WO1997046535A1

WO1997046535A1 - 3-cyanoaryl pyrazoles and use thereof as herbicides

Info

Publication number: WO1997046535A1
Application number: PCT/EP1997/002580
Authority: WO
Inventors: Otto Schallner; Karl-Heinz Linker; Karl-Julius Reubke; Markus Dollinger
Original assignee: Bayer Aktiengesellschaft
Priority date: 1996-06-03
Filing date: 1997-05-21
Publication date: 1997-12-11
Also published as: EP0906285A1; JP2000512275A; CN1227545A; CA2256508A1; BR9709521A; DE19622189A1; AU2958597A

Abstract

The invention relates to novel 3-cyanoaryl pyrazoles of the general formula (I) in which Q is oxygen (O), sulphur (S), SO or SO2, R1 is hydrogen or possibly substituted alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkyl alkyl, R2 is hydrogen or possibly substituted alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkyl alkyl, R3 is hydrogen, halogen or possibly substitued alkyl, R4 is hydrogen or halogen, and R5 is hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen or one of the radicals -Q-R?6, -NH-R6¿, -NH-O-R6, -NH-SO¿2-R?6, -N(SO¿2-R?6)2, -CQ?1-R6, -CQ1-Q2-R6, -CQ1-NH-R6, -Q2-CQ1-R6¿, -NH-CQ1-R6, -N(SO¿2?-R?6)(CQ1-R6), -Q2-CQ1-Q2-R6¿, -NH-CQ?1-Q2-R6 or -Q2-CQ1-NH-R6¿ where Q?1 and Q2¿ are oxygen or sulphur and R6 is possibly substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkyl alkyl, aryl, arylalkyl, heterocyclyl or heterocyclyl alkyl, where the compounds 1-methyl-3-(4-cyano-2-fluoro-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-phenyl)-4-bromo-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-5-nitro-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-5-ethyl sulphonylamino-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-5-ethoxy carbonyl methoxy-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-chloro-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-chloro-5-methylthio-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-5-amino-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-5-hydroxy-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-5-chloro-phenyl)-4-chloro-5-difluoro methoxy pyrazol, 1-methyl-3-(4-cyano-2-fluoro-5-aminosulphonyl-phenyl)-4-chloro-5-difluoro methoxy pyrazol and 1-methyl-3-(4-cyano-2-fluoro-5-fluoro-sulphonyl-phenyl)-4-chloro-5-difluoro methoxy pyrazol are excepted by disclaimer; process for their production, novel intermediate products and the use of the 3-cyanoaryl pyrazoles as herbicides.

Description

3-CYANOARYL PYRAZOLE AND THEIR USE AS HERBICIDES

The invention relates to new 3-cyanoaryl-pyrazoles, processes for their preparation, new intermediates and their use as herbicides

It is known that certain substituted 3-arylpyrazoles have herbicidal properties (cf. EP 361114, EP 447055, WO 92/02509, WO 92/06962, WO 94/26109, WO 95/33728, WO 96/01255 ). However, the herbicidal activity and the tolerability of these compounds to crop plants are not always entirely satisfactory

The new 3-cyanoaryl-pyrazoles of the general formula (I) have now been found

in which

Q represents oxygen (O), sulfur (S), SO or SO ₂ ,

R ^{1 represents} hydrogen or represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl,

R "stands for hydrogen or for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl,

R ^ represents hydrogen, halogen or optionally substituted alkyl,

represents hydrogen or halogen and R for hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen, or for one of the residues -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -N (SO ₂ - R ⁶ ) ₂ ,

-CQ ^] -R ⁶ , -CQ '-QR ⁶ , -C NH-R ⁶ , -Q ² -CQ R ⁶ , -NH-CQ ^] -R ⁶ ,

-N (SO ₂ -R ⁶ ) (CQ ¹ -R ⁶ ), -QCQQR ⁶ , -NH-C Q '-Q ² -R ⁶ or -Q ² -CQ ^] -NH-R ⁶ ,

where Q ¹ and Q ² each represent oxygen or sulfur and R ⁶ represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,

where the compounds l-methyl-3- (4-cyano-2-fluorophenyl) -4-chloro-5-difluoro-methoxy-pyrazole, 1-methyl-3- (4-cyano-2-fluorophenyl) -4-bromo-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-nitro-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- ( 4-cyano-2-fluoro-5-ethylsulfonylamino-phenyl) -4-chloro-5-di-fluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-ethoxycarbonylmethoxyphenyl) -4 -chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-chlorophenyl) -4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3- (4-cyano-2- fluoro-5-methylthio-phenyl) -

4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminophenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4th -cyano-2-fluoro-5-hydroxy-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l -methyl-3- (4-cyano-2-fluoro-5-chlorophenyl) -4- chlorine- 5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminosulfonylphenyl) -4-chloro-5-difluoromethoxy-pyrazole and 1-methyl -3- (4-cyano-2 -fluoro-5-fluorosulfonylphenyl) -4-chloro-5-difluoromethoxy-pyrazole (known from WO 96/01255) are excluded by disclaimers.

The new 3-cyanoaryl-pyrazoles of the general formula (I) are obtained if

Hydrazine or its derivatives of the general formula (II)

H ₂ N-NH-R ^] (II),

in which

R ^{1 has} the meaning given above,

with cyanoarylcarbonyl compounds of the general formula (III)

in which

R, R and R have the meaning given above,

Q ^{J stands} for oxygen or sulfur and

R is hydrogen or alkyl, preferably hydrogen or C _j -C ₆ - alkyl group,

and / or optionally tautomers of the compounds of the formula (III)

if appropriate in the presence of a diluent,

and optionally on the compounds of the formula (I) thus obtained, within the scope of the above definition of substituents, by further conversions by customary methods

The compounds of general formula (I) can be prepared by customary methods into other compounds of general formula (I) according to the above definition Substituentendefi¬ converted, for example, by conventional alkylation, acylation or sulfonylation reactions rungs- (eg R ² H ^■ CH _3, CHF 2 'C ₂ H ₅ ,

CH ₂ CH-CH ₂ ; R ⁵ OH → OCH ₃ , OC ₂ H ₅ , OCHF ₂ , OCH ₂ CH = CH ₂ , OCOCH,

SH → SCH ₃ , SC ₂ H ₅ ; NH ₂ → NHC ₃ H ₇ , NHCOCH ₃ , NHSO ₂ CH ₃ ), by sulfurization reactions (e.g. QR ² .OH -> SH), by oxidation reactions (z BS -> ^■ SO, SO ₂ ) or by electrophilic or nucleophilic substitution reactions (e.g. R ³ H → Cl, Br, R ⁵ : F → OH, SH, NH ₂ ) - cf. also the manufacturing examples. The new 3-cyanoaryl -pyrazoles of the general formula (I) are notable for strong herbicidal activity.

