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CA2256508A1 - 3-cyanoaryl pyrazoles and use thereof as herbicides - Google Patents

3-cyanoaryl pyrazoles and use thereof as herbicides Download PDF

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Publication number
CA2256508A1
CA2256508A1 CA002256508A CA2256508A CA2256508A1 CA 2256508 A1 CA2256508 A1 CA 2256508A1 CA 002256508 A CA002256508 A CA 002256508A CA 2256508 A CA2256508 A CA 2256508A CA 2256508 A1 CA2256508 A1 CA 2256508A1
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Prior art keywords
cyano
methyl
chloro
phenyl
fluoro
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French (fr)
Inventor
Otto Schallner
Karl-Heinz Linker
Karl-Julius Reubke
Markus Dollinger
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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-R6, -NH-R6, -NH-O-R6, -NH-SO2-R6, -N(SO2-R6)2, -CQ1-R6, -CQ1-Q2-R6, -CQ1-NH-R6, -Q2-CQ1-R6, -NH-CQ1-R6, N(SO2-R6)(CQ1-R6), -Q2-CQ1-Q2-R6, -NH-CQ1-Q2-R6 or -Q2-CQ1-NH-R6 where Q1 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

. ~ , CA 022~6~08 1998-11-30 ~- ~ Le A 31 691 - ~orei~n Countries / WA/m/S-P
, I
3-Cyanoalyl-py~azoles The invention relates to novel 3-cyanoaryl-pyrazoles, to processes for their preparation, to novel intermediates and to their use as herbicides It is known that certain substituted 3-aryl-pyrazoles have herbicidal properties (cf. EP
5 361114, EP 447055, WO 92/02509, WO 92/06962, WO 94/26109, WO 95/33728, WO
96/01255). However, the herbicidal activity and the crop plant safety of these compounds is not always entirely satisfactory.

This invention, accordingly, provides the novel 3-cyanoaryl-pyrazoles of the general formula (I) R~ Q_R2 N~
N~R3 10 R4~ (1), ~Rs CN
in which Q represents oxygen (O). sulphur (S)~ SO or SO..

R' represents hydrogen or represents alkyl. all~enyk all~inyl. cycloall;yl or cycloall;ylall~yl. each of ~hich is optionally substituted I ~ R- represents hy drogen or represents all~yl. allien~ 1. all~invl cycloall;yl or cycloall~ylall; y l each of ~hicll is optionally substituted.

R-' represellts hydro<~en. halo~en or optionally substituted all;yl.

CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries R4 represents hydrogen or halogen and R~ represents hydrogen, hydroxyl, mercapto. amino, hydroxyamino, halogen~ or represents one of the radicals -Q-R6, -NH-R6, -NH-O-R6, -NH-SO7-R6, -N(SO2-R6)l, -CQI-R6, -CQ'-Q'-R6, -CQ'-NH-R6, -Q'-CQ'-R6, -NH CQI R6, S -N(SOl-R6)(CQI-R6), -Q'-CQ'-Q'-R6, -NH-CQI-Q--R6 or -Q'-CQI-NH-R6, where Q' and Q' each represent oxygen or sulphur and R6 represents alkyl.
alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, each of which is optionally substituted, except for the compounds l-methyl-3-(4-cyano-2-fluoro-phenyl)-4-chloro-10 S-difiuoromethoxy-pyrazole, I-methyl-3-(4-cyano-2-fluoro-phenyl)-4-bromo-5-difluoromethoxy-pyrazole. 1-methyl-3-(4-cyano-2-fluoro-5-nitro-phenyl)-4-chloro-5-difiuoromethoxy-pyrazole. I-methyl-3-(4-cyano-2-fluoro-5-ethylsulphonylamino-phenyl)-4-chloro-5-difiuoromethoxy-pyrazole. 1-methyl-3-(4-cyano-2-fluoro-5-ethoxycarbonylmethoxy-pllellyl)-4-chloro-5-difluoromethoxy-pyrazole. 1-methyl-3-(4-15 cyano-2-chloro-pllenyl)-4-cllloro-S-difluorometlloxy-pvrazole~ I-methyl-3-(4-cyano-?-fluoro-S-methylthio-phenyl)-4-chloro-~-ditluoromethoxy-pyrazole. 1-methyl-3-(4-cyano-2-fluoro-5-amino-phen! 1)-4-chlolo-5-difluorometlloxy-pyrazole. 1-methyl-3-(4-cyano-2-fluoro-5-llydroxy-phell! 1)-4-cllloro-5-difiuorometlloxy-pyrazole. 1-metllyl-3-(4-cyano-2-tluoro-5-cllloro-pllell~ l)-icllloro-S-difluoromethoxy-pyrazole. I-methyl-3-(4-20 cyano-~-fluoro-S-amhlosulplloll! I-phen! 1)-4-cllloro-5-difluorometlloxy-pyrazole and I -methyl-3-(4-cyano-2-tluol-o-5-fluol-osulpllollyl-pllellyl )-4-cllloro-5-difluol-ometlloxy-pyl-azole (i~no~ll fi-om ~AO 96/Oi'~SS). ~iliCh are excluded ~ disclaill1er The no~el 3-c!anoal-!1-p!razoles of the ~enelal t'ollllula (1) are oltahled \~heh! drazille or del i~ ati~ es thereof of the (~ellelal fol mula ( 11 ) '5 H~-Ni i-RI (Il llicll CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries , R is as defined above are reacted with cyanoarylcarbonyl compounds of the general formula (111) R R

O~R3 R4~ (111), ~R5 CN
in which 5 R3 R~ and R5 are each as defined above Q~ represents oxygen or sulphur and R represents hydrogen or alkyl. preferably represents hydrogen or C -C6-alkyl - and/or. if appropriate~ tautomers of the compounds of the formula (111) -.

if appropriate in the presence of a diluent.

10 and. if appropriate. further conversions within the scope of the above definition of the substituents are carried out by customary methods on the resulting compounds of the formula (1).

The compoul1ds of the Jeneral formula (I ) can be converted by customar methods into other compounds of the ~eneral formula (1) in accordance ith the above definition of 15 the substituents for e.~;ample b customar alkylations. ac lations or sulphonylations (for example R-: I{ ~ CH . CIIF. C~ll . Cl-{.CH=CH7; R': 011 ~ OCH~. OC H5.

CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries OCHF~, OCH,CH=CH" OCOCH3; SH ~ SCH3, SC,H5; NH ~ NHC~H7~ NHCOCH3.
NHSO,CH3), by sulphurizations (for example QR-: OH ~ SH), by oxidations (for example S ~ SO, SO,) or by electrophilic or nucleophilic substitutions (for example R3:
H ~ Cl, Br; R5: F ~ OH, SH, NH,) - cf. also the Preparation Examples.

The novel 3-cyanoaryl-pyrazoles of the general formula (1) have strong herbicidal activity.

In the definitions, the saturated or unsaturated hydrocarbon radicals, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents 10 fluorine, chlorine or bromine and in particular represents fluorine or chlorine.

