MXPA99000958A - Substituted 1-(3-pyrazolyl)-pyrazoles - Google Patents

Abstract

The invention relates to new substituted 1-(3-pyrazolyl)-pyrazoles having general formula (I) in which R1, R2, R3, R4, R5 and R6 have the meanings indicated in the description, processes for the production thereof and their use as herbicides.

Description

l- (3-PIRAZ0LIL) -PIRAZ0LES SUBSTITUTED WITH EFFECT HERBICIDE AND INTERMEDIATE PRODUCTS FOR ITS OBTAINING FIELD OF THE INVENTION The invention relates to new substituted 1- (3-pyrazolyl) -pyrazoles, processes for their preparation and their use as herbicides.

DESCRIPTION OF THE PREVIOUS TECHNIQUE Potential substituted pyrazoylpyrazole herbicides, such as for example the compound 4-cyano-5-methyl-1- (4-chloro-5-difluoromethoxy-1-methyl-pyrazol-3-yl) -pyrazole, have already become known. 4'-chloro-5'-difluoromethoxy-1 ', 5'-dimethyl- (1,3'-bis-lH-pyrazole) -4-carbonitrile, (see EP 542388, WO 94/08999). These compounds, however, have not acquired any special significance.

DETAILED DESCRIPTION OF THE INVENTION New substituted 1- (3-pyrazolyl) -pyrazoles of the general formula (I) have now been found REF .: 29272 - - in which R1 means alkyl having 1 to 6 carbon atoms, optionally substituted by hydroxy, by cyano, by carboxy by halogen, by alkoxy with 1 to 4 carbon atoms, by alkyl-carbonyl with 1 to 4 carbon atoms or by alkoxy -carbonyl with 1 to 4 carbon atoms or means cycloalkyl with 3 to 6 carbon atoms, R2 means hydrogen, hydroxy, halogen, cyano, nitro, N (RUR12) or means alkyl, aralkyl, alkoxy or alkylthio substituted, where appropriate, by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms, with respectively 1 to 6 carbon atoms in the alkyl part, R3 means hydroxy , cyano, nitro or means a radical, substituted, if appropriate by cyano, by halogen or alkoxy with 1 to 4 carbon atoms, from the group consisting of alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl respectively 1 to 6 carbon atoms, or R3 means a radical, substituted, if appropriate, by halogen, of the series consisting of alkenyl or alkynyl with 2 to 6 carbon atoms, R4 is hydrogen, halogen, or alkyl with 1 to 6 carbon atoms; carbon atoms optionally substituted by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms, R5 means hydrogen, cyano, nitro, amino or halogen, means alkyl having 1 to 6 carbon atoms, optionally substituted by cyano , by hydroxy, by halogen or by alkoxy with 1 to 4 carbon atoms, means the grouping - (CH2) m-0-R7, the grouping - (CH2) mS (0) n-R8, the grouping - (CH? Jm-CO-R9, the grouping - (CH2) m-CO-0-R10, the grouping - (CH2) m-CQ-N (Rn, R12), R6 means hydrogen, cyano, amino, halogen, means alkyl with 1 to 6 carbon atoms, optionally substituted by cyano, by hydroxy, by carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxycarbonyl having 1 to 4 carbon atoms, R6 further denotes alkenyl or alkynyl with 2 to 6 carbon atoms respectively, optionally substituted by cyano or by halogen or means alkoxymethyleneamino with 1 to 4 carbon atoms in the group alkoxy, R6 further denotes phenyl optionally substituted by nitro, by cyano, by halogen, by alkyl with 1 to 4 carbon atoms, by halogenalkyl with 1 to 4 carbon atoms, by alkoxy with 1 to 4 carbon atoms or by halogenalkoxy with 1 to 4 carbon atoms, R6 further denotes pyrrolyl, pyrrolidinyl, piperidinyl or morpholinyl substituted, where appropriate, by alkyl with 1 to 4 carbon atoms, means the grouping - (CH2) m_ R12, means the grouping - (CH2) m-0-R7, the grouping - (CH2) mS (0) n-R8 / the grouping - (CH2) m- CO-R, the grouping - (CH2) m-C0 -0-R, the grouping - (CH2) mN (Ru, R12) or the grouping (CH2) m-CQ-N (Ru, R12) or the grouping - (CH2) m-N = CH-R12, R6 also means one of the following groupings - - which are respectively substituted, if appropriate, by halogen or by alkyl with 1 to 4 carbon atoms, R7 is hydrogen, means alkyl having 1 to 6 carbon atoms, optionally substituted by cyano, by carboxy, by nitro, by hydroxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxycarbonyl with 1 to 4 carbon atoms, R7 also means alkenyl or alkynyl with 2 to 6 carbon atoms, respectively substituted optionally by cyano or by halogen, R7 further denotes alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl with respectively up to 6 carbon atoms, optionally substituted by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms, or R7 furthermore cycloalkyl or cycloalkylalkyl with respectively 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, optionally substituted by cyano, carboxy, halogen or alkyl with 1 to 4, respectively carbon atoms, R8 means alkyl having 1 to 6 carbon atoms, optionally substituted by cyano, by carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms; arbono or alkoxycarbonyl having 1 to 4 carbon atoms, or means alkenyl or alkynyl with respectively 2 to 6 carbon atoms substituted, where appropriate, by cyano or by halogen, R9 means hydrogen, means alkyl having from 1 to 6 carbon atoms; carbon optionally substituted by cyano, by carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxy-carbonyl with 1 to 4 carbon atoms or means alkenyl or alkynyl with respectively 2 to 6 carbon atoms, substituted respectively, where appropriate, by cyano or by halogen, R10 is hydrogen, means alkyl having 1 to átomos carbon atoms, optionally substituted by cyano, carboxy, halogen, alkoxy with 1 to 4 carbon atoms or by alkoxycarbonyl with 1 to 4 carbon atoms, or means alkenyl or alkynyl with respectively 2 to 6 carbon atoms - substituted respectively by cyano or by halogen, Ru means hydrogen or milo, means alkyl with 1 to 6 carbon atoms, optionally substituted by cyano, by carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxycarbonyl having 1 to 4 carbon atoms, Ru further denotes alkenyl or alkynyl with respectively 2 to 6 carbon atoms substituted, where appropriate, by cyano or by halogen or means a radical, respectively substituted given by cyano, by halogen or by alkoxy with 4 carbon atoms, of the series consisting of alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl alkylsulfonyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, cycloalkylaminocarbonyl or cycloalkylsulfonyl with respectively up to 6 carbon atoms in the alkyl group or in the cycloalkyl group, R 11 further denotes hetarylcarbonyl or arylcarbonyl, R 12 denotes hydrogen, carbamoyl, means alkyl or alkoxy with 1 to 6 carbon atoms, optionally substituted by cyano, carboxy, halogen, alkoxy with 1 to 4 carbon atoms or alkoxycarbonyl with 1 to 4 carbon atoms, R12 also means alkenyl or alkynyl with 2 to 6 carbon atoms respectively substituted, where appropriate, by cyano or by halogen or means a radical substituted respectively by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms of the series consisting of alkoxy, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminthiocarbonyl, dialkylaminthiocarbonyl, alkylsulfonyl, cycloalkyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, cycloalkylaminocarbonyl or cycloalkylsulfonyl with respectively up to 6 carbon atoms in the alkyl groups or in the groups cycloalkyl or means phenylalkyl with 1 to 2 át carbon atoms, phenyl-alkylcarbonyl having 1 to 2 carbon atoms, phenoxy, benzoyl or furanyl substituted respectively by fluorine or chlorine, R12 further denotes hetarylcarbonyl or arylcarbonyl, Q means O or S, m means the numbers 0, 1, 2 or 3 and n means the numbers 0, 1 or 2. The new substituted 1- (3-pyrazolyl) -pyrazoles of the general formula (I) are obtained when the hydrazinopyrazoles of the general formula (II) - - R2 (II) NH / NH2 in which R1, R2 and R3 have the meanings indicated above, they are reacted with the cyanoalkenyl ethers of the general formula (III) in which R 4 and R 5 have the meaning indicated above, if appropriate in the presence of an auxiliary agent of the reaction and, if appropriate, in the presence of a diluent and, if appropriate, they are carried out in the compounds of the formula (I) ), obtained in this way, other transformations, according to usual methods, in the field of - the definitions of the abovementioned substituents. The compounds of the general formula (I) can be converted according to customary methods into other compounds of the general formula (I) according to the definition of the substituents indicated above, for example by customary alkylation, acylation or sulfonylation reactions (for example R5) : CN? COOH, CONH2, CSNH2; R6; NH2? NHC2H5, NHCOCH3, NHS02CH3) - see also Preparation Examples. The new substituted 1- (3-pyrazolyl) -pyrazoles of the general formula (I) are characterized by a potent herbicidal activity. They also show good compatibility against the most important crop plants, such as for example wheat, barley, soybean and sugar beet. In the definitions the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkynyl - even in combination with heteroatoms, such as in alkoxy or in alkylthio - are respectively straight-chain or branched chain. In general halogen means fluorine, chlorine, bromine or iodine, preferably means fluorine, chlorine or bromine, especially fluorine or chlorine.