In the definitions, the saturated or unsaturated hydrocarbon radicals, such as alkyl, alkenyl or alkynyl, are each straight-chain or branched

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably

Fluorine, chlorine or bromine, especially for fluorine or chlorine

The invention preferably relates to compounds of the formula (I)

in which

Q represents oxygen (O), sulfur (S), SO or SO ₂ ,

R ¹ for hydrogen, for optionally by cyano, halogen or CC ₄ -

Alkoxy-substituted alkyl having 1 to 6 carbon atoms, represents in each ge optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C _j -C each ₄ -alkyl-substituted cycloalkyl or cycloalkylalkyl having 3 each up to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,

R ² for hydrogen, for alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen, C _] -C ₄ alkoxy or C _j -C ₄ alkylthio, for each optionally substituted by halogen alkenyl or alkynyl each having 2 to 6 carbon atoms , or for cycloalkyl or cycloalkylalkyl which is optionally substituted by cyano, halogen or C 1 -C ₄ -alkyl and has in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,

R ^{3 represents} hydrogen, halogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by cyano, halogen, CC ₄ -alkoxy or C ₁ -C ₄ -alkylthio,

R ^{4 represents} hydrogen or halogen and R ^{5 represents} hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen, or one of the radicals -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -N (SO ₂ -R ⁶ ) ₂ ,

-CQ ^] -R ⁶ , -CQ'-Q ^ R ⁶ , -CQ NH-R ⁶ , -Q ² -CQ ¹ -R ⁶ , -NH-CO R ⁶ ,

-N (SO ₂ -R ⁶ ) (CQ ¹ -R ⁶ ), -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ -Q ² -R ⁶ or -Q ² -CQ ¹ -NH -R ⁶ stands,

wherein Q ¹ and Q ² each represent oxygen or sulfur and R ^{6 represents} optionally by cyano, halogen, C, -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ -alkoxy-carbonyl or C _j -C ₄ -Alkylamιno- carbonyl-substituted alkyl with 1 to 6 carbon atoms, each optionally by cyano, carboxy, halogen, C -.- C ₄ -alkyl carbonyl,

C _j -C ₄ alkoxy-carbonyl or C _] -C ₄ -Alkylamιno-carbonyl substituted alkenyl or alkynyl each having 2 to 6 carbon atoms, for each optionally by cyano, carboxy, halogen, C ₁ -C ₄ alkyl carbonyl or C _] -C ₄ -alkoxy-carbonyl-substituted cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thio - carbamoyl, C ₁ -C ₄ alkyl, C <-C ₄ haloalkyl, C ^ C ^ alkoxy, C _j -C ₄ - haloalkoxy, C _r C ₄ -Alkylthιo, C _r C ₄ -Halogenalkylthιo, C _r C _4- alkyl-sulfinyl, C _] -C ₄ -alkylsulfonyl, C _j -C ₄ -alkylamino or dimethylamino substituted aryl or arylalkyl each having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, or for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarb amoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C _r C ₄ alkoxy, C _r C ₄ haloalkoxy, C _r C ₄ alkylthio, C _r C ₄ haloalkyl thio, C _r C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylamino or dimethylamino-substituted heterocyclyl or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and or 1 or 2 oxygen atoms and / or one Sulfur atom in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl part,

where the compounds l-methyl-3- (4-cyano-2-fluorophenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluorophenyl) -4-bromo-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-nιtro-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- ( 4-cyano-2-fluoro-5-ethylsulfonylaminophenyl) -4-chloro-5-dι- fluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-ethoxycarbonylmethoxy- phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-chlorophenyl) -4-chloro-5-difluoromethoxypyrazole, l-methyl-3- (4- cyano-2-fluoro-5-methylthio-phenyl) - 4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminophenyl) -4-chloro-5 -difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-hydroxy-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3- (4-cyano-2- fluoro-5-chloro-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminosulfonyl-phenyl) -4-chloro-5-difluoromethoxy-pyrazole and 1-methyl-3- (4-cyano-2-fluoro-5-fluorosulfonylphenyl) -4-chloro-5-difluoromethoxy-pyrazole (known from WO 96/01255) are excluded by disclaimers

The invention relates in particular to compounds of the formula (I)

in which

Q represents oxygen (O), sulfur (S), SO or SO ₂ ,

R ¹ for hydrogen, for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, for each optionally by fluorine, chlorine or bromine-substituted propenyl, butenyl, propynyl or butynyl, or for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyl Im optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl ethyl stands,

R ² for hydrogen, for each optionally by cyano, fluorine, chlorine,

Methoxy, ethoxy, methylthio or ethylthio substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for propenyl, butenyl, propynyl or butynyl, each optionally substituted by fluorine, chlorine or bromine, or for cyclopropyl, cyclobutyl, cyclopentyl optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl,

Cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,

R ^{3 is} hydrogen, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-, which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio. Butyl stands, R ^{4 represents} hydrogen or fluorine, chlorine or bromine and

R ⁵ for hydroxy, mercapto, amino, fluorine, chlorine, bromine or for one of the

Residues -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -N (SO ₂ -R ⁶ ) ₂ , -CQ R ⁶ ,

- CQ ¹ - Q ² - R ⁶ , - CQ '- NH -R ⁶ , - Q ² - CQ ¹ - R ⁶ , - NH - CQ' - R ⁶ , -N (SO ₂ -R ⁶ ) (CQ ¹ -R ⁶ ), -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ -Q ² -R ⁶ or

-Q ² -CQ ¹ -NH-R ⁶ ,

1 ? Λ wherein Q and Q each represent oxygen or sulfur and R each optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, in each case optionally by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, n- or i-butyroyl , Methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl substituted propenyl, butenyl, propynyl or butynyl, each optionally with cyano, carboxy, fluorine, chlorine, bromine, acetyl , Propionyl, methoxycarbonyl or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally with hydroxyl, mercapto, amino, cyano, carboxy, carbamoyl,

Thiocarbamoyl, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, methylamino, ethylamino or phenyl, phenyl, substituted or phenethylamino for each optionally by hydroxy, mercapto,

Amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, meth ¬ oxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, methyl¬ sulfonyl, ethylsulfonyl, methylamino, ethylamino or dimethylamino substituted heteroxycyllanyl, auseroxycyliryl, ausderylcyllanyl, ausercyclyl, or ausercyclyl, or ausercyclyl, or ausercyclyl, or ausercyclyl, or ausercyclyl, or ausercyclyl, or ausercyclyl, or from, , Dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, Pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl,

where the compounds l-methyl-3- (4-cyano-2-fluorophenyl) -4-chloro-5-difluoro-methoxy-pyrazole, l-methyl-3- (4-cyano-2-fluorophenyl) -4-bromo-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-nitro-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- ( 4-cyano-2-fluoro-5-ethylsulfonylamino-phenyl) -4-chloro-5-di-fluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-ethoxycarbonylmethoxy-phenyl) -4 -chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-chlorophenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2- fluoro-5-methylthio-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminophenyl) -4-chloro-5-difluoromethoxy-pyrazole , l-methyl-3- (4-cyano-2-fluoro-5-hydroxy-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5- chlorophenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminosulfonyl-phenyl) -4-chloro-5-difluoromethoxy-pyrazole and l-methyl -3- (4-cyano-2-fluoro-5-fluorosulfonylphenyl) -4-chloro-5-difluoromethoxy-pyra zol (known from WO 96/01255) are excluded by disclaimers.

3-Cyanoaryl-pyrazole of the formulas are very particularly preferred

H

where each R ^{5 has} the meanings given above.

The general or residual definitions given above or in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the preferred ranges indicated.

If, for example, methylhydrazine and 2-chloro-2- (4-cyano-2-fluoro-5-methoxy-benzoyl) -acetic acid ethyl ester are used as starting materials, the course of the reaction in process (a) according to the invention can be outlined by the following formula become:

Formula (II) provides a general definition of the hydrazine derivatives to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I). In formula (II), R ¹ preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R ¹

The starting materials of the formula (II) are known synthetic chemicals.

Formula (III) provides a general definition of the cyanoarylcarbonyl acetic acid derivatives to be used further as starting materials in process (a) according to the invention. In formula (III), R ³ , R ⁴ and R ^D preferably or in particular have those meanings which are already related above with the description of the compounds of formula (I) according to the invention preferably or as particularly preferred for R, R ⁴ and R ⁵ ;

R preferably represents hydrogen or alkyl having 1 to 4 carbon atoms, in particular hydrogen, methyl or ethyl.

The starting materials of the formula (III) are, with the exception of the compound ethyl 2- (4-cyano-2-fluorobenzoyl) acetic acid - alias ethyl 3- (4-cyano-2-fluorophenyl) -3-oxo propionate (cf. WO 96/01255) - not yet known from the literature; with the exception of 2- (4-cyano-2-fluoro-benzoyl) acetic acid ethyl ester, they are the subject of the present application as new substances.

The new cyanoarylcarbonyl compounds of the formula (III) in which Q ^{3 represents} oxygen are obtained if malonic acid or its derivatives of the general formula (IV)

in which

R and R ^{J have} the meaning given above,

or salts of compounds of formula (IV) -

with cyanobenzoyl halides of the general formula (V)

in which

R and R have the meaning given above and

X ^{1 represents} halogen,

optionally in the presence of an acid acceptor, such as, for example, methylamine, optionally in the presence of a reaction auxiliary, such as, for example, magnesium chloride and, if appropriate, in the presence of a diluent, such as, for example, acetonitrile, at temperatures between -20 ° C. and + 50 ° C. and on works in the usual way (see the manufacturing examples)

The malonic acid derivatives of the formula (IV) required as products are known organic synthetic chemicals With the exception of the compounds 4-cyano-3-methoxy-benzoyl chloride (cf. Arch Pharm 323 (1990), 507-512; EP 166609) and 4-cyano-2-fluoro-, the cyanobenzoyl halides of the formula (V) which are further required as precursors are benzoyl chloride (cf. WO 96/01255) not yet known from the literature; With the exception of 4-cyano-3-methoxy-benzoyl chloride and 4-cyano-2-fluoro-benzoyl chloride, they are the subject of the present application as new substances

The new cyanobenzoyl halides of the formula (V) are obtained if cyanobenzoic acids of the general formula (VI)

in which

R ⁴ and R ^{5 have} the meaning given above,

with halogenation agents. such as phosgene (or its dimer or trimer) or thionyl chloride, optionally in the presence of a reaction auxiliary, such as BN, N-dimethylformamide, and optionally in the presence of a diluent, such as carbon tetrachloride, at temperatures between 0 ° C and

120 ° C (see the manufacturing examples)

The cyanobenzoic acids of the formula (VI) required as precursors are known and / or can be prepared by processes known per se (cf. Arch. Pharm 323 (1990), 507-512, Collect Czech Chem Commun 40 (1975), 3009-3019, Chem Pharm Bull 27 (1979), 3039-3048, J Chem Soc, Perkin Trans. I

1994, 1679-1684, Tetrahedron Lett 31 (1990), 7223-7226, EP 166609, EP 351856, WO 93/15078)

Not yet known from the literature and the subject of the present application as new substances are the compounds of the general formula (Via)

in which

R has the meaning given above and

X ^{2 represents} halogen, in particular fluorine or chlorine

The new cyanobenzoic acids of the formula (Via) are obtained if nitro-methylbenzonitriles of the general formula (VII)

in which

R ⁵ and X ^{2 have} the meaning given above,

with oxidizing agents, e.g. Potassium permanganate, optionally in the presence of a diluent, e.g. Acetone, at temperatures between 0 ° C and 50 ° C (see. The preparation examples; see also J. Chem Soc. 1949, 3374).