The invention preferably provides compounds of the formula (I) in ~hich Q represents oxygen (O)~ sulphur (S)~ SO or SO"

R' represents hydrogen. represents optionally cyano-~ halogen- or C ,-C ,-alkoxy-substituted alkyl havin~a, I to 6 carbon atoms, represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by halo2en~ or represents cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkvl group and if appropriate I to 4 carbon atoms hl the all;yl moiety and behlc in each case optionally substituted by cyano. halogell or C I -C ,-all;yl R- represents hydrogell represents optionally cyallo-. halogell-~ C,-C~-alko.~;y- or C~-C j-alkylthio-substituted all;yl having I to 6 carbon atoms represellts all;enyl or alkinyl ha~ ing in each case 2 to 6 carbon atoms and behlg in each case optionally substituted by halo~em or represents cvcloalkyl or cycloalkylalkyl CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries having in each case 3 to 6 carbon atoms in the cycloalkyl group and. if appropriate, I to 4 carbon atoms in the alkyl moiety and being in each case optionally substituted by cyano, halogen or C,-C~-alkyl, R3 represents hydrogen, halogen or optionally cyano-, halogen-, C,-C,-alkoxy- or S C~-C,-alkylthio-substituted alkyl having I to 6 carbon atoms, R' represents hydrogen or halogen and R' represents hydrogen, hydroxyl, mercapto, amino, hydroxyamino, halogen, or represents one of the radicals -Q-R6, -NH-R6, -NH-O-R6, -NH-SO,-R6, -N(SO,-R6)" -CQ'-R6, -CQ'-Q'-R6, -CQ'-NH-R6, -Q'-CQ'-R6, -NH CQ' R6, -N(SO,-R6)(CQI-R6), -Q'-CQ~-Q'-R6, -NH-CQI-Q'-R6 or -Q'-CQ'-NH-R6, where Ql and Q' each represent oxygen or sulphur and R6 represents optionally cyano-, halogen-~ C,-C,-alkoxy- Cl-C,-alkylthio-~ C,-C,-alkyl-carbonyl-, C,-C,-alkoxy-carbonyl- or C,-C,-alkylamino-carbonyl-substituted alkyl having I to 6 carbon atoms represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano carboxyl, halogen C,-CI-alkyl-carbonyl C,-C,-alkoxy-carbonyl or Cl-C,-alkylamino-carbon~,!l represents cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and if appropriate~ I to 4 carbon atoms in the alkyl moietv and being in each case optionally substituted by cyano carboxyl. halogen. C,-C,-alkyl-carbonyl or C,-C,-alkoxy-carbonyl. represents aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl _roup and. if appropriate I to 4 carbon atoms hl the alkyl moiety and bein g in each case optionally substituted bv hydroxyl. mercapto amino. cyano. carboxyl.
carbamoyl thiocarbamoyl Cl-CJ-alk~ l C~-C~-halogelloalkyl C,-C~-all~oxy.
2~ C~-C~-halogenoalkoxy. C,-C,-alkyltllio C,-C,-halogelloall;yltllio C~-C,,-alkylsulphillyl C,-CI-alkylsulphony h C,-C~-alkylamino or dimethylamino. or represents heterocyclyl or heterocyclylalkyl havin~ 2 to 6 carbon atoms and I
to 3 nitrogen atoms and/or I or 2 oxy~Jen atoms and/or one sulpllur atom hl the CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries heterocyclyl group and, if appropriate, I to 4 carbon atoms in the alkyl moiety and being in each case optionally substituted by hydroxyl, mercapto. amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, C,-C~-alkyl, C,-C,-halogenoalkyh Cl-C,-alkoxy, C,-C~-halogenoalkoxy, Cl-CI-alkylthio, C,-C~-halogenoalkylthio, S C, -C ~-alky lsulphinyl, C, -C4-alkylsulphony l, C ~ -C ~-alkylamino or d imethy lam i no~

except for the compounds l-methyl-3-(4-cyano-2-fluoro-phenyl)-4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-phenyl)-4-bromo-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-5-nitro-phenyl)-4-chloro-5-difluoromethoxy-pyrazole, I-methyl-3-(4-cyano-2-fluoro-5-ethylsulphonylamino-10 phenyl)-4-chloro-5-difluoromethoxy-pyrazole~ 1-methyl-3-(4-cyano-2-fluoro-5-ethoxycarbonylmethoxy-phenyl)-4-chloro-5-difluoromethoxy-pyrazole~ 1-methyl-3-(4-cvano-2-chloro-phellyl)-4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-5-methylthio-phenyl)-4-chloro-5-difluoromethoxy-pyrazole~ 1-methyl-3-(4-cyano-2-fluoro-5-amino-phenvl)-4-chloro-5-difluoromethoxy-pyrazole. 1-methyl-3-(4-cyano-15 2-fluoro-5-hydroxy-pllenyl)-4-chloro-5-difluorotnethoxy-pyrazole~ 1-methyl-3-(4-cvano-2-fluoro-5-chloro-phenyl)-4-cllloro-5-difluorometho,Yv-pvrazole~ l-methvl-3-(4-cyano-2-fluoro-5-amillosulpllonvl-pllenyl)-4-chloro-5-difluorometlloxy-pyrazole and I -methyl-3-(4-c! ano-7-fluoro-S-fluol-osulpllonvl-phenvl)-4-cllloro-S-difluorometlloxy-pyrazole (l~no~ll from ~O 96/01755) ~hicll are excluded by disclaimer.

70 The illVelltiOIl ill particular relates to compounds of the formula (I) llicl Q replesellts ox!gell (O). sulpll-ll (S) SO or SO~

Rl replesellts h! dlo(~ell repl-esellts nletll! I etl-! 1 n- or i-prop! l n- i- s- Or t-l ut! 1 eacll c f'\\llich is optiollall! sul~stituted t)! c!ano fluorille chlorille nletllox! or ethox! . replesellts propell! l. buten! 1. plOpill! I or butill! 1. eacll of' \\hicll is optionall! substituted b! fluorille. chlorille or bromille. or represellts CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries -cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl~
cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl, R' represents hydrogen, represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio, represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine, chlorine or bromine, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by cyano, fluorine, chlorine~ bromine, methyl or ethyl, R' represents hydrogen, fluorine, chlorine, bromine, or represents optionally cyano-, fluorine-~ chlorine-, methoxy-, ethoxy-~ methylthio- or ethylthio-substituted methyl, ethyl, n- or i-propyl, n-~ i-. s- or t-butyl.

15 R~ represents hydrogen or fluorine, chlorine or bromine and R' represents hydroxyl. mercapto. amino. fluorine. chlorine. bromine or represents one of the radicals -Q-R6. -NH-R6, -NH-O-R6, -NH-SO,-R6. -N(SO,-R6),.
-CQ'-R6 -cQ' Q~ R6 -CQ'-NH-R6, -Q--CQ'-R''. -NH-CQI-R6, -N(SO,-R6)(CQ'-R"). -Q--CQ'-Q--R6. -NH-CQ'-Q--R6 or -Q--CQ'-NH-R6.