The object of the invention are preferably compounds of the formula (I), in which R 1 is methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl respectively substituted by hydroxy, by cyano, by carboxy, by fluorine, by chlorine, by methylene, by ethoxy, by acetyl, by propionyl, by methoxycarbonyl or by ethoxycarbonyl, R2 means hydrogen, hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, N (RnR12) or means methyl, ethyl, n-propyl, i-propyl, n-, i-, s- or t-butyl, methoxy or ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio or phenyl-alkyl with 1 to 4 carbon atoms substituted, where appropriate, by cyano, fluorine, chlorine, methoxy or ethoxy, R3 means hydroxy, cyano, nitro, means methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i- propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulphonyl, n- or i-propylsulphonyl, each optionally substituted by cyano, by fluorine, by chlorine, by methoxy or by ethoxy, or means a residue substituted, respectively, by fluorine, chlorine or bromine, of the series consisting of ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, R4 means hydrogen, fluorine, chlorine, bromine or means a radical optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy in the series consisting of methyl, ethyl, n- or i-propyl, n-, i-, t-butyl, R5 means hydrogen, cyano, nitro, amino, fluorine, chlorine, bromine, means a radical optionally substituted by cyano, hydroxy, fluorine, chlorine, methoxy or ethoxy the series consisting of methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, means the grouping - (CH2) m-0-R7, the grouping - (CH2) mS (0 ) n-R8, the grouping - (CH2) m_ CO-R, the grouping - (CH2) m-CO-0-R, the grouping - (CH2) m-CQ-N (Rp, R12), R6 means halogen , cyano, amino, fluorine, chlorine, bromine, means a radical, substituted, if appropriate, by cyano, hydroxy, carboxy, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, by ethoxycarbonyl, by n- or i-propoxycarbonyl of the series formed by ethyl methyl, n- or i-propyl, n-, i-, s- or t-butyl, - - R6 also means a radical substituted respectively by cyano, by fluorine, by chlorine or by bromine, of the series consisting of ethenyl, propenyl, butenyl, ethynyl, propinyl or butynyl, means methoxymethyleneamino or ethoxymethyleneamino, R6 further denotes phenyl optionally substituted by nitro, by cyano, by fluorine, by chlorine, by bromine, by methyl, by ethyl, by n- or i-propyl, by n-, i-, s- or t-butyl, by trifluoromethyl, by methoxy, by ethoxy, by n- or i-propoxy, by n-, i-, s- or t- butoxy, by difluoromethoxy, or by trifluoromethoxy, means pyrrolyl pyrrolidinyl, piperidinyl, or morpholinyl, respectively substituted, if appropriate, by methyl and / or ethyl, means the grouping - (CH2) m -R12 means the grouping - (CH2) m-0 -R7, the grouping - (CH2) m- S (0) "- R8, the grouping - (CH2) m-C0-R9, the grouping - (CH2) m-CO-0-R10, the grouping - (CH2) ) m- N (Rn, R12), the grouping - (CH2) m-CQ-N (Rn, R12) or the grouping - (CH2) m-N = CHR12, R6 also means one of the following groupings, - which are respectively substituted, if appropriate, by fluorine, chlorine, bromine, methyl or ethyl, R7 is hydrogen, means methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted respectively by cyano, by carboxy, by nitro, by hydroxy, by fluorine, by chlorine, by methoxy, by ethoxy, by n- or i-propoxy, by methoxycarbonyl, by ethoxycarbonyl, by n- or i-propoxycarbonyl R7 also means ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl substituted, where appropriate, by cyano, fluorine, chlorine or bromine, R7 is also acetyl, propionyl, n- or i-butyroyl methoxycarbonyl, ethoxycarbonyl, - or i- propoxycarbonyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butylsulfonyl respectively substituted, where appropriate, by cyano, by fluorine, by chlorine, by methoxy, by ethoxy, by n- or i-propoxior R further denotes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl substituted respectively where appropriate by cyano, carboxy, fluorine, chlorine, methyl or ethyl, R8 means methyl, ethyl, - or i-propyl, n-, i-, s- or t-butyl substituted, where appropriate, by cyano, carboxy, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, for ethoxycarbonyl, for n- or i-propoxycarbonyl, or R8 further means ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl substituted, where appropriate, by cyano, fluorine, chlorine or bromine, R9 means hydrogen, means methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by cyano, carboxy, fluorine, chlorine, methoxy, ethoxy, n- or i -propoxy, by methoxycarbonyl, by ethoxycarbonyl, by n- or i- propoxycarbonyl, or R means ad more preferably ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl substituted, where appropriate, by cyano, fluorine, chlorine or bromine, R10 means hydrogen, means methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl substituted respectively by cyano, by carboxy, by fluorine, by chlorine, by methoxy, by ethoxy, by n- or i-propoxy, by methoxycarbonyl, by ethoxycarbonyl, by n- or i- propoxycarbonyl, or R 10 further denotes ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl substituted, where appropriate, by cyano, by fluorine, by chlorine or by bromine, R 11 means hydrogen or formyl, means methyl, ethyl, n- or i- propyl, n-, i-, s- or t-butyl optionally substituted by cyano, carboxy, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, by n- or i-propoxycarbonyl, R 11 also means substituted propenyl, butenyl, propinyl or butynyl respectively In the case given by cyano, by fluorine, by chlorine or by bromine, or Ru also means acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i- - propoxycarbonyl, methylaminocarbonyl, ethyloxycarbonyl, n- or i-propylaminocarbonyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butylsulfonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylaminocarbonyl, cyclohexylaminocarbonyl, cyclopropylsulfonyl , cyclobutylsulfonyl, cyclopentylsulphonyl, cyclohexylsulfonyl respectively substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or by i-propoxy or thiophenylcarbonyl, R12 means hydrogen, carbamoyl, means methyl, ethyl n- or i-propyl, n-, i-, s- or t-butyl substituted, where appropriate, by cyano, carboxy, fluorine, chlorine, methoxy, ethoxy, n- or ip ropoxy, by methoxycarbonyl, by ethoxycarbonyl, by n- or i-propoxycarbonyl, R12 also means propenyl, butenyl, propinyl or butynyl substituted, if appropriate by cyano, by fluorine, by chlorine or by bromine, or R12 means cyclopropyl, cyclobutyl cyclopentyl or cyclohexyl optionally substituted by methyl, R12 further denotes methoxy, ethoxy, acetyl propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylamino, dimethylamino, methylaminocarbonyl, ethylaminocarbonyl, n- i- propylaminocarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylchloroethyl, dimethylaminocarbonyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butylsulfonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylaminocarbonyl, cyclohexylaminocarbonyl, cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopen tyl sulfonyl, cyclohexyl sulfonyl, benzoyl, furoyl, phenoxy, thiophenylcarbonyl, o-, i-, p-chlorobenzylcarbonyl substituted, where appropriate, by cyano, by fluorine, by chlorine, by methoxy, by ethoxy, by n- or i-propoxy or means