The nitromethylbenzometriles of the formula (VTI) are not yet known from the literature; as new substances, they are the subject of the present application

The new compounds of the formula (VII) are obtained if halobenzonitriles of the general formula (VTII)

in which

R and X have the meaning given above and

X ^{3 represents} halogen, in particular fluorine or chlorine,

with nitromethane in the presence of an acid acceptor, such as 1,8-diazabicylo-

[5 4 0] -undec-7-ene (DBU) and optionally in the presence of a diluent, such as ethyl acetate, at temperatures between -20 ° C and + 40 ° C (see the preparation examples)

The precursors of the formula (VIII) are known and / or can be prepared by known processes (cf. EP 191 185, EP 433124, EP431373, EP 497239, EP 557949, EP 566268, EP 635486)

The cyanobenzoic acids of the formula (Via) can also be obtained starting from known halogenated benzoic esters of the formula (IX) - see J Chem Eng Data 13 (1968), 587-588, cited in CA 69 106150 - according to the following formula scheme (R alkyl , in particular methyl or ethyl, X ³ halogen, in particular fluorine or chlorine)

The new cyanoarylcarbonyl compounds of the formula (III) in which Q ^{3 is} sulfur are obtained if cyanoaryl ketones of the general formula (X)

in which

R ³ , R ⁴ and R ^{5 have} the meaning given above,

with carbon disulfide (carbon disulfide, CS ₂ ) in the presence of an acid acceptor, such as, for example, potassium t-butoxide, and in the presence of a diluent, such as, for example

Tetrahydrofuran, and optionally subsequently - preferably without intermediate insulation - with an alkylating agent, such as methyl iodide, at temperatures between -30 ° C and + 30 ° C (see the preparation examples)

The starting materials of the formula (III) obtained in this way can, if appropriate, also be reacted with hydrazine derivatives of the formula (II) according to the process of the invention to give the active compounds of the formula (I) without intermediate isolation

The precursors of the formula (X) are known and / or can be prepared by known processes (cf. Chem Pharm Bull 33 (1985), 1360-1366, EP 166609, EP 628550, WO 94/05153, production examples)

As a diluent for carrying out the process according to the invention for

Preparation of the new compounds of the formula (I) are, above all, organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane , Dichloromethane, chloroform, carbon tetrachloride, ether, such as

Diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone, butanone or methyl isobutyl ketone, carboxylic acids such as acetic acid or propionic acid, nitriles such as acetonitrile, propionitrile or butyronitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide, esters such as methyl acetate or ethyl acetate, Sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or 1-propanol, ethylene glycol monomethyl ether, ethyl englykolmonoethyl ether, ethylene glycol monomethyl ether or diethylene glycol monoethyl ether

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C. and 150 ° C., preferably between 20 ° 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 increased or reduced pressure - generally between 0.1 bar and 10 bar

To carry out the process according to the invention, the starting materials are generally used in approximately aquimolar 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 and the reaction mixture is generally carried out for several hours Stirred 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, haulm killers and in particular as weed killers

Weeds in the broadest sense are understood to mean all plants which grow up in places where they are undesirable. Whether 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

Dicot weeds of the genera Sinapis, Lepidium, Galium, Stellaria,

Matπcaπa, 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, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum

Dicotyledon cultures of the genera Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita

Monocotyledonous weeds of the genera Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharisemumum, Scirpum Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera

Monocot cultures of the genera Oryza, Zea, Triücum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants

Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and track systems and on paths and squares with and without tree cover. The compounds for weed control in permanent crops, for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa and berry fruit can also be used. and hop plants, on ornamental and sports turf and pasture land and for selective weed control in annual crops

The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both in the pre-emergence and in the post-emergence

method

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers

Fabrics These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks like

Calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins 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, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations, also in a mixture with known herbicides, for weed control, finished formulations or tank mixes being possible.

Known herbicides are suitable for the mixtures, for example

Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Asulam, Atrazine, Azimsulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bentazon, Benzofenap - ethyloylpropyl ), Bialaphos, Bifenox, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butylate, Cafenstrole, Carbetamide, Chlomethoxyfen, Chloramben, Chloridazon,

Chlorimuron (-ethyl), chloronitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop (-propargyl), clomazone, clopyralid, clopyra-sulfuron, cloransulam (-methyl), cumyluron, cyclamidyl, cyclamate, cyclamate, cyclamate, cyclamate Cyhalofoρ (-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedi- pham, dialate, dicamba, diclofop (-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, Dimethametryn, Dimethenamid, Diitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Etobenzanid, Fenoxapropethyl, Flamprop (-isopropyl), Flamprop ), Flam-prop (-methyl), flazasulfuron, fluazifop (-butyl), flumetsulam, flumiclorac (-pentyl),

Flumioxazin, Flumipropyn, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurenol, Fluridone, Fluroxypyr, Flurprimidol, Flurtamone, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropethyl- safonammonium) ), Hexazinones, 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, metoxuron sulfuron (-methyl), metribuzin, molinate, monohnuron, naproanilide, naprop-amide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxy-fluorfen, paraquat, pendimethalin, phenmedipham, piperophos, primitilonlor (pretilonachlor) , Prometryn, Propachlor, Propanil, Propaquizafop, Propyzamide, Prosulfocarb, Prosulfuron, Pyrazolate, Pyrazosulfuron (-ethyl), Pyrazoxyfen, Pyπ- buücarb, Pyridate, Pyrithiobac (-sodium), Quinchlorac, Quin erac, Quιzalofop (Quιzalofop ( -p-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Tebutam, Tebutthiuron, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thifulfurium ), Thiobencarb, tiocarbazil, tralkoxydim. Tπ-allate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, triflurahn and triflusulfuron

A mixture with other known active ingredients, such as fungicides, insecticides, acacids, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The use is carried out in a customary manner, for example by pouring, spraying Spray, sprinkle

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing

The amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha

The preparation and use of the active compounds according to the invention can be seen from the examples below Manufacturing examples:

example 1

171 g (0.676 mol) of ethyl 2- (4-cyano-2,5-difluoro-benzoyl) -acetate are placed in 300 ml of acetic acid and, at an internal temperature of approx. 40 ° C, dropwise with 36.3 g ( 0.80 mol) of methylhydrazine are added. The mixture is then heated to 90 ° C. to 100 ° C. for about 90 minutes, a light yellow solid precipitating. The mixture is allowed to cool slowly and then poured onto about 2 liters of ice water. The solid product is isolated by suction, washed with water and dried in a water jet vacuum. Then it is stirred with 600 ml of dichloromethane, suction filtered and dried again in a water jet vacuum.

125 g (79% of theory) of 3- (4-cyano-2,5-difluorophenyl) -5-hydroxy-1-methyl-1H-pyrazole of melting point 198 ° C. are obtained.