~here Q' and Q- each represent oxygen or sulphur and R~ represents methyl.
ethyl n- or i-proryl. n-. i-. s- or t-butyl. each of ~hicll is optionally substituted b cyano fluorille chlorine. methoxy. ethoxy. methylthio ethylthio. acetyl.
propionyl. methoxycarbonyl. ethoxycarbonyl. methylaminocarbollyl or ethylaminocarbonyl repl-esellts propenyl. butenyl propinyl or butinyl. each of ~hicll is optionally substituted by cyano carboxyl. fluorhle. chlorille. bromhle.
acetyl. propionyl. n- or i-butyroyl. methoxycarbonyl. ethoxycarbonyl. n- or i-propoxycarbonyl methylaminocarbonyl. ethylaminocarbonyl n- or CA 022~6~08 1998-11-30 Le A 31 691 - E~orei~n Countries i-propylaminocarbonyl, represents cyclopropyl, cyclobutyl~ cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by cyano. carboxyl, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, represents phenyl, benzyl or phenylethyl. each of which is optionally substituted by hydroxyl, mercapto, amino~ cyano, carboxyl, carbamoyl, thiocarbamoyl, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, methylamino, ethylamino or dimethylamino, or represents heterocyclyl or heterocyclylalkyl selected from the group consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl. pyrimidinylmethyl, each of which is optionally substituted by hydroxyl, mercapto. amino, cyano~ carboxyh carbamoyl thiocarbamoyl, methyl, ethyl, n- or i-propyl. n-. i-, s- or t-butyl, difluoromethyl. dichloromethyl, trifluoromethyl. trichloromethyl. chlorodiRuoromethyl. fluorodichloromethyl, methoxy. ethoxy. diRuoromethoxy, trifluoromethoxy. methylthio. ethylthio, diRuoromethylthio. triRuoromethylthio. methylsulphinyl. ethylsulphinyl.
methylsulphonyl. ethylsulphonyl. methylamino, ethylamhlo or dimethylamino, except for the compounds l-methyl-3-(4-cyano-~-Ruoro-phell) 1)-4-chloro-~ -d i fl uoro methox) -pv razo l e. I -met hy 1-3 -(4-cyano-2-fl uo ro- plle n) 1 )-4-bro mo-2~ ~-difluorometllo.~ -pyrazole. I -meth) 1-3-(4-cyano-2-flLIoro-~-nitro-pllellyl )-4-cllloro-~-diRuorometllox)-pyrazole. I-methyl-3-(4-cyano-2-Ruoro-~-eth) Isulphollylamino-phellyl)-4-cllloro-~-difluorolllctllox)--pyrazole. 1-methyl-3-(4-cyano-2-fluoro-~-ethoxycarbonylmethox~-phellyl)-4-clllol-o-~-diRuorometllox)-p! razole l -methyl-3-(4-cyano-2-cll loro-p lleny I )-4-c h l o ro-~ -d i R uo ro m ethox) -py razo l e. I -m ethy 1-3 -(4-cyano-2-30 fluoro-~-metll) Ithio-phell) 1)4-cllloro-~-diRuololllctlloxy-pyrazole~ l-methyl-3-(4-cyano-2-fluol-o-~-amino-phenyl)-4-cllloro-~-difluorometho.~;y-pyrazole. 1-methyl-3-(4-cyano-Le A 31 691 - Forei~n Countries 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~ 1-methyl-3-(4-cyano-2-fluoro-5-aminosulphonyl-phenyl)-4-chloro-5-difluoromethoxy-pyrazole and I -methyl-3-(4-cyano-2-fluoro-5-fluorosulphonyl-phenyl)-4-chloro-5-difluoromethoxy-pyrazole (known from WO 96/01255), which are excluded by disclaimer.

Very particular preference is given to 3-cyanoaryl-pyrazoles of the formulae /N~ H3C, ~OCH2F2 ~ ~
N~--H N~--H N~--H

~Rs ~ S F~ Rs CN CN CN

H3C~ ~ SO2CH3 ~N~ H3C' ~ SCHF2 ~ N V H ~

\¢~\Rs ~ S F~Rs CN CN CN

H3C~ SO2CHF2 H3C~ OCH3 H3C~ OCHF2 N/N~ H N/N~ Br N/N~~'Br ~\Rs ~1~ 5 F~Rs CN CN CN

Le A 31 691 - Foreign Countries H3C~ ~ S02CH3 ~N ~
N ~ Br N ~ Br ~Rs --~J~ S F~[~Rs CN CN CN

H3C' ~ SCHF2H3C~N SO2CHF2 N f N/~~Br N/~'Br N/~ CI

~Rs ~Rs F~RS
CN CN CN

H3C~ ~ OCHF2H3C~ ~ OHH3C~ ~ S02CH3 ~Rs --~l s F ~Rs CN CN CN

N ~ H3C ~ SCHF2 H3C~ ~ SO2CHF2 R ~ Rs ~ R
CN CN CN

CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries H3C~ OH H3C~ OCHF2 ~~ Rs \~l~ 5 CN CN

where in each case R5 is as defined above.

The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or 5 intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the preferred ranges stated.

Using, for example. methylhydrazine and ethyl 2-chloro-2-(~-cyano-2-fluoro-5-methoxy-benzoyl)-acetate as starting materials. the course of the reaction in the process 10 (a) according to the invention can be illustrated by the following equation:

, CH3 ~ ~ ' C2Hs H3C~ N ~~C l H

NH2 F~OCH3 ~ F~ OCH3 CN CN

The formula (Il) provides a gelleral defhlition of the h~dl-azine derivati~es to be used as starting materials in the process accordillg to the invelltioll for preparillg compounds of the formula (1). In the fonnula (Il). R' pref'erably and hl particular has those 15 meani~ s ~hich ha~e already been mentioned above hl connectioll ~ith the description of compounds of the formula (I) accordhl=, to the invention as behlg preferred and as CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries being particularly preferred, respectively, for R'.

The starting materials of the formula (Il) are known chemicals for synthesis.

The formula (111) provides a general definition of the cyanoarylcarbonylacetic acid derivatives further to be used as starting materials in the process (a) according to the S invention. In the formula (111), R3, R~ and Rs each preferably and in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred and as being particularly preferred, respectively, for R3, R~ and Rs;

R preferably represents hydrogen or alkyl having I to 4 carbon atoms, in particular 10 hydrogen, methyl or ethyl.

Except for the compound ethyl 2-(4-cyano-2-fluoro-benzoyl)-acetate - alias ethyl 3-(4-cyano-2-fluoro-phenyl)-3-oxo-propionate (cf. WO 96/01255) -~ the starting materials of the formula (111) have hitherto not been disclosed in the literature; except for ethyl 2-(4-cyano-2-fluoro-benzoyl)-acetate~ they form, as novel substances. part of the subject 15 matter of the present appl ication.

The novel cyanoarylcarbollyl compounds of the formula (111) in which Q' represents oxygen are obtained v~-hen malonic acid or derivatives thereof of the general formula (IV) 0~,0~

( I V ).