o-, m-, p-chlorobenzyl, Q means O or S, m means the numbers 0, 1, 2 or 3, and n means the numbers 0, 1 or 2. The invention relates especially to the compounds of the formula (I), wherein R 1 is methyl, ethyl, n- or i-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, respectively substituted, if appropriate, by cyano, fluorine, chlorine, methoxy or ethoxy, R 2 is hydrogen, hydroxy, fluorine , chlorine, bromine, cyano, nitro, N (RnR12) or means methoxy, ethoxy, no i-propoxy, methylthio, ethylthio, n- or i-propylthio, methyl, ethyl, n- or i-propyl, n-, i - s- or t-butyl, benzyl, phenylethyl, phenyl-1-prop-2-yl, phenyl-1-yl-3-yl, phenyl-l-but-2-yl, phenyl-l-but-3-yl , phenyl-l-but-4-yl, phenyl-1- (1-methyl) -prop-3-yl, phenyl-1- (2-methyl) -pr op-3-yl, phenyl-1- (3-methyl) -prop-3-yl, respectively substituted, if appropriate, by cyano, by fluorine, by chlorine, by methoxy or by ethoxy, R3 means methoxy, cyano, nitro or means methyl, ethyl, n- or i-propyl substituted respectively by cyano, by fluorine, by chlorine, by methoxy or by ethoxy, R4 means hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl optionally substituted by cyano, by fluorine, by chlorine, by methoxy or by ethoxy, R5 means hydrogen, cyano, fluorine, chlorine, bromine, means methyl, ethyl, n- or -propyl substituted respectively by cyano, by fluorine, by chlorine, by methoxy or by ethoxy, respectively means the grouping - (CH2) m-0-R7, the grouping - (CH2) m- S (0) n-R8 , the grouping - (CH2) m-C0-R9, the grouping - (CH2) m-CO-0-R10, the grouping - (CH2) m- CQ-N (RU, R12), R6 means hydrogen, cyano, amino, fluorine, chlorine, bromine, means methyl, ethyl, n- or i-propyl substituted respectively by cyano, by carboxy, by fluorine, by chlorine, by methoxy, by ethoxy, by n- or i-propoxy, by methoxycarbonyl or by ethoxycarboni R6 also means propenyl, butenyl, propynyl or butynyl substituted, where appropriate, by cyano, fluorine, chlorine or bromine, R6 further denotes ethoxymethyleneamino or ethoxymethyleneamino, R6 further denotes phenyl optionally substituted by nitro, by cyano by fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy, R6 also represents pyrrolyl, pyrrolidinyl, piperidinyl or morpholinyl, respectively substituted by methyl and / or or by ethyl, means the grouping - (CH2) mR means the grouping - (CH2) m-R7 the grouping - (CH2) m- - - S (0) n-R8, the grouping - (CH2) m-C0- R9, the grouping - (CH2) m-C0-0-R10, the grouping - (CH2) m- N (Rn, R12), the grouping - (CH2) m-CQ-N (Ru, R12) or the grouping - (CH2) mN = CHR12, R7 means hydrogen, means methyl, ethyl, n- or i-propyl substituted respectively, optionally cyano, carboxy, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, means propenyl, butenyl, propynyl or butynyl, optionally substituted by cyano, by fluorine, by chlorine or by bromine, means acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or ethylsulfonyl respectively substituted, if appropriate, by cyano, fluorine, chlorine, methoxy or ethoxy, or R7 further denotes cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl substituted, where appropriate, by cyano, by fluorine, by chlorine, by methyl or ethyl, R8 means methyl, ethyl, n- or i-propyl substituted, where appropriate, by cyano, by fluorine, by chlorine, by methoxy, by etox i, by methoxycarbonyl or by ethoxycarbonyl, or R8 means also propenyl, butenyl, propynyl or butynyl substituted, where appropriate, by cyano, by fluorine, by chlorine or by bromine, R9 means hydrogen, means methyl, ethyl, n- or i- propyl optionally substituted by cyano, by fluorine by chlorine, by methoxy, by ethoxy, by methoxycarbonyl or by ethoxycarbonyl, or by R10 means, in addition, propenyl, butenyl, propinyl or butynyl substituted, where appropriate, by cyano, by fluorine, by chlorine or by bromine, R10 means hydrogen, means methyl, ethyl, n- or i-propyl substituted respectively by cyano, by fluorine, by chlorine, by methoxy, by ethoxy, by methoxycarbonyl or by ethoxycarbonyl, or R10 also means propenyl, butenyl, propynyl or butynyl substituted, where appropriate, by cyano, fluorine, chlorine or bromine, R 11 means hydrogen or formyl, means methyl, ethyl, n- or i-propyl, substituted on the If given by cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, Ru also means propenyl, butenyl, propinyl or butynyl substituted, where appropriate, by cyano, fluorine, chlorine or bromine, respectivelyor Ru further denotes acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, methylsulfonyl, ethylsulphonyl, cyclopropylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopentyloxycarbonyl, cyclohexyl-oxycarbonyl, cyclopentylaminocarbonyl, cyclohexyl-aminocarbonyl, cyclopropylsulfonyl, cyclopentyl-sulfonyl, cyclohexylsulfonyl or thiophenylcarbonyl each substituted, where appropriate, by cyano, fluorine, chlorine, methoxy or ethoxy, R12 means hydrogen, means methyl, ethyl, n- or i-propyl substituted, where appropriate, by cyano, by fluorine, by chlorine, by methoxy, by ethoxy, by methoxycarbonyl or by ethoxycarbonyl, R12 further denotes propenyl, butenyl, propynyl or butynyl substituted, if appropriate, by cyano, fluorine, chlorine or bromine, or R12 further denotes methylcyclopropyl, cyclopropyl, cyclobutyl or cyclohexyl, R12 also means methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylamino, dimethylamino, methylaminocarbonyl, ethylaminocarbonyl, ethoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonyl-chloroethyl, dimethylaminocarbonyl, methylsulfonyl, ethylsulfonyl, cyclopropylcarbonyl, cyclopentyl- - - carbonyl, cyclohexylcarbonyl, cyclopentyloxy- carbonyl, cyclohexyloxycarbonyl, carbonyl ciclopentilamino-, cyclohexylaminocarbonyl, cyclopropylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, benzoyl, furoyl, phenoxy, thiophenylcarbonyl each substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or p-chlorobenzylcarbonyl, Q means 0 or S, m means numbers 0, 1, 2 or 3, n means the numbers 0, 1 or 2. The definitions of the remains given above in a general way or in the preferred ranges are valid both for the final products of the formula (I) and also for the corresponding manner for the respective compounds of starting or intermediate products necessary for the preparation. These definitions of the remains can be combined arbitrarily with each other, even also between the preferred ranges indicated. Examples of the compounds according to the invention of the formula (I) have been indicated in the following groups: Group 1 R1, R2 and R3 have in this case, in an exemplary manner, the meanings indicated in the following list: - - Group i (Continuation) - - Group 1 (Continuation) - - Group 1 (Continuation) Group l (Continued) group 1 (Continued) Group l (Continued) Group l (Continued) SdB & (Continuation) Group 1 (Continued) Group 2 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 3 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 4 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Team 5 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 6 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 7 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 8 COOCH, Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 9 COOCH (CH3) 2 Here, R have in this case in an exemplary way the meanings indicated above in Group 1.