Example 2

A mixture of 47 g (0.20 mol) of 3- (4-cyano-2,5-difluorophenyl) -5-hydroxy-1-methyl-1H-pyrazole and 350 ml of N, N-dimethylformamide is mixed with 55 g of potassium carbonate are added and the mixture is heated to 50 ° C. for about 60 minutes. Then, at an internal temperature between 60 ° C. and 70 ° C., 100 g (1.16 mol) of chlorodifluoromethane are introduced within about 6 hours. The mixture is then concentrated in a water jet vacuum and the residue is taken up in 500 ml of water. The aqueous suspension is acidified with 2N hydrochloric acid and extracted with dichloromethane. The organic phase is washed with water, dried with magnesium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and the residue is four times Hot digested with 500 ml of hexane each. The solvent is carefully distilled off from the combined hexane fractions in a water jet vacuum

24.6 g (43% of theory) of 3- (4-cyano-2,5-difluorophenyl) -5-difluoromethoxy-1-methyl-1H-pyrazole of melting point 80 ° C. are obtained

From the extraction residue, which is practically insoluble in hexane, the isomeric compound 3- (4-cyano-2,5-difluorophenyl) -2-difluoromethyl-l-methyl-pyrazole-5- can be extracted by column chromatography (with dichloromethane on silica gel). be isolated from the melting point 128 ° C. Example 3

A solution of 2.85 g (10 mmol) of 3- (4-cyano-2,5-difluorophenyl) -2-difluoromethyl-1-methyl-pyrazol-5-one in 20 ml of dichloromethane is added Room temperature (about 20 ° C) with stirring a solution of 1.9 g (12 mmol) of bromine in 5 ml of dichloromethane. The mixture is stirred for three hours at about 20 ° C., diluted with 20 ml dichloromethane, washed with saturated aqueous sodium bicarbonate solution and with saturated aqueous sodium chloride solution, dried with magnesium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum

3.5 g (96% of theory) of 4-bromo-3- (4-cyano-2,5-difluorophenyl) -5-di-fluoromethoxy-1-methyl-1H-pyrazole of melting point 79 ° C. are obtained

Example 4

1.5 g (4 mmol) of 4-bromo-3- (4-cyano-2,5-difluorophenyl) -l-methyl are added to a solution of 0.5 g (6 mmol) of sodium methylate in 40 ml of acetonitrile -5-difluoro-methoxy-1H-pyrazole. After stirring for 16 hours at room temperature (approx. 20 ° C.), the mixture is poured onto water, acidified with hydrochloric acid, and the precipitated solid is filtered off, washed with water and dried in a water jet vacuum.

1.1 g (75% of theory) of 4-bromo-3- (4-cyano-2-fluoro-5-methoxyphenyl) -1-methyl-5-difluoromethoxy-1H-pyrazole of melting point 155 ° C. are obtained .

Example 5

To a solution of 18.8 g (0.05 mol) of 4-bromo-3- (4-cyano-2-fluoro-5-methoxyphenyl) -l-methyl-5-difluoromethoxy-1H-pyrazole in 100 ml of dichloromethane 150 ml (0.15 mol) of a 1 molar solution of boron tribromide in dichloromethane are added at room temperature (approx. 20 ° C.). After stirring for 16 hours at room temperature, water and dichloromethane are added to the reaction mixture. The organic phase is separated off and washed successively with water, saturated sodium bicarbonate and sodium chloride solution, dried over magnesium sulfate and freed from the solvent in a water jet vacuum. The crude product thus obtained is purified by column chromatography using dichloromethane as the eluent

8.3 g (46% of theory) of 4-bromo-3- (4-cyano-2-fluoro-5-hydroxyphenyl) -l-methyl-5-difluoromethoxy-1H-pyrazole of melting point 129 ° C. are obtained

Example 6

To a solution of 1.9 g (6.0 mmol) of 4-chloro-3- (4-cyano-2-fluoro-5-hydroxyphenyl) -5-difluoromethoxy-1-methyl-1H-pyrazole in 50 ml Acetonitrile is added 2.8 g of 20 mmol of potassium carbonate and 1.0 g (8 mmol) of bromoacetonite. The reaction mixture is stirred for about 16 minutes at room temperature (about 20.degree. C.) and then concentrated in a water jet vacuum. The residue is washed with 50 ml of water added, acidified with 2N hydrochloric acid and extracted with dichloromethane. The organic phase is washed with saturated aqueous sodium hydrogen carbonate solution and with saturated aqueous sodium chloride solution, dried with magnesium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and this is the residue The crude product obtained is purified by column chromatography (dichloromethane, silica gel)

1.0 g (47% of theory) of 5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2-cyano-4-fluorophenoxyacetonitrile with a melting point of 104 ° C. are obtained

Analogously to preparation examples 1 to 6 and in accordance with the general description of the preparation process according to the invention, the compounds of the formula (I) listed in table 1 below can also be prepared, for example

Table 1: Examples of the compounds of the formula (I)

The compound listed in Table 1 as Example 47 can be produced, for example, as follows'

A solution of 6.0 g (23 mmol) of 3- (4-cyano-2,5-difluorophenyl) -1-methyl-5-methylmercapto-1H-pyrazole in 80 ml of dichloromethane is added at room temperature (approx. 20 ° C) while stirring a solution of 4.2 g (26 mmol) of bromine in 10 ml of dichloromethane. The reaction mixture is stirred for about 60 minutes at room temperature, diluted with 20 ml of dichloromethane and washed successively with dilute sodium hydrogen sulfite, saturated sodium hydrogen carbonate and sodium chloride solution, dried over magnesium sulfate and freed from the solvent in a water jet vacuum

7.0 g (88.5% of theory) of 4-bromo-3- (4-cyano-2,5-difluorophenyl) -1-methyl-5-methylmercapto-1H-pyrazole are obtained as a crystalline solid of melting point 100 ° C.