O'R

''O ill ~ lliCIl R and R' are each as defined above CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries - or salts of compounds of the formula (IV) -are reacted with cyanobenzoyl halides of the general formula (V) O~X' R4~ (V), ~R5 CN

in which 5 R~ and R' are each as defined above and X' represents halogen, if appropriate in the presence of an acid acceptor. such as. for example. triethylamine, if appropriate 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~
10 acetonitrile at temperatures between -20~C and +50~C~ and are worked up in a customary manner (cf. the Preparation Examples).

The malonic acid derivatives of the formula (IV) required as intermediates are l;no~vn or~anic chemicals for synthesis.

Except for the compounds ~-cyano-3-metlloxy-bellzoyl chloride (cf. Arch Pharm. 323 (1990) 507-512: EP 166609) and ~-cyallo-2-fluoro-bellzoyl chlol-ide (cf. WO
96/01255) the cyallobellzo~lllalides of the forlllula (V) ~hich are furtller required as intermediates are hitherto not l;no~ll from the literature: except for ~-cyallo-3-metllo.~;y-benzoyl chloride and ~-c~ ano-2-fluoro-bellzo~ l chloride they form as novel substances. part of the subject matter of the present application.

CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries The novel cyanobenzoyl halides of the formula (V) are obtained when cyanobenzoicacids of the general formula (Vl) Oq~OH

(Vl), CN
in which 5 R~ and R5 are each as defined above are reacted with halogenating agents, such as, for example. phosgene (or its dimer or trimer) or thionyl chloride. if appropriate in the presence of a reaction auxiliary. such as, for example. N~N-dimethylformamide and if appropriate in the presence of a diluent, such as~ for example~ carbon tetrachloride, at temperatures between 0~C and 10 120~C (cf. the Preparation Examples).

The cyanobenzoic acids of the formula (Vl) required as intermediates 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. 1 1994~ 1679- 1684; Tetrahedron Lett. 31 (1990), 7223-7~26; EP 166609; EP 351856; WO 93/ 15078).

Hitherto not l;nown from the literature and. as novel substances. part of the subject matter of the present application. are the compounds of llle gelleral formula (Vla) CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries O OH

x2~ (Vla), CN

in which R5 is as defined above and X' represents halogen. in particular represents fluorine or chlorine.

5 The novel cyanobenzoic acids of the formula (Vla) are obtained when nitromethylbenzonitriles of the general formula (Vll) ~NO2 x2~ (Vll).
s CN
in which R' and X- are each as defned above 10 are reacted ~vitll o.~idizing agents. sucll as. for e.~ample. potassium permanganate~ if appropriate in the presence of a diluellt. sucl~ as. for e.~ample. acetone. at temperatures bet~een 0~C and ~0~C (cf. the Preparation E.~amples: cf. also J. Chem. Soc. 1949.
~7~ ).

The nitrometll~lbenzollitliles of the formula (Vll) al-e hitllerto not l~no~vn from the 15 literature: the~ form. as novel substances part of the subject matter of the present CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries application.

The novel compounds of the formula (Vll) are obtained when halogenobenzonitriles of the general formula (Vlll) x2~
(Vlll), ~R5 CN

5 in which R5 and X' are each as defined above and X3 represents halogen, in particular represents fluorine or chlorine are reacted ~vith nitromethane in the presence of an acid acceptor, such as. for example 1.8-diazabicyclo-[5 4.0]-undec-7-ene (DBU) and, if appropriate. in the presence of a 10 diluent. such as. for example. ethyl acetate. at temperatures between -20~C and +40~C
(cf the Preparation Examples) The intermediates of the formula (Vlll) are kno~n and/or can be prepared by known methods (cf EP 191185. EP 433124 EP 431373. EP 497239. EP 557949. EP 566268, EP 635486) 15 The cyanobellzoic acids of the formula (Vla) can also be prepared stat-tin~T from known halo~Tellated benzoic esters of the formula (IX) - cf J. Cl1em Eng Data 13 (1968).
587-588 cited in C A 69:106150 - according to the t'ollo~ing equatioll (R: alkyl. in particular methyl or ethyl: X-': halo~ell hl particulal- tluorhle or chlorille):

CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries O~OR o OR O~OH

X2 ~ - NaX ~ + H20 x2~R

(IX) CN CN (Vla) The novel cyanoarylcarbonyl compounds of the formula (111) in which Q3 represents sulphur are obtained when cyanoarylketones of the general formula (X) ~/\ R

R4~ ~ (X)~
~R5 CN

S in which R', R~ and R' are each as defined above are reacted with carbon disulphide (CS,) in the presence of an acid acceptor~ such as.
for example~ potassium t-butoxide~ and in the presence of a diluent~ such as forexample tetrallydrofuran and~ if appropriate~ subsequently - preferably without 10 intermediate isolation - ~ith an alkylating a~ent~ such as~ for example~ methyl iodide~
at temperatures bet~een -30~C and +30~C (cf. the Preparation Examples).

The starting materials of the formula (111) obtained in this manner can be reacted if appropriate ~ithout intermediate isolatiom ~ith h~drazille derivatives of the formula (Il) hl accordance ~ith the process according to the invelltioll to ~ e the active 1~ compounds of the formLIla (1).

The hltermediates of tlle formula (X~ are kllo~ll and/or can be prepared by l;no~n processes (cf. Chem. Pharm. Bull. 33 (1985). 1360-1366: EP166609: EP 6~8~0 WO

.
CA 022~6~08 1998-11-30 ~' Le A 31 691 - Forei~n Countries 94/05153; Preparation Examples) Suitable diluents for carrying out the process according to the invention for the preparation of the novel compounds of the formula (I) are in particular organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally 5 halogenated hydrocarbons, such as, for example, benzine, 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 ether orethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl 10 ketone; carboxylic acids, such as, for example, acetic acid or propionic acid, nitriles.
such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide. N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulphoxides~ such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, 15 n- or i-propanol. ethylene glycol monomethyl ether. ethylene glycol monoethyl ether.
diethylene glycol monomethyl ether or diethylene glycol monoethyl ether When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively ~vide range In general. the reaction is carried out at temperatures bet~een 0~C and 150~C. preferably bet~veen 20~C and 120~C.

20 The process according to the invention is generally carried out under atmospheric pressure Ho~;ever. it is also possible to carry out the process according to theinvention under elevated or reduced pressure - in ~eneral bet~veen 0 1 bar and 10 bar.

When carrying out the process accordhlg to the invention. the starting materials are generally emplo~ed hl appro~;imately equimolar amounts Ho~ever. it is also possible 25 to employ a relati~ely large excess of one of the components. The reaction is gellerally carried out hl a suitable diluent and the reaction mixture is generally stirred for a number of hours at the temperatul-e required Worl~-up is carried out by customary methods (cf the Preparation Examples) CA 022~6~08 1998-11-30 ~ Le A 31 691 - Forei~n Countries The active compounds according to the invention can be used as defoliants, desiccants.
haulm killers and, especially, as weed killers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted.
Whether the substances according to the invention act as total or selective herbicides 5 depends essentially on the amount used.