Group 10 COOCH, Here, R1, and R have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 11 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 12 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- Group 13 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 14 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 15 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 16 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 17 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 18 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- Group 19 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 20 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 21 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 22 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 23 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 24 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 25 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 26 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 27 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 28 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 29 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 30 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 31 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 32 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 33 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 34 Here, R1, R have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 35 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 36 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 37 Here, R1, R2 and R3 have in this case, in an exemplary manner, the meanings indicated above in Group 1.

Group 38 Here, R1, and R have in this case in an exemplary manner the meanings indicated above in Group 1.

- - GROUP 39 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 40 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 41 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 42 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 43 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 44 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 45 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 46 Here, R1, and R have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 47 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 48 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 49 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 50 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 51 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 52 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 53 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 55 R- Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 56 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 57 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 58 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 59 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 60 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 61 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 62 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 63 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 64 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 65 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 66 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 67 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- - Group 68 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 69 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

- Group 70 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

Group 71 Here, R1, R2 and R3 have in this case in an exemplary manner the meanings indicated above in Group 1.

If, for example, 5-difluoromethylthio-1,4-dimethyl-3-hydrazinopyrazole and ethoxymethylene-malonitrile are used as starting materials, the development of the reaction in the case of the process according to the invention can be schematized by means of the The following formulas: The hydrazinopyrazoles to be used as starting materials in the process according to the invention for the preparation of the compounds of the formula (I) are generally defined by the formula (I). In formula (II), R.sup.1, R.sup.2 and R.sup.3 preferably have or especially those meanings which have already been mentioned above in a preferred manner or, more preferably, for R.sup.1, R.sup.2 and R.sup.3 in relation to the description of the compounds of the invention. Formula (I) according to the invention.

- The hydrazinopyrazoles of the general formula (II) are not yet known in the literature; as new products are also an object of the present application. The novel hydrazinopyrazoles of the general formula (II) are obtained if pyrazoles of the general formula (IV) are reacted R 'R' N R3 (IV) N R4 wherein R1, R2 and R3 have the meaning indicated above, with an alkali metal nitrite, for example with sodium nitrite or with potassium nitrite, in the presence of an acid, such as for example hydrochloric acid and in the presence of a For example, in the case of a diluent, such as water, at temperatures between -20 ° C and + 20 ° C, the reaction mixture is subsequently reacted with zinc (II) chloride (dihydrate), if appropriate in the presence of a acid, such as for example hydrochloric acid, at temperatures between -20 ° C and +20 ° C and finally it is reacted with sodium hydroxide solution at temperatures between -20QC and + 20 ° C (see Preparation Examples). The pyrazoles, necessary as starting materials, of the general formula (IV) are only partially known and / or can be prepared according to known processes (see WO 94/08999, Examples of Preparation) . These can be prepared, for example, according to the scheme of the following formulas: - - NH, SOCI, '-t COCÍ NaOH / Br, The cyanoalkenyl ethers to be used as starting materials in addition in a process according to the invention for the preparation of the compounds of the formula (I) are generally defined by the formula (III). In the formula (III), R 4 and R 5 have preferably or especially those meanings which have already been mentioned above in a preferred manner or, more preferably, for R 4 and R 5 in connection with the description of the compounds of the formula I) according to the invention; in this case R is preferably alkyl having 1 to 4 carbon atoms, especially methyl or ethyl. The starting compounds of the formula (III) are known and / or can be prepared according to known processes. Suitable diluents for carrying out the process according to the invention are, in particular, inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; ketones, such as acetone, butanone or ethyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- -formanilide, N-methyl-pyrrolidone or hexamethylphosphorustriamide; Such esters are such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water. As the reaction auxiliaries for the process according to the invention, the usual inorganic or organic acid bases or acceptors are generally suitable. These preferably include acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates of alkali metals or alkaline earth metals, such as, for example, sodium, potassium or calcium acetate, lithium amide, sodium, potassium or sodium amide. calcium, sodium, potassium or calcium carbonate, sodium, potassium or calcium bicarbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, methanolate, ethanolate, n- or i-propanolate, n-, i-, s- or sodium or potassium t-butanolate; furthermore basic organic nitrogenous compounds such as for example trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl- -dicyclohexylamine, N, N-dimethyl-aniline, N, N- dimethylbenzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2, 2, 2] -octane (DABCO), 1,5-diazabicyclo [4, 3, 0] -non-5-ene (DBN), or 1,8-diazabicyclo [5, 4, 0] -undec-7-ene (DBU). The reaction temperatures in carrying out the process according to the invention can vary within wide limits. In general, work is carried out at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C. The process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under higher pressure or at a lower pressure - generally comprised between 0.1 bar and 10 bar. For carrying out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of an auxiliary agent of the reaction and the reaction mixture is generally stirred for several hours at the required temperature.