The compound listed in Table 1 as Example 79 can be produced, for example, as follows:

A mixture of 2.4 g (10 mmol) of 3- (4-cyano-2,5-difluorophenyl) -5-hydroxy-1-methyl-1H-pyrazole, 6.7 g (30 mmol) of phosphorus (V. ) -sulfide and 50 ml of xylene is heated under reflux for 9 hours. The mixture is then concentrated in a water-jet vacuum and the residue is stirred with 50 ml of 2N sodium hydroxide solution. Then the mixture is filtered and the filtrate is acidified with 2N hydrochloric acid. The product which is obtained in crystalline form is filtered off with suction isolated

1.6 g (64% of theory) of 3- (4-cyano-2,5-difluorophenyl) -1-methyl-5-mercapto-1H-pyrazole of melting point 137 ° C. are obtained

The compound listed in Table 1 as Example 79 can also be prepared, for example, as follows

A solution of 10.9 g (0.06 mol) is added dropwise at -20 ° C. to a suspension of 13.5 g (0.12 mol) of potassium t-butoxide in 100 ml of tetrahydrofuran in about 30 minutes. 1- (2,5-difluoro-4-cyano-phenyl) -ethanone in 50 ml of tetrahydrofuran. The mixture is stirred at -20 ° C. for about 30 minutes and then with 4.6 g (0.06 mol) of carbon disulphide (CS ₂ ) After a further 30 minutes, 7.3 g (0.12 mol) of acetic acid and 5.6 g (0.12 mol) of methylhydrazine are added in succession and the reaction mixture is allowed to warm to room temperature within 2 hours. The reaction mixture is then poured onto 250 ml of ice water and washed with dichloromethane. The aqueous phase is adjusted to pH 1 with hydrochloric acid and extracted several times with dichloromethane. The extracts of the hydrochloric acid solution are washed with sodium chloride solution, dried over magnesium sulfate and freed from the solvent in a water jet vacuum 5.6 g (37% of the theory) of 3- (4-cyano-2,5-difluorophenyl) -1-methyl-5-mercapto-1H-pyrazole are obtained as a crystalline yellow solid with a melting point of 137 ° C.

The compound listed in Table 1 as Example 80 can be prepared, for example, as follows

A solution of 5 g (0.02 mol) of 3- (4-cyano-2,5-difluorophenyl) -5-mercapto-1-methyl-1H-pyrazole in 80 ml of N, N-dimethylformamide is used 8.3 g (0.06 mol) of potassium carbonate are added and the mixture is heated to 50 ° C. At this temperature, about 10.4 g (0.12 mol) of chlorodifluoromethane are introduced within 3 hours. After the reaction has ended, the majority of the The solvent is removed in a water jet vacuum and the residue is taken up in 50 ml of water. The aqueous suspension is acidified with 2N hydrochloric acid and extracted with dichloromethane. The organic phase is washed with water, dried over magnesium sulfate and freed from the solvent in a water jet vacuum

5.2 g (86% of the theories) of 3- (4-cyano-2,5-difluorophenyl) -5-difluoromethylmercapto-1-methyl-1H-pyrazole of melting point 104 ° C. are obtained

The compound listed in Table 1 as Example 82 can be made, for example, as follows

A solution of 5.5 g (16 mmol) of 4-bromo-3- (4-cyano-2,5-difluorophenyl) -1-methyl-5-methylmercapto-1H-pyrazole in 100 ml of dichloromethane is added -5 ° C with stirring, a suspension of 9.9 g (40 mmol) of 70% 3-chloro-perbenzoic acid in 130 ml of dichloromethane. The reaction mixture is stirred for 16 hours

Room temperature (about 20 ° C) stirred, the precipitated solid is filtered off and the filtrate is washed successively with saturated sodium thiosulfate, saturated sodium hydrogen carbonate and saturated sodium chloride solution, dried over magnesium sulfate and freed from the solvent in a water jet vacuum

5.5 g (91% of the theory) of 4-bromo-3- (4-cyano-2,5-difluorophenyl) -1-methyl-5-methylsulfonyl-1H-pyrazole are obtained as a crystalline solid with a melting point of 176 ° C.

The compound listed in Table 1 as Example 83 can be made, for example, as follows

To a solution of 5.1 g (17 mmol) of 3- (4-cyano-2,5-difluorophenyl) -5-difluoromethylmercapto-1-methyl-1H-pyrazole in 20 ml dichloromethane are added at room temperature. temperature (approx. 20 ° C.) with stirring, a solution of 4.8 g (30 mmol) of bromine in 15 ml of dichloromethane. The reaction mixture is heated under reflux for 18 hours, diluted with 20 ml of dichloromethane and successively with dilute sodium hydrogen sulfite, saturated sodium hydrogen carbonate. and sodium chloride solution, dried over magnesium sulfate and freed from the solvent in a water jet vacuum

5.8 g (90% of theory) of 4-bromo-3- (4-cyano-2,5-difluorophenyl) -5-difluoromethylmercapto-1-methyl-1H-pyrazole are obtained as a crystalline solid of melting point 100 ° C

For example, the compound listed in Table 1 as Example 87 can be prepared as follows

To a solution of 6.2 g (22 mmol) of l- (4-cyano-2,5-difluorophenyl) -3,3-bis- (methylthio) -2-propen-l-one in 60 ml of acetonitrile 2.5 g (55 mmol) of methylhydrazine at room temperature (about 20 ° C.) The reaction mixture is refluxed for 90 minutes and then discharged onto ice water. The solid which has precipitated is filtered off with suction, washed with water and dried in vacuo

5.0 g (86% of theory) of 3- (4-cyano-2,5-difluorophenyl) -1-methyl-5-methylmercapto-1H-pyrazole of melting point 1 18 ° C. are obtained Starting materials of formula (III):

Example (III- 1)

To a mixture of 251 g (1.48 mol) of potassium monoethyl malonate in 2 liters of acetonitrile, 147 g (1.46 mol) of triethylamine and 170 g (1.80 mol) are added in succession at 10 ° C. to 15 ° C. Magnesium chloride (anhydrous). The mixture is stirred for about 150 minutes at room temperature (about 20 ° C.), then cooled to -10 ° C. to -5 ° C. and at this temperature in succession with 145 g (0.72 mol) of 4-cyano-2.5 difluoro-benzoyl chloride and 14.7 g (0.146 mol) of triethylamine are added. The reaction mixture is then stirred for about 18 hours at room temperature and then concentrated. The residue is mixed with 1.2 liters of toluene and then with 1 liter of 13% hydrochloric acid The mixture is stirred for 3 hours at room temperature, the precipitated solid is filtered off and the organic phase is separated from the filtrate. It is washed with 13% hydrochloric acid and then with water, dried with magnesium sulfate and filtered. The solvent is carefully removed from the filtrate in a water jet vacuum distilled off.

173 g (95% of theory) of ethyl 3- (4-cyano-2,5-difluorophenyl) -3-oxo-propionate of melting point 44 ° C. are obtained as a light yellow, solid residue Example (III-2)

If potassium monoethyl methyl malonate is used instead of potassium monoethyl malonate, the compound 3- (4-cyano-2,5-difluorophenyl) -2-methyl-3-oxo-propionic acid ethyl ester in is obtained analogously to Example (III-1) 93.6% yield as a yellow liquid.