The active compounds according to the invention can be used, for example. in connection with the following plants:

Dicotyledonous weeds of the ~enera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Protulaca, 10 Xanthium, Convolvulus, Ipomoea. Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum. Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura. Viola, Galeopsis, Papaver. Centaurea, Trifolium, Ranunculus and Taraxacum Dicotvledonous crops of the oenera: Gossypium. Glycine, Beta. Daucus. Phaseolus,Pisum, Solanum. Linum, Ipomoea~ Vicia Nicotiana~ Lycopersicon, Arachis, Brassica.
15 Lactuca~ Cucumis and Cucurbita Monocotvledonous weeds of the oenera: Echinochloa~ Setaria Panicum, Digitaria, Phleum~ Poa~ Festuca Eleusine~ Brachiaria~ Lolium~ Bromus Avena Cyperus.
Sorghum~ Agropyrom Cynodon~ Monochoria~ Fimbristylis Sagittaria~ Eleocharis, Scirpus Paspalum~ Ischaemum Sphenoclea Dactyloctenium Agrostis. Alopecurus and 20 Apera Monocot~ ledonous crops of the <~enera: Oryza Zea Triticum. I lordeum Avena, Secale~
Sorghum Panicum. Saccharum Ananas Asparagus and Allium.

Ho~\ever the use of the active compoullds accordhlg to the invelltioll is in no way restricted to these -~enera. but also extends in the same mallller to other plants.

25 The compounds are suitable. depending on the concelltration. for the total control of CA 022~6~08 1998-11-30 Le A 31 691 - Foreig~n Countries weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for the control of weeds in perennial erops for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations. coffee plantations. tea 5 plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, in lawns, turf and pasture land, and for the selective control of weeds in annual cultures.

The compounds of the formula (I) according to the invention are suitable in particular for the selective control of monocotyledonous and dicotyledonous weeds in 10 monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.

The active compounds can be converted into the eustomary formulations, such as solutions. emulsions, wettable powders. suspensions, powders, dusting agents, pastes, soluble powders. granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances 15 These formulations are produced in a known manner, for example by mixing the active compounds with extenders. that is liquid solvents and/or solid carriers. optionally ~vith the use of surface-active agents. that is emulsifying agents and/or dispersing agents and/or foam-forming agents.

If the extender used is water. it is also possible to employ for example organic solvents 20 as auxiliary solvents. Suitable liquid solvents are essentiall! the followillg: aromatics, such as xy lene toluene or alkylnaphtllalenes. chlorinated aromatics and chlorhlated aliphatic hy drocarbons. such as chlorobellzelles. chloroetllylenes or methylene chloride.
aliphatic hydrocarbons such as cyclollexalle or paraffins. for example petroleumfractions milleral and vegetable oils. alcohols. such as butanol or glycol alld also their 25 ethers and esters. I;etones. such as acetone methyl ethyl ketolle metllyl isobutyl ketone or cyclollexallolle strongly polar solvents sucll as dimetll~ltorlnamide and dimethyl sulpho~;ide and also ~ater CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates;
suitable solid carriers for granules are: for example crushed and fractionated natural 5 rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example 10 alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose Tacl;ifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders. granules or latexes, such as gum arabic, polyvinyl alcohol and 15 polyvinyl acetate. as well as natural phospholipids. such as cephalins and lecithins, and synthetic phospholipids. can be used in the formulations. Other possible additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments. for example iron oxide.
titanium oxide and Prussian Blue. and organic dyes. such as alizarin dyes, azo dyes and 20 metal phthalocyanine dyes. and trace nutrients such as salts of iron, manganese. boron, copper~ cobalt. molybdenum and zinc.

The formulations hl general contain bet~een 0.1 and 95 per cent bv ~eight of active compound. preferably bet~een 0 ~ and 90%

For the control of ~eeds the active compoullds accordhl= to the hlvelltioll. as such or ~5 in the form oftheir formulations Call also be used as mi.~tures ~ith l;no~ll herbicides.
finislled formulations or tank mixes beil-g possible Possible componellts for the mixt-lres are l~no~n herbicides. tor example -CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium). ametryne, amidochlor, amidosulphuron, asulam, atrazine, azimsulphuron, benazolin, benfuresate~
bensulphuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos. bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, S chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen~ chlor-sulphuron, chlortoluron, cinmethylin, cinosulphuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulphuron, cloransulam(-methyl), cumyluron. cyanazine, cycloate, cyclosulphamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican.
10 dimefuron, dimepiperate, dimethachlor, dimethametryn. dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymrom, EPTC. esprocarb, ethalfluralin.
ethametsulphuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxapropethyl, flamprop(-isopropyl), flamprop(-isopropyl-L). flamprop(-methyl)~ flazusulphuron,fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl). flumioxazin, flumipropyn, 15 fluometuron fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil. flurenol.
fluridone. fluroxypyr. flurprimidol. flurtamone. fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium). halosafen, haloxyfop(-ethoxyethyl). hexazinone, imazamethabenz(-methyl). imazamethapyr. imazamox. imazapyr. imazaquin.
imazethapyr. imazosulphuron. ioxynil. isopropalin. isoproturon. isoxaben. isoxaflutole, ~0 isoxapyrifop. Iactofen. Ienacil. Iinuron. MCPA. MCPP. mefenacet, metamitron.
metazachlor. methabenzthiazurom metobenzuron. metobromuron. metolachlor, metosulam. metoxuron. metsulphuron(-metl1yl). metribuzin. molinate. monolinuron.naproanilide. napropamide. neburon. nicosulphuron. norflurazon orbencarb. oryzalin.
oxadiazol1 oxyfluorfen. paraquat. pendimethalin. phenmedipham. piperophos~
~5 pretilachlor. primisulplluron(-metl1!1). prometryl1. propachlor. propanil. propaquizafop propyzamide prosulphocarb. prosulpllul-oll pyrazolate. pyrazosulpll-lron(-ethyl).
pyrazo~;yfen. pyributicarb. pyridate. P! rithiobac(-sodium ). quillchlorac quillmerac.
quizaloi'op(-etll!-l). quizalofop(-p-tel-flr!l) l-illlsulpllul-oll. sethox!dilll. simazille.
shlletr! n. sulcotrione. sulphelltrazolle. sulpllometuron(-llletll! l). sulphosate. tebutam.
~0 tebuthiul-oll. terbutll! lazhle. terbutr! n. thellylchlol-. thiafluamide. thiazop! r. thidiazimin.
thit'ellsulpllul-on(-metll!l). thiobellcal-b tiocarbazil. trall;ox!dim triallate triasulplluroll.
tribenuroll(-metl1!1). triclopyr. tridiphalle tritluralin and triflusulphurol1 CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the S use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspension, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

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

10 The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between I g and 10 kg of active compound per hectare of soil surface, preferablybetween 5 g and 5 k~, per ha.

The preparation and the use of the active compounds according to the invention can be 15 seen from the examples below.

