or 6-membered heteroaryl, having 1 to 3 heteroatoms; R 11, R 12, are H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, C 3 alkynyl C5, C3-C5 haloalkynyl, C3-C7 cycloalkyl, unsubstituted or substituted, or phenyl, or R11 + R12 together with the carbon atom to which they bind, form a saturated ring of 3 to 8 members, which, if desired, it may also contain methylene members, one or two oxygens, sulfur and / or aza ring members; R 13 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 cyanoalkyl, di (C 1 -C 4 alkyl) amino- (C 1 -C 4 alkyl) -C 1 -C 4 alkoxy-C 1 -C 4 alkyl ), alkylthio-C? -C4-C-C4-alkyl, C3-C5-alkenyl, C3-C5-haloalkenyl, di (C1-C4-alkyl) -3-C5-amino-alkenyl, C1-C4-alkoxy - C3-C5alkenyl, C12-C5alkyl-C3-C5alkenyl, C3-C5alkynyl, C3-C5-haloalkynyl, C3-C7-cycloalkyl, unsubstituted or substituted, phenyl or a 5- or 6-membered heteroaryl , which has 1-3 heteroatoms; X, Z is a C1-C4 alkylene chain, unsubstituted or substituted; and its salts; they are used as herbicides; to dry / defoliate plants.