1H-NMR (CDCI ₃ , d, ppm): 1.20 (t, 3H), 1.50 (d, 3H), 4.17 (q, 2H), 4.32 (q, 1H), 7, 48 (dd, 1H), 7.73 (dd, 1H).

Example II-3

To a suspension of 13.5 g (0.12 mol) of potassium t-butoxide in 100 ml of tetrahydrofuran, a solution of 10.9 g (0.06 Mol) l- (4-cyano-2,5-difluorophenyl) ethanone in 50 ml of tetrahydrofuran. The mixture is stirred at -20 ° C. for about 30 minutes and then 4.6 g (0.06 mol) of carbon disulfide (CS ₂ ) are added. After a further 30 minutes, 17.0 g (0.12 mol) of methyl iodide are added and the reaction mixture is allowed to warm to room temperature within two hours. The reaction mixture is poured onto 500 ml of ice water, adjusted to pH 1 with hydrochloric acid and extracted with 1500 ml of ethyl acetate. The organic phase is washed with sodium chloride solution, dried over magnesium sulfate and freed from the solvent in a water jet vacuum. The crude product obtained as a residue is stirred with about 20 ml of acetonitrile, the precipitated solid is filtered off and dried. 6.9 g (40% of theory) of l- (4-cyano-2,5-difluorophenyl) -3,3-bis (methylthio) -2-propen-l-one are obtained as a crystalline light yellow solid of Melting point 188 ° C.

Starting materials of formula (V):

Example (V-l)

6.7 g (56 mmol) are added dropwise to a mixture of 3.4 g (19 mmol) of 4-cyano-2,5-difluoro-benzoic acid, 30 ml of carbon tetrachloride and a drop of N, N-dimethylformamide. Thionyl chloride. The reaction mixture is then refluxed for about 6 hours. When the evolution of gas has ended, the mixture is allowed to cool and filtered. The volatile components are then carefully distilled off from the filtrate in a water jet vacuum.

3.6 g (95.5% of theory) of 4-cyano-2,5-difluoro-benzoyl chloride are obtained as a yellow liquid.

1H NMR (CDC1 ₃ , d, ppm): 7.95 (dd, 1H), 7.54 (dd, 1H).

Starting materials of formula (VI):

Example (VI- 1)

A solution of 5.74 g (29 mmol) of 2,5-di-fluoro-4-nitromethyl- is added to a suspension of 8.0 g (50 mmol) of potassium permanganate (finely milled) in 100 ml of acetone at a maximum of 40 ° C. Benzonitrile added dropwise in 30 ml of acetone. The reaction mixture is then stirred for about 16 hours at room temperature (about 20 ° C.) and then acidified with 2N hydrochloric acid. The precipitated manganese dioxide is removed by filtration and the filtrate is concentrated in a water jet vacuum. The residue is taken up in ethyl acetate, washed with water, dried with magnesium sulfate and filtered. The filtrate is concentrated, the residue is stirred with a little dichloromethane and suction filtered

3.4 g (64% of theory) of 4-cyano-2,5-difluoro-benzoic acid are obtained as a crystalline product with a melting point of 159 ° C.

H NMR (DMSO-D ₆ , d, ppm) 7.92 (dd, 1H), 8.15 (dd, 1H), 14.10 (s - broad, 1H)

Example (VI-2)

step 1

A mixture of 9.5 g (50 mmol) of 2,4,5-trifluoro-benzoic acid methyl ester, 2.7 g (55 mmol) of sodium cyanide and 100 ml of N, N-dimethylformamide is 3 days at about 25 ° C. stirred and then filtered over activated carbon. The filtrate is concentrated in a water jet vacuum and the residue is recrystallized from cyclohexane / ethyl acetate (Vol 9 1)

4.0 g (41% of theory) of 4-cyano-2,5-difluoro-benzoic acid methyl ester of melting point 60 ° C. are obtained

Level 2

A mixture of 0.83 g (4.4 mmol) of 4-cyano-2,5-difluoro-benzoic acid methyl ester, 0.49 g (4.4 mmol) of potassium t-butoxide, 50 ml of diethyl ether and 10 ml of water is stirred for 12 hours at about 23 ° C. The mixture is then acidified with concentrated hydrochloric acid, the organic phase is separated off, dried over sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum

0.50 g (62% of theory) of 4-cyano-2,5-difluoro-benzoic acid is obtained as a crystalline product with a melting point of 159 ° C.

Analogously to example (VI-1) or (VI-2), the compounds 5-chloro-4-cyano-2-fluoro-benzoic acid (melting point 147 ° C.) and 2-chloro-4-cyano-5-fluorine benzoic acid (melting point 163 ° C) can be produced

Starting materials of formula (VII):

Example (VII- 1)

3.7 g (60 mmol) of nitromethane are introduced together with 80 ml of ethyl acetate and 18.2 g (120 mmol) of diazabicycloundecene (DBU) and cooled to -10 ° C. Then a solution of 8.7 g (50 mmol) of 5-chloro-2,4-difluoro-benzonitrile in 50 ml of ethyl acetate are added dropwise, the reaction mixture is stirred for about 15 hours in an ice bath and then acidified with 2N hydrochloric acid. The organic phase is separated off, shaken with saturated aqueous sodium chloride solution, dried with magnesium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum

9.7 g (73.6%, i.e. 67% of theory) of 5-chloro-2-fluoro-4-nitromethylbenzonitrile are obtained as an amorphous residue which can be used for the next reaction stage without further purification

Analogously to example (VII-1), the compounds 2,5-difluoro

4-Nιtromethyl-benzonitrile (melting point. 100 ° C) and 2-chloro-5-fluoro-4-nitro-methyl-benzonitrile (melting point 35 ° C) are prepared

Starting materials of formula (X):

Example (X-l

5.16 g (24 mmol) of 2,5-difluoro-4- (1-nitro-ethyl) -benzonitrile are dissolved in 50 ml of acetic acid, the mixture is heated under reflux for 8 hours and after cooling in about 200 ml of water are then added, the mixture is extracted with dichloromethane, the organic phase is washed in succession with water, saturated sodium bicarbonate solution and with saturated sodium chloride solution, dried with magnesium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and the residue is washed several times with hot Extracted n-hexane The solvent is carefully distilled off from the combined extraction solutions in a water jet vacuum

2.72 g (62% of theory) of 1- (2,5-difluoro-4-cyano-phenyl) -ethanone are obtained as a colorless, crystalline residue with a melting point of 42 ° C.