CA 022~6~08 1998 - I I - 30 Le A 31 691 - Forei~n Countries Preparation Examples:

~,Y:lrnple 1 IN ~/

N~
F~
ll F
CN

171 g (0.676 mol) of ethyl 2-(4-cyano-2,5-difluoro-benzoyl)-acetate are initially 5 charged in 300 ml of acetic acid and, at an internal temperature of about 40~C, admixed dropwise with 36.3 g (0.80 mol) of methylhydrazine. The mixture is subsequently heated at 90~C to 100~C for about 90 minutes. and a bright yellow solid precipitates out. The mixture is allo~ved to cool slowly and then poured into about 2 litres of ice-~vater. The solid product is isolated by filtration with suction. washed with 10 water and dried under water pump vacuum. It is then stirred with 600 ml of dichloromethane. filtered off with suction and once more dried under water pump vacuum.

This gives 125 ~J (79% of theory) of 3-(4-cyano-2 5-difluoro-phenyl)-5-llydro.Yy-l-methvl-lH-pvrazole of melting point 198~C.

CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries F~ le 2 N ~/

F~N~
ll ~F
CN

A mixture of 47 g (0.20 mol) of 3-(4-cyano-2 5-difluoro-phenyl)-5-hydroxy-1-methyl-I H-pyrazole and 350 ml of N N-dimethyl-formamide is admixed ~ith 55 g of 5 potassium carbonate and heated at 50~C for about 60 minutes. At an internal temperature between 60~C and 70~C 100 g (1.16 mol) of chlorodifluoromethane are then introduced over a period of about 6 hours. The mixture is subsequently concentrated under vater pump vacuum and the residue is taken up in 500 ml of water.
The aqueous suspension is acidified with 2N hydrochloric acid and extracted with10 dichloromethane. The organic phase is washed with water dried with magnesium sulphate and filtered. The filtrate is concentrated under vater pump vacuum and the residue is digested four times ~ ith 500 ml of hot hexane in each case. From thecombined hexane fractions. the solvent is carefully distilled off under ater pump vacuum .

This _ives 24.6 ~ (43% of theory) of 3-(4-cvano-2 5-difluoro-phen 1)-5-difluoro-methoxy- I -methyl- I I l-pyrazole of melting pohlt 80~C.

From the extraction residue. ~ hich is virtually insoluble hl hexalle. the isomeric compound~ c!ano-25-dinuoro-pllellyl)-2-difluolometll!l-1-methyl-p!lazol-5-olleof meltill2 pOillt 128~C can be isolated by column chlolllato~rapll (USill l dichlol-ollletllalle 20 o er silica ~el).

CA 022~6~08 1998-11-30 - Le A 31 691 - Forei~n Countries Example 3 H3C N~O--CHF2 N~Br F~F
CN

At room temperature (approximately 20~C) a solution of 1.9 g (12 mmol) of bromine in 5 ml of dichloromethane is added with stirring to a solution of 2.85 g (10 mmol) of 3-(4-cyano-2,5-difluoro-phenyl)-2-difluoro-methyl-1-methyl-pyrazol-5-one in 20 ml of dichloromethane. The mixture is stirred at about 20~C for 3 hours~ diluted with 20 ml of dichloromethane, washed with saturated aqueous sodium bicarbonate solution and with saturated aqueous sodium chloride solution, dried with magnesium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump I 0 vacuum.

This gives 3.5 g (96% of theory) of 4-bromo-3-(4-cyano-2 5-difluoro phenyl)-5-difluoromethoxy-l-methyl-lH-pyrazole of melting point 79~C.

CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries le 4 CN
~T~O~cH

F~/
N\~ Br N
CH3 ~--CHF2 1.5 g (4 mmol) of 4-bromo-3-(4-cyano-2,5-difluoro-phenyl)-1-methyl-5-difluoro-methoxy-lH-pyrazole are added to a solution of 0.5 g (6 mmol) of sodium methoxide 5 in 40 ml of acetonitrile. The mixture is stirred at room temperature (approximately 20~C) for 16 hours, poured into ~vater and acidified with hydrochloric acid, and the precipitated solid is filtered off, washed with water and dried under water pumpvacuum .

This gives 1. I g (75% of theory) of 4-bromo-3-(4-cyano-~-fluoro-5-methoxy-phellyl)- 1-10 methyl-5-difluoromethoxy-lH-pyrazole of melting point 155~C.

CA 022~6~08 1998-ll-30 Le A 31 691 - Forei~n Countries Examllle ~

CN
F /~ 3--OH

N~ Br N
CH3 ~--CHF2 At room temperature (approximately 20~C), 150 ml (0.15 mol) of a l-molar solution of boron tribromide in dichloromethane are added to a solution of 18.8 g (0.05 mol) of 4-bromo-3-(4-cyano-2-fluoro-5-methoxy-phenyl)- 1 -methyl-S-difluoromethoxy- I H-pyrazole in l O0 ml of dichloromethane. The reaction mixture is stirred at room tem~erature for 16 hours and then admixed with water and dichloromethane. The organic phase is separated off and washed successively with water~ saturated sodium bicarbonate solution and sodium chloride solution, dried over magnesium sulphate and freed from the solvent under water pump vacuum. The resulting crude product is purified by column chromatography using dichloromethane as mobile phase.

This give 8., g (46% of theory) of 4-bromo-3-(4-cyano-2-fluoro-5-hydroxy-phenyl)-1-methyl-S-difluoromethoxv- I H-pyrazole of melting point l 29~C).

CA 022~6~08 1998-11-30 - Le A 31 691 - Forei~n Countries F~mi~le 6 H3C ~ ~~CHF2 N~CI
F~r ~

~O CN
CN

2.8 g 20 mmol) of potassium carbonate and 1.0 g (8 mmol) of bromoacetonitrile are added to a solution of 1.9 g (6.0 mmol) of 4-chloro-3-(4-cyano-2-fluoro-5-hydroxy-5 phenyl)-5-difluoromethoxy-1-methyl-lH-pyrazole in 50 ml of acetonitrile. The reaction mixture is stirred at room temperature (approximately 20~C) for about 16 minutes and then concentrated under water pump vacuum. The residue is admixed with 50 ml of water acidifed with 2N hydrochloric acid and extracted with dichloromethane. Theorganic phase is vashed ~vith saturated aqueous sodium bicarbonate solution and with 10 saturated aqueous sodium chloride solution dried vith magnesium sulphate and filtered. The filtrate is concentrated under vater pump vacuum and the crude product vhich is obtained as residue is purifed by column chromatography (dichloromethane silica gel).

This gives 1.0 g (47% of theory) of 5-(4-chloro-5-difiuoromethoxy-1-methyl-1 H-pyrazol-3-yl)-2-cyano-4-fiuoro-phenoxyacetonitrile of melting point 104~C.

By the methods of Preparatioll E.~;amples 1 to 6 and hl accordance ~ ith the general description of the preparation process accordhl2 to the inventioll it is also possible to prepare for exalllplc the compounds of the formula (I) listed hl Table 1 belo CA 02256508 l998-ll-30 Le A 31 691 - Foreip~n Countries 3-Cvanoaryl-py~zoles R~ Q - R2 N~/
N~R3 R4~ (1) 1~

CN

Table 1: Examples of compounds of the formula (I) Ex. Q Rl R2 R3 R~ R~ Melting No. point (~C) 7 O CH.~ CHF7 Cl F F 77 8 O CH., CHF7 Cl F OC.H~ 80 9 O CH; CHF7 C H3 F CH3 55 ~~~

O Cl 1~ CHF7 Br F OC.H~ 94 1 0 11 O CH ~ CHF. Br F OC~ i 93 12 O CH~ Cl IF. Br F \ ~ 96 13 O Cll~ CIIF. Br F NHSO.CII~ 138 14 O Cll H CH~ F F 171 O Cll~ CIIF~ Cll~ F F 10 16 O CH~ CHF7 Cll~ F O(CII,).OCII~ 4-- Le A 31 691 - Forei~n Countries Ex. Q R' R2 R3 R~ R~ Melting No. point (~C) 17 ~ CH3 CHF, Cl F CH3 70 'oJ~

18 ~ CH3 CHF~ Cl F OCH3 150 S 19 O CH3 CHF, Cl F O(CH,),OCH3 43 ~ CH3 CHF, Cl F OC3H7-i 48 21 ~ CH3 CHF, Cl F OCH,CF3 99 22 ~ CH3 CHF, Cl F ~ ~'~? 90 23 O CH~ CHF, Cl F CH3 47 'oJ~

24 O Cl-{~ CHF, Cl F CH3 26 '~J'l O Cl~ CI IF~ Cl F OCH~C(,H~ 88 26 O Cl 1~ Cl IF~ Cl F ~ (alno~-~ pllo~ls) ~ Le A 31 691 - Forei~n Countries Ex. Q R' R2 R3 R~ Rs Melting No. point (~C) 27 ~ CH3 CHF2 Cl F ~O~O (amor-phous) 28 O CH3 CHF~ Cl F o 100 \~0 29 O CH3 CHF, Cl F ~ 75 ~?

O CH~ CHF~ Cl F 1 82 31 0 CH CHF. Cl F OCI l(CH.F). 60 32 0 CH Cl IF. Cl F OC,I{ -n ~6 33 O Cl l ~ Cl IF. Cl F O(C.I I ,O)~CH ~ (amor-s ) l O 3~ 0 Cl-l CHF. Cl F ~ ~ ~6 CA 02256508 l998-ll-30 ~ Le A 31 691 - Foreign Countries Ex. Q Rl R2 R3 R~ Rs Melting No. point (~C~) O CH3 CHF. Cl F ~ (amor-b phous) 36 ~ CH3 CHF, Cl F 1 76 O ~CN

37 S CH , CH , H F F 11 6 38 O CH~ CHF. Cl F OCH,CH,F 78 39 O C~{3 CHF~ Cl F OCH.COOCH3 110 O Cl 13 Cl IF. Cl F CH3 44 ~OJ~o OC2Hs ~1 O Cll~ CIIF. Cl F CH3 1 13 \o~o 4~ O Cll~ CHI:~ Cl 1- OCII~CHF~ 73 O Cl-l C~ Cl f~ \ ~f~o I 1 OC3H, -i Le A 31 691 - Forei~n Countries Ex. Q R' R2 R3 R~ R~ Melting No. I)oint (~C) 44 O CH3 CHF, Cl F CH3 56 ~OJ~o OC3H7-i O CH3 CHF, Cl F N(SO~CH3), 175 46 ~ CH3 CHF~ Cl F NHSO.CH3 139 47 S CH3 CH3 Br F F 100 48 ~ CH3 CHF, Br F OC3H7-n 71 49 O CH3 CHF~ Br O~ 46 O CH3 CHF7 Br F CH3 69 ~0/~

51 O Cl-l. CIIF, Br F CH3 70 \o~

52 O CH.~ CHF. Br F O(CH.),OCH3 36 53 O CH, CHF. Br F O(C.II,O).CH, 33 54 O CH~ CIIF. Br F OCH~CF 109 O CH~ CHF. Br F OCH(CH~F). 98 ' Le A 31 691 - Forei~n Countries Ex. ~2 R' R2 R3 R~ Rs Melting No. point (~C~
56 ~ CH3 CHF, Br F OCH,C6H5 75 57 O CH3 CHF, Br F o 122 ~0 58 ~ CH3 CHF2 Br O
~?

59 O CH3 CHF. Br O 103 O CH. CHF. Br F F 83 ~0~

61 O CH., CHF7 Br F ~ 40 ~>

.

Le A 31 691 - Foreign Countries Ex. Q Rl R2 R3 R~ Rs Melting No. point (~C) 62 0 CH3 CHF7 Br F 0 40 'O

63 0 CH3 CHF, Br F ~ 35 ~'1CH3 64 0 CH~ CHF7 Br F ~ (amor-~ ~ phous) 0 CH~ CHF. Br F Nl{SO~C.I 1~ 95 66 0 Cl 1~ CHF. Br F \ ,~o 111 0~2Hs 67 0 Cl-l. CHE~. Br F ~ ~o 86 OC3H7-i 68 0 Cll CIIF~ Br F CH3 '~8 ~0~~
OC2Hs CA 02256508 l998-ll-30 Le A 31 691 - Forei~n Countries Ex. Q R' R2 R3 R~ R' Melting No. point (~C) 69 O CH3 CHF, Br F OCH,CHF7 88 O CH3 CHF, Br F OCH,CH,F 89 71 ~ CH3 CHF, Br F OCH2CN 108 72 ~ CH3 CHF. Br F CH3 56 ~0~~
OC3H7-i 73 O CH3 CHF, Br F OCH7COOCH3 89 74 O CH3 CHF, Br F 1 74 O ~ CN

75 O CH3 Cl IF, Br F CH3 104 ~0~~

76 O CH.~ Cl{F. Br F -N(SO7CH,). 64 77 o CH3 CHF, Br F -N(SO7CH3)- 58 (COC6H~) 78 O Cl{; CHF7 Cl F -N(SO.CH3)- 60 (COC6l{~) 79 S CH~ 11 H F F 137 S Cll1 CHF, 11 F F 104 I 5 81 S CH~ Cl l, Br F O(CH7).0CI 1~ 99 82 SO. CH3 Cl l ~ Br F F 176 Le A 31 691 - Forei~n Countries Ex. Q R' R2 R3 R~ Rs Melting No. point (~C~) 83 S CH3 CHF, Br F F 100 84 SO, CH3 CH3 Br F O(CH,),OCH3 153 S CH3 CHF2 Br F CH3 ~0~

86 S CH3 CHF, Br F O(CH,),OCH3 88 89 S CH3 CHF, Br F ~O 105 SO, CH3 CH~ Br F ~ 131 91 S CH~ CHF, Br F ~ 1~5 Le A 31 691 - Forei~n Countries Ex. Q Rl R2 R3 R~ Rs Melting No. point (~C) 92 SO, CH3 CH3 Br 93 S CH3 CHF, Br F ~ 105 94 SO, CH3 CH; Br F ~O 123 S CH3 CH; Cl F F 75 96 S CH~ CH~ Br F CH3 101 ~0~

97 SO. CH1 CH~ Br F F 176 98 S Cl-l~ CF, H F F 67 99 S CH~ Cl IF~ Br F ~ 105 ~?

CA 02256508 l998-ll-30 Le A 31 691 - Foreip~n Countries Ex. Q R' R2 R3 R' R~ Melting No. point (~C) 100 SO~ CH3 CH3 Br F ~ O 131 ~?

101 S CH3 CHF, Br F OCH(CH3)~ 125 102 S CH3 CHF~ Br F ~ 105 103 SO, CH3 CH3 Br F OCH(CH3)~ 182 104 SO. CH3 CH3 H F ~O 123 105 S CH3 CH3 Cl F F 75 106 S CH3 CH3 Br F CH3 101 ~o,J\~

107 S Cll CHF~ Cl F F 57 Le A 31 691 - Forei~n Countries Ex. Q R' R2 R3 R' Rs Melting No. point (~C) 108 SO, CH3 CH3 Br F CH3 76 ~0~

109 SO, CH3 CH3 Br F OCH3 195 11 0 SO, CH3 CH3 Br F ~O 11 7 07 CH3 CH3 Br O~~ 130 11 2 S CH3 CHF, Cl F ~ ~ 82 I l3 SO, CH3 CH; Cl F F 151 114 SO, CH3 CH3 Br F -OCH.CH.F 139 1 15 SO, CH~ CH3 Br CH3 I l6 SO. Cl{; CH~ Br F -NHSO.CH3 185 I l7 S CH; CH.F 1{ F F 129 I l8 SO. CH; Cll.F Cl F F 79 1 19 SO. CHl Cll, Cl F CH3 140 ~ol~

Le A 31 691 - Forei~n Countries Ex. Q R' RZ R3 R~ R~ Melting No. point (~C) 120 SO, CH3 CH3 Cl F ~O 107 121 S CH3 CH,F Br F F 58 122 S CH3 CHF, Cl F ~ 116 123 S CH~ Cl{F, Cl F -OCH.CH.OCH3 (amor-phous) 124 S CH~ CHF, Cl F CH3 42 ~0~

125 S CH, CH,F Br F CH3 88 ol~

126 S Cll, CIIF~ Cl F OCH(CII~). 105 127 S Cll~ CIIF~ Cl F \ 78 CA 02256508 l998-ll-30 Le A 31 691 - Forei~n Countries Ex. Q R' R2 R3 R~ Rs Melting No. point (~C) 128 S CH3 CHF2 Cl F -OCH7CH2F 85 129 SO2 CH3 CH2F Br F F 145 130 S CH3 CH2F Br F ~O 146 ~?

131 SO, CH3 CH~F Br F ~ 166 ~?

I 32 S CH3 CH~F Br F -OCH(CH~)~ 122 133 S CH3 CH.F Br F -OCH.CH~OCH3 54 134 SO, CH3 CH~F Br F -OCH.CH~OCH3 122 135 S CH3 CH,F Br F -OCH~CH7F I15 136 S CH3 CH~F Br F ~ ~ 129 137 S CH3 Cll.F Br F ~ 97 0~

138 SO~ Cll; Cll.F Br F ~ ~ 146 CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries The compound listed in Table I as Example 47 can be prepared, for example~ as follows:

CN
F ~J F

N\~Br N

At room temperature (approximately 20~C). a solution of 4 2 g (26 mmol) of bromine in 10 ml of dichloromethane is added with stirring to a solution of 6.0 g (23 mmol) of 3-(4-cyano-2,5-difluoro-phenyl)- 1 -methyl-5-methylmercapto- I H-pyrazole in 80 ml of dichloromethane. The reaction mixture is stirred at room temperature for about 60 minutes, diluted with 20 ml of dichloromethane and washed successively with dilute sodium hydrogen sulphite solution. saturated sodium bicarbonate solution and sodium chloride solution. dried over magnesium sulphate and freed from solvent under water pump vacuum This gives 7.0 _ (88.5% of theory) of 4-bromo-3-(4-cyano-2.5-diiluoro-phenyl)-1-methyl-5-metllylmercapto-11~-pvrazole as a crystalline solid of melting point 100~C.

The compound listed in Table I as Example 79 can be prepared. for example. as I ~ follo~ s:

--Ni N~

F~'F
CN

CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries A mixture of 2.4 g ( 10 mmol) of 3-(4-cyano-2,5-difluoro-phenyl)-S-hydroxy-l -methyl-I H-pyrazole, 6.7 g (30 mmol) of phosphorus(V) sulphide and 50 ml of xylene is heated under reflux for 9 hours. The mixture is subsequently concentrated under water pump vacuum and the residue is stirred with 50 ml of 2N aqueous sodium hydroxide S solution. The mixture is then filtered and the filtrate is acidified with 2N hydrochloric acid. The crystalline product which is obtained is isolated by filtration with suction.

This gives 1.6 g (64% of theory) of 3-(4-cyano-2,5-difluoro-phenyl)- 1 -methyl-S-mercapto- I H-pyrazole of melting point 1 37~C.

The compound listed in Table I as Example 79 can also be prepared, for example~ as 1 0 follows:

CN

F~'' N,~
N

At -20~C. a solution of 10.9 c (0.06 mol) of 1-(2.5-diRuoro-4-cyallo-phenyl)-ethanone in 50 ml of tetrahvdrofuran is added dropwise over a period of about 30 minutes to a suspension of 13.5 ~, (0.12 mol) of potassium t-butoxide hl 100 ml of tetrahydrofurall.
15 The mixture is stirred at -20~C for appro.~;imately 30 mhlutes and then admixed with 4.6 g (0.06 mol) of carbon disulpllide (CSl). After a further 30 minutes. 7.3 g (0.1~ mol) of acetic acid and 5.6 (1 (0.12 mol) of methvlhvdrazine are added successivel!. and the reaction mixture is allo~ed to ~arm to room temperature over a period of ' hours. The reactioll mixture is thell poured hlto ~50 ml of ice-~ater and 20 ~ashed ~ith dichloromethalle. The aqueous phase is ad justed to pl I i usin<~hydrochloric acid and extracted repeatedl~ ith dichloromethalle. The extracts from the hydrocllloric-acid solution are ~-ashed ~ith sodium chloride solution. dried over CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countriçs magnesium sulphate and freed from the solvent under water pump vacuum.

This gives 5.6 g (37% of theory) of 3-(4-cyano-2,5-difluoro-phenyl)-1-methyl-5-mercapto-lH-pyrazole as a crystalline yellow solid of melting point 137~C.

The compound listed in Table I as Example 80 can be prepared, for example, as S follows:

CN
~,, F

N~
,N

A solution of 5 g (0.02 mol) of 3-(4-cyano-2.5-difluoro-phenyl)-5-mercapto-1-methyl-1 H-pyrazole in 80 ml of N.N-dimethyl-formamide is admixed with 8.3 g (0.06 mol) of potassium carbonate