Working up is carried out by customary methods (see the Preparation Examples). The active compounds according to the invention can be used as defoliants, desiccants, herbicidal agents and especially as weed killers. By weeds, in the broadest sense, we must understand the plants that grow in places where they are unwanted. The fact that the substances according to the invention act as total or selective herbicides depends essentially on the amount used. The active compounds according to the invention can be used, for example, in the following plants: Bad dicotyledonous herbs of the following classes: Sinapis Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Geleopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacu.

Dicotyledonous crops of the following classes: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Bad monocotyledonous herbs of the following kinds: Echinochloa Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Oats, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Cultures of monocotyledonous classes: Oryza, Zea, Triticum, Hordeum, Avena, Sécale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium. The use of the active compounds according to the invention is, however, not limited in any way to these classes, but they also extend to other plants in the same way. The compounds are suitable, depending on the concentration, to completely combat the weeds, for example, in industrial and road installations and in roads and squares, with and without tree growth. In the same way, compounds can be used to control weeds in permanent crops, for example, in forest facilities, ornamental trees, fruit trees, vineyards, citrus trees, walnut trees, bananas, coffee, tea, rubber oil palms, cocoa, berries and hops, on ornamental and sports paths and on surfaces for meadows and to selectively control weeds in mono-annual crops. The compounds according to the invention of the formula (I), according to the invention, are especially suitable for the control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous cultures both in the pre-emergence procedure and in the post-emergence procedure. The active compounds can be converted into the customary formulations, such as solutions, emulsions, sprayable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compound , as well as micro-encapsulations in polymeric materials. These formulations are prepared in known manner, for example, by mixing the active ingredients with extender materials, that is, with liquid solvents and / or solid excipients, where appropriate, using surfactants, that is, emulsifiers and / or dispersants and / o foam generating means.

In the case of using water as a filler, it is also possible, for example, to use organic solvents as auxiliary solvents. Particularly suitable liquid solvents are aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons, such as chlorobenzenes., chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane, or paraffins, for example, fractions of crude petroleum, mineral and vegetable oils, alcohols such as butanol, or glycol, as well as their esters and ethers, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water. Suitable solid excipients are, for example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earths and molten synthetic minerals, such as silicic acid, highly dispersed , aluminum oxide and silicates, as solid excipients for granulates come into consideration: for example, natural-broken and fractionated minerals such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granules of inorganic and organic flours, as well as as granulates of organic materials, such as sawdust, coconut husks, corn ears and tobacco stems; suitable emulsifiers and / or foam generators are, for example, nonionic and anionic emulsifiers, such as polyoxyethylenated esters of fatty acids, for example, alkylaryl polyglycol ether, alkylsulfonates, alkyl sulfates, arylsulfonates, as well as albumin hydrolysates; Suitable dispersants are, for example, sulfitic leaching of lignin and methylcellulose. Adhesives such as carboxymethylcellulose, natural and synthetic polymers powdery, granulated or in the form of latex, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids can be used in the formulations. , Other additives can be mineral and vegetable oils. Dyes, such as inorganic pigments, for example, iron oxide, titanium oxide, ferrocyanic blue and organic dyes, such as alizarin dyes, metal azo and de-phthalocyanine dyes and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The formulations generally contain between 0.1 to 95 weight percent active product, preferably between 0.5 and 90%. The active compounds according to the invention can be used as such or in their formulations also for combating weeds in admixture with herbicides, ready-to-use preparations or tank mixtures being possible. Suitable mixtures are known herbicides, for example acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron (-methyl). , bentazon, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bromobutide, bromophenoxy, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron , clethodim, clodinafop (-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam (-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (butyl), 2,4-D, 2,4-DB, 2, 4-DP, desmedipham, diallate, dicamba, diclofop (-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalflurali n, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, framprop (-isopropyl), flamprop (-isopropyl-L), flamprop (-methyl), flazasulfuron, fluazifop (-butyl), flumetsulam, flumiclorac ( -pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate (-ammonium), glyphosate (-isopropyl-ammonium), halosafen, haloxyfop (-ethoxyethyl), hexazinone, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, methoxuron, metsulfuron (-methyl), metribuzin, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiaz on, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron (-methyl), prometryn, propachlor, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac ( -sodium), quinchlorac, quinmerac, quizalofop (-ethyl), quizalofop (-p-tefuril), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfo-meturon (-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron. A mixture with other known active substances is also possible, such as fungicides, insecticides, acaricides, nematicides, protective substances against ingestion by birds, nutrient substances of the plants and means for improving the structure of the ground. The active compounds can be used as such, in the form of their formulations or of the forms of application prepared therefrom by further dilutions, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The use is carried out in the usual way, for example, by watering, spraying, spraying, spreading. The active products according to the invention can be applied both before and after the outbreak of the plants. They can also be incorporated into the soil before sowing. The quantities of active product used can vary within a wide range. These depend fundamentally on the type of the desired effect. In general, the amounts used are between 1 g and 10 kg of active product per hectare of land surface, preferably between 5 g and 5 kg per hectare. The preparation and use of the active substances according to the invention is apparent from the following examples.

Preparation examples Example 1 Combine 7.8 g (40 mmol) of 5-difluoromethoxy-3-hydrazino-1,4-dimethyl-pyrazole in 100 ml of ethanol, with 5.1 g (42 mmol) of ethoxymethylene dimethyl ether, stir for 12 hours at reflux temperature , it is cooled to 15 ° C and the precipitated product is isolated by filtration. 5.7 g (53% of theory) of 5-amino-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-pyrazole-carbonitrile having a melting point of 165 ° C are obtained.

Example 2 C2Hs - - 3.5 g (18 mmol) of 5-difluoromethoxy-3-hydrazino-1,4-dimethyl-pyrazole are stirred in 100 ml of ethanol with 3. 38 g (20 mmol) of ethyl-2- (ethoxymethylene) -2-cyanoacetate and 1.08 g (0.02 mol) of sodium methylate, for 3 hours at the reflux temperature. After cooling, it is concentrated by evaporation, the residue is stirred with water and the precipitated product is isolated by filtration. 2.5 g (44% of theory) of 5-amino-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-pyrazole carboxylate of ethyl with a melting point of 12 ° Z are obtained. .

Example 3 Combine 1.7 g (5.6 mmol) of 5-methyl-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-pyrazolcarbonyl chloride in 30 ml of acetonitrile with 0.64 g (11.2 mmol) of cyclopropylamine and the mixture is continued stirring for about 2 hours at about 25 ° C. It is then concentrated by evaporation, the residue is stirred with water, acidified with concentrated hydrochloric acid and the product that precipitates slowly is isolated after 5 hours by filtration. 0.9 g (50% of theory) of 5-methyl-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-pyrazole carboxamide having a melting point of 155 ° C are obtained.

Example 4 Combine 1.0 g (3.7 mmol) of 5-amino-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-pyrazole-carbonitrile in 30 ml of acetonitrile with 0.37 g (3.7 mmol) of triethylamine and then with 0.29 g (3.7 mmol) of acetyl chloride and the mixture is stirred for 12 hours at 25 ° C. It is then concentrated by evaporation, stirred on water, extracted with methylene chloride, dried over sodium sulphate and concentrated again by evaporation. The crude product is purified through silica gel with cyclohexane / ethyl acetate 7: 1. 0.58 g (50.5% of theory) of 5-acetylamino-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-pyrazolecarbonitrile having a melting point of 133 ° C are obtained.

Example 5 0.6 g (2.2 mmol) of 5-methyl-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-pyrazole-carbonitrile in 10 ml of thioacetic acid is stirred for 2 hours at the reflux temperature it is concentrated by evaporation, stirred with water, extracted with methylene chloride, dried over sodium sulfate, then dissolved in diethyl ether, precipitated with petroleum ether and isolated by filtration. 0.4 g (60.4% of theory) of 5-methyl-1- (5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl) -4-thiocarbamoyl-pyrazole with a melting point of 151 ° C are obtained. In a manner analogous to that of Examples 1-5 and according to the general description of the preparation processes according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) indicated in the following Table 1.

Table 1: Examples of the compounds of the formula (I) E-J R1 Non-physical data CH, OCHF, «'» CN Br Fp .: 7I'C CH, OCHF, CH, CN NH, \ Fp .: IS6 «C CH, CN CH, OCHF, CH, COOCjH, CH,? -NR (CDQ,): 1.95; 2.55; 30-4 J ppm CH, OCHF, CH, COOH CH, Fp .: 177-C tO CH, OCHF. CH, CONH CH, Fp .: 96 «C I I CH, OCHFj CH, CN I Cll, Fp .: ßt-C - Starting products of the formula (II) Example (II-i; Dissolve in 68 ml of water and 135 ml of concentrated hydrochloric acid, 10.5 g (59 mmol) of 5-difluoro-methoxy-3-amino-1,4-dimethyl-pyrazole, drop by drop to -10. ° C, a solution of 5.52 g (80 mmol) of sodium nitrite in 24 ml of water and the mixture is stirred for one hour at -10 ° C. Then, dropwise, 38 g (0.17 mol) of tin (II) chloride dihydrate - dissolved in 49 ml of concentrated hydrochloric acid - are added dropwise at the same temperature. The mixture is further stirred for 1.5 hours and then, dropwise, at -10 ° C, 250 ml of sodium hydroxide lye is added dropwise. 32%. The mixture is extracted several times with methylene chloride and with ethyl acetate, the organic phase is dried over sodium sulphate and concentrated by evaporation under vacuum of the water pump. 9.9 g (87% of theory) of 5-difluoromethoxy-3-hydrazino-1,4-dimethylpyrazole are obtained as an amorphous product. 'H-NMR (CDC13): 2.00; 3.70; 6.45; 7.25 ppm.

Starting products of the formula (IV): Example (IV-1) - - Stage 1 First 168 g (0.92 mol) of 5-hydroxy-3-ethoxycarbonyl-1,4-dimethyl-pyrazole are stirred with 317 g. (2.3 moles) of potassium carbonate in 700 ml of dimethylformamide for 1 hour at 80 ° C. Subsequently, chlorodifluoromethane is introduced at 110 ° C for approximately 2 hours. After cooling to 25 ° C, they are separated by suction filtration, the filtrate is concentrated on a rotary evaporator, the residue is stirred with water, acidified with concentrated hydrochloric acid, stirred for 12 hours at 25 ° C and the precipitated product it is isolated by filtration. 185 g (86% of theory) of 5-difluoromethoxy-3-ethoxycarbonyl-1,4-dimethylpyrazole are obtained with a melting point of 59 ° C.

Stage 2 92.5 g (0.39 mol) of 5-difluoromethoxy-3-ethoxycarbonyl-1,4-dimethyl-pyrazole are introduced under stirring in 500 ml of 20% sodium hydroxide solution, stirred for 1 hour at 80 ° C. it is stirred on ice water, acidified with concentrated hydrochloric acid and the precipitated product is isolated by filtration. 58 g (72% of theory) of 5-difluoromethoxy-3-carboxy-1,4-dimethylpyrazole are obtained with a melting point of 175 ° C.

Stage 3 58 g (0.28 mol) of 5-difluoromethoxy-3-carboxy-1,4-dimethyl-pyrazole in 400 ml of toluene are combined with 5 drops of dimethylformamide, added dropwise to 80 ° C, in the course of 30 minutes, 42 g (0.35 moles) of thionyl chloride, then stirred at reflux temperature until the gas evolution is complete, is cooled to 25 ° C and concentrated by evaporation in a vacuum. the rotary vacuum evaporator of the water pump. 62.0 g (98% of theory) of 5-difluoromethoxy-3-chlorocarbonyl-1,4-dimethyl-pyrazole are obtained as oil. 'H-NMR (CDC13): 2.20; 3.90; 6.58 ppm.

Stage 4 36.9 g (0.16 mol) of 5-difluoromethoxy-3-chlorocarbonyl-1,4-dimethyl-pyrazole are placed in 250 ml of acetonitrile and gaseous ammonia is rapidly introduced at maximum 40 ° C (cooling with an ice bath) into the reactor. 30 minutes. The mixture is stirred for another 30 minutes, separated by filtration by suction at 20 ° C and the residue washed thoroughly with water. The filtrate is concentrated by evaporation under vacuum of the water pump, the residue is stirred with water, separated by filtration by suction and washed with water. The two residues of the filtration are combined. This gives 31.8 g (97% of theory) of 5-difluoromethoxy-3-carbamoyl-1,4-dimethylpyrazole with a melting point of 128 ° C.

Stage 5 Add dropwise to 63 g (1.6 moles) of sodium hydroxide in 300 ml of water at 5 ° C, 50 g (0.31 moles) of bromine and then introduce at the same temperature 57 g ( 0.28 moles) of 5-difluoromethoxy-3-carbamoyl-1, -dimethyl-pyrazole. The mixture is stirred once the cooling bath has been removed until a clear solution is formed. It is then heated to 80 ° C, stirred for about 2 hours at this temperature, then cooled to 25 ° C, extracted several times with methylene chloride and with ethyl acetate, the organic phase is dried over Sodium sulphate and concentrated by vacuum evaporation of the water pump. 41 g (82.7% of theory) of 5-difluoromethoxy-3-amino-1,4-dimethylpyrazole are obtained as oil. 'H-NMR (CDCl 3): 1.85; 3.55; 6.45 ppm. Additional examples of the intermediate products of the formula (IV): Table 2 Table 2 (Continued) The H-NMR spectra were collected in deuterochloroform (CDCI3) with tetra-ethylsilane (TMS) as internal standard. The chemical shift has been given as a value d in ppm.

Application Examples: In the application examples the following compound is used as a comparative substance: 4-Cyano-5-methyl-1- (4-chloro-5-difluoromethoxy-1-methyl-pyrazol-3-yl) -pyrazole alias 4'-chloro-5'-difluoromethoxy-1 ', 5-dimethyl- (1,3 '-bi-lH-pyrazole) -4-carbonitrile (known from EP 542388, WO 94/08999).

Example A Pre-emergence trial. Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether In order to obtain a convenient preparation of the active compound, 1 part by weight of the active compound is mixed with the indicated solvent amount, the amount of emulsifier indicated is added and the concentrate is diluted with water to the desired concentration. Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active product in such a manner that the desired amount of active product is applied respectively per unit area. The concentration of the sprayable broths will be chosen in such a way that the quantities of the active product respectively desired are applied in 1000 liters of water / ha. After three weeks, the degree of damage of the plants is evaluated in% of damages compared to the development of the untreated control.

Mean: 0% = no effect (same as untreated controls) 100% = total destruction.

In this test, for example, the compounds according to Preparation Examples 6 and 7 are shown, with application rates of 30, 60 and 125 g / ha, with a good compatibility with the crop plants, such as, for example wheat (0%), barley (0%), soybean (0%) and cotton (0%), a very potent effect against weeds such as Amaranthus (100%), Solanum (10Q%), Chenopodium (100%), Veronica (100%), Sorghum (90%), Stellaria (95%), Viola (99%), Echinocloa (80%) and Digitaria (100%).

Table Ai: Pre-sprout / greenhouse test or cn Table A2: Pre-sprout / greenhouse test Table A3; Pre-sprout / greenhouse test Example B Post-emergence trial Solvent: 5 Parts by weight of acetone Emulsifier: 1 Part by weight of alkylaryl polyglycol ether To obtain a convenient preparation of the active compound, 1 part by weight of the active compound is mixed with the indicated amount of solvent, the amount of emulsifier indicated is added and the concentrate is diluted with water to the desired concentration. With the preparation of the active product, test plants are sprayed, having a height of 5-15 cm, in such a way that the desired quantities of active compound per unit area are respectively applied. The concentration of the spray liquors is chosen in such a way that the desired quantities of the active compound are applied respectively in 1000 liters of water / ha. After three weeks, the degree of damage of the plants is evaluated in% of damages compared to the development of the untreated controls.

-They mean: 0% = no effect (same as the untreated controls) 100% = total destruction. In this test they show, for example, the compounds according to the preparation examples 6 and 11, with application rates of 60 or 125 g / ha, with a compatibility with the crop plants, such as, for example, wheat ( 10%), barley (20%) and corn (20%), better than (A) (90%, 40%, 90%), a very potent effect against weeds such as Amaranthus (100%), Datura (100%), Ipomoea (100%) Polygonum (100%), Solanum (100%), Abutilon (95-100%), Chenopodium (95-100%), Stellaria (95-100%) and Viola (90-95%).

Table Bl: Post-emergence / greenhouse trial Table B2: Post-emergence / greenhouse trial I It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (8)

- - CLAIMS

1. - The 1- (3-pyrazolyl) -pyrazoles of the general formula (I)

characterized in that R 1 means alkyl having 1 to 6 carbon atoms, optionally substituted by hydroxy, by cyano, by carboxy by halogen, by alkoxy with 1 to 4 carbon atoms, by alkyl carbonyl with 1 to 4 carbon atoms or by alkoxycarbonyl with 1 to 4 carbon atoms or means cycloalkyl with 3 to 6 carbon atoms, R2 means hydrogen, hydroxy, halogen, cyano, nitro, N (RpR12) or means alkyl, aralkyl, alkoxy or alkylthio substituted respectively in case given by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms, with respectively 1 to 6 carbon atoms in the alkyl part,

R3 means hydroxy, cyano, nitro or means a radical, substituted respectively by cyano, by halogen or alkoxy with 1 to 4 carbon atoms, of the group consisting of alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl with respectively

1 to 6 carbon atoms, or

R3 is a radical, substituted, if appropriate, by halogen, of the series consisting of alkenyl or alkynyl with 2 to 6 carbon atoms,

R 4 is hydrogen, halogen, or alkyl having from 1 to 6 carbon atoms, optionally substituted by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms;

R5 means hydrogen, cyano, nitro, amino or halogen, means alkyl having 1 to 6 carbon atoms, optionally substituted by cyano, hydroxy, halogen or alkoxy with 1 to 4 carbon atoms,

means the grouping - (CH2) m-0-R7, the

grouping - (CH2) m-S (0) n-R8, the grouping - (CH2) m- g in CO-R, the grouping - (CH2) m-CO-0-R, the

grouping - (CH2) m-CQ-N (R11, R12), - -R6 means hydrogen, cyano, amino, halogen, means alkyl having 1 to 6 carbon atoms, substituted, if appropriate by cyano, by hydroxy, carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxy-carbonyl with 1 to 4 carbon atoms, R6 also means alkenyl or alkynyl with 2 to 6 carbon atoms respectively, optionally substituted by cyano or by halogen or means alkoxymethyleneamino with 1 to 4 carbon atoms in the alkoxy group, R6 further denotes phenyl optionally substituted by nitro, by cyano, by halogen, by alkyl with 1 to 4 carbon atoms, by haloalkyl with 1 to 4 carbon atoms, by alkoxy with 1 to 4 carbon atoms or by halogenalkoxy with 1 to 4 carbon atoms, R6 also means pyrrolyl, pyrrolidinyl, piperidinyl or morpholinyl substituted, where appropriate, by alkyl with 1 to 4 carbon atoms, ignites the grouping - (CH2) m- R12, means the grouping - (CH2) ra-0-R7, the grouping - (CH2) mS (O) n -R8 ^ the grouping - (CH2) m- CO-R O , the grouping - (CH2) ra-CO-0-R10, the grouping - (CH2) mN (Rn, R12) or the grouping

(CH2) m-CQ-N (Rn, R12) or the grouping - (CH2) rn-N = CH-R12,

R6 also means one of the following groupings

which are respectively substituted, if appropriate, by halogen or by alkyl having 1 to 4 carbon atoms, R7 is hydrogen, means alkyl having from 1 to 6 carbon atoms, optionally substituted by cyano, by carboxy, by nitro, by hydroxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxycarbonyl with 1 to 4 carbon atoms, R7 further denotes alkenyl or alkynyl with 2 to 6 carbon atoms respectively, optionally substituted by cyano or by halogen, R7 means in addition alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl with respectively up to 6 carbon atoms, each optionally substituted - by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms, or R7 further means cycloalkyl or cycloalkylalkyl with respectively 3 to 6 carbon atoms carbon in the cycloalkyl groups and, optionally, 1 to 4 carbon atoms in the alkyl groups substituted, where appropriate, by cyano, by carboxy, by halogen or by alkyl with 1 to 4 carbon atoms, R8 means alkyl having 1 to 6 carbon atoms, optionally substituted by cyano, carboxy, halogen, alkoxy with 1 to 4 carbon atoms or by alkoxycarbonyl having 1 to 4 carbon atoms, or means alkenyl or alkynyl with respectively 2 to 6 carbon atoms substituted, where appropriate, by cyano or by halogen, R9 means hydrogen, means alkyl with 1 to 6 carbon atoms substituted optionally by cyano, by carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxycarbonyl having 1 to 4 carbon atoms or by alkenyl or alkynyl with 2 to 6 carbon atoms, each substituted respectively case given by cyano or by halogen, - -R10 means hydrogen, means alkyl having 1 to 6 carbon atoms, optionally substituted by cyano, by carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms or by alkoxy- carbonyl having 1 to 4 carbon atoms, or means alkenyl or alkynyl with respectively 2 to 6 carbon atoms substituted, where appropriate, by cyano or by halogen, R 11 means hydrogen or formyl, means alkyl having 1 to 6 carbon atoms substituted on case given by cyano, by carboxy, by halogen, by alkoxy with 1 a

4 carbon atoms or by alkoxycarbonyl having 1 to 4 carbon atoms, R 11 further denotes alkenyl or alkynyl with 2 to 6 carbon atoms each substituted respectively by cyano or by halogen or means a radical, respectively substituted optionally cyano-, halogen- or alkoxy having to 4 carbon atoms, from the group consisting of alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl alkylaminocarbonyl, cycloalkyl-carbonyl, cycloalkyloxycarbonyl, cycloalkylamino carbonyl or cycloalkylsulphonyl having in each case up to 6 carbon atoms in the alkyl group - or in the cycloalkyl group, - -R 11 further denotes hetarylcarbonyl or arylcarbonyl,

R12 represents hydrogen, carbamoyl, denotes alkyl or alkoxy having 1 to 6 carbon atoms substituted carbon optionally cyano, carboxy, halogen, alkoxy having 1 to 4 carbon atoms or alkoxycarbonyl having 1 to 4 carbon atoms, R12 means also alkenyl or alkynyl having in each case 2 to 6 carbon atoms each substituted optionally cyano- or halogen or a radical substituted in each case optionally cyano-, halogen or alkoxy having 1 to 4 carbon atoms of the series comprising alkoxy, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylamino, alkylaminocarbonyl, dialkylamino- carbonyl, alkylaminothiocarbonyl, dialquilaminotio- alkylcarbonyl, alkylsulfonyl, cycloalkyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, cycloalkylaminocarbonyl or cycloalkylsulfonyl with respectively up to 6 carbon atoms in the alkyl groups or in the cycloalkyl groups or means phenyloalkyl with 1 to 2 carbon atoms, phenyl-alkylcarbonyl with 1 to 2 carbon atoms, phenoxy, benzoyl or furanyl substituted in each case optionally fluorine or chlorine, R12 means further hetarylcarbonyl or arylcarbonyl, represents O or S, m represents the numbers 0, 1 , 2 or 3 and n means the numbers 0, 1 or 2.

2. - Process for the preparation of l- (3-pyrazolyl) -pyrazoles of the general formula (I)

wherein R1, R2, R3, R4, R5 and R6 have the meanings recited in claim 1, characterized in that the cyanoalkenyl ethers of the general formula are reacted

(II)

wherein - R1, R2 and R3 have the meanings given above, with the cyanoalkenyl ethers of the general formula (III)

wherein R 4 and R 5 have the meaning indicated above, optionally in the presence of an auxiliary agent of the reaction and, if appropriate, in the presence of a diluent.

3. - Herbicidal agents, characterized in that they have a content of at least one 1- (3-pyrazolyl) -pyrazole of the formula (I) according to claim 1.

4. - Procedure for the control of undesirable plants, characterized in that the undesirable plants and / or their environment are treated with 1- (3-pyrazolyl) -pyrazoles of the formula (I) according to claim 1.

- - 5.- Use of 1- (3-pyrazolyl) -pyrazoles of the formula (I) according to claim 1, for the control of undesirable plants.

6. - Process for the preparation of herbicidal agents, characterized in that l- (3-pyrazolyl) -pyrazoles of the formula (I) according to claim 1 are mixed with extenders and / or surfactants.

7. - The hydrazinopyrazoles of the general formula (II)

characterized in that R 1 represents alkyl having from 1 to 6 carbon atoms, optionally substituted by hydroxy, by cyano, by carboxy, by halogen, by alkoxy with 1 to 4 carbon atoms, by alkyl carbonyl with 1 to 4 carbon atoms or by alkoxycarbonyl having 1 to 4 carbon atoms, R2 means alkoxy or alkylthio having 1 to 6 carbon atoms respectively, optionally substituted by cyano, by halogen or by alkoxy with 1 to 4 carbon atoms, R3 means hydroxy , cyano, or a radical substituted in each case optionally cyano-, halogen or alkoxy having 1 to 4 carbon atoms the group consisting of alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms or R3 means a radical substituted respectively by halogen in the series consisting of alkenyl or alkynyl with 2 to 6 carbon atoms, respectively.

8. - The pyrazoles of the general formula (IV)

characterized in that the substituents have in the formula (IV) the following associations - -