Example (X-2)

5.4 g (0.11 mol) of sodium cyanide (ground) in 200 ml of N, N-dimethylformamide with 17.4 g (0.10 mol) of 2,4,5-trifluoroacetophenone for 12 hours The mixture is filtered off with suction, the filtrate is filtered through activated carbon and the solvent is carefully distilled off from the filtrate in a water jet vacuum 10.4 g (57% of theory) of 1- (2,5-difluoro-4-cyano-phenyl) -ethanone are obtained as an amorphous residue

IR spectrum 1698 cm ^-1 (CO), 2240 cm ^-1 (CN)

Examples of use:

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone emulsifier, 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier 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 active compound preparation, so that the desired amounts of active compound are applied per unit area. The concentration of the spray series is chosen so that in each case 1000 l of water / ha desired amounts of active ingredient are applied

After three weeks, the degree of damage to the plants is rated in%

Damage compared to the development of the untreated control It mean

0% = no effect (like untreated control)

100% = total annihilation

In this test, at application rates of 60 and 125 g / ha, the compounds according to Preparation Examples 3, 4, 7, 8, 10, 11, 12, 13 and 15, for example, show good tolerability to cultivated plants, such as maize (5% ), Soy (0-30%) and cotton (0-30%) very strong against weeds such as Digitaria (80-100%), Setaria (70-100%), Amaranthus (100%), Datura (90-100 %) and Solanum (100%) Example B

Post emergence test

Solvent 5 parts by weight of acetone

Emulsifier 1 part by weight of alkylaryl polyglycol ether

Test plants which have a height of 5-15 cm are sprayed with the active compound preparation in such a way that the desired amounts of active compound are applied per unit area. The concentration of the spray mixture is chosen so that the respectively desired amounts of active compound are applied in 1000 l of water / ha

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control

Mean it

0% = no effect (like untreated control) 100% = total destruction

In this test, at application rates of 20 and 60 g / ha, the compounds according to Preparation Examples 3, 4, 7, 8, 10, 11, 12, 13 and 15, for example, show very strong activity against weeds such as abutilone (100%), chenopodium ( 95-

100%), Solanum (100%), Digitaria (70-100%) and Setana (80-100%)

Claims

1 3 cyanoaryl pyrazole of the general formula (I)

characterized in that

Q represents oxygen (O), sulfur (S), SO or SO ₂ ,

R ^{1 represents} hydrogen or alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl, which are optionally substituted,

R ^{2 stands} for hydrogen or for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl,

R ^{J represents} hydrogen, halogen or optionally substituted alkyl,

R ^{4 represents} hydrogen or halogen and

R ⁵ for hydrogen, hydroxy, mercapto, amino, hydroxyamino,

Halogen, or for one of the radicals -QR ⁶ , -NH-R ⁶ , -NH-OR ⁶ , -NH-SO ₂ -R ⁶ , -N (SO ₂ -R ⁶ ) ₂ , -CQ'-R ⁶ , -CQ QR ⁶ , -CQ ^ NH-R ⁶ ,

-Q CQΛR ⁶ , -NH-CQ'-R ⁶ , -N (SO ₂ -R ⁶ ) (CQ ¹ -R ⁶ ), -Q ² -CQ ¹ -Q ² -R ⁶ , -NH-CQ ¹ - Q ² -R ⁶ or -Q ² -CQ ¹ -NH-R ⁶ ,

where the compounds l-methyl-3- (4-cyano-2-fluorophenyl) -4-chloro-5-di-fluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluorophenyl) -4-bromo-5-di-fluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-nitro-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3 - (4-cyano-2-fluoro-5-ethylsulfonylamino-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-ethoxycarbonylmethoxy-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3- (4-cyano-2-chlorophenyl) -4-chloro-5-difluoromethoxy-pyrazole, 1 - methyl-3- (4-cyano- 2-fluoro-5-methylthio-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminophenyl) -4-chloro-5-difluoro - methoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-hydroxy-phenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2- fluoro-5-chlorophenyl) -4-chloro-5-difluoromethoxy-pyrazole, l-methyl-3- (4-cyano-2-fluoro-5-aminosulfonylphenyl) -4-chloro-5-difluoromethoxy -pyrazole and 1-methyl-3- (4-cyano-2-fluoro-5-fluorosulfonyl-phenyl) -4-chloro-5-difluoromethox y-pyrazole are excluded.

Process for the preparation of 3-cyanoaryl-pyrazoles of the general formula (I)

in which

R ι l, t R> 2, τ R> 3 ^J , τ R> 4, τ R> 5 and Q have the meanings given in claim 1,

characterized in that one Hydrazine or its derivatives of the general formula (II)

^ N-NH-R ¹ (II),

in which

R ^{1 has} the meaning given above,

with cyanoarylcarbonyl compounds of the general formula (III)

in which

R ³ , R ⁴ and R ^{5 have} the meanings given above,

Q ^{3 represents} oxygen or sulfur and

R represents hydrogen or alkyl,

and / or optionally tautomers of the compounds of the formula (III)

and, if necessary, further conversions are carried out on the compounds of the formula (I) thus obtained within the scope of the definition of the subscriber according to conventional methods.

Cyanoaryl compounds of the general formula (III)

in which

R> 3, _D R4 and R have the meanings mentioned in claim 1 and

stands for oxygen or sulfur and

R represents hydrogen or alkyl

Cyanobenzoyl halides of the general formula (V)

in which

R and R have the meanings mentioned in claim 1 and

X represents halogen

4-cyanobenzoic acids of the general formula (Via)

in which

R and R have the meanings given in claim 1,

Nitromethylbenzonitriles of the general formula (VII)

in which

R ^{3 has} the meanings mentioned in claim 1 and

X ^{2 represents} halogen

Herbicidal agents, characterized in that they contain at least one 3-cyanoarylpyrazole of the general formula (I) according to Claim 1

Process for controlling unwanted plants, characterized in that 3-cyanoarylpyrazoles of the general formula (I) according to Claim 1 are allowed to act on undesired plants and / or their habitat.

9 Use of 3-cyanoarylpyrazoles of the general formula (I) according to claim 1 for combating undesirable plants 10. A process for the preparation of herbicidal compositions, characterized in that 3-cyanoarylpyrazoles of the general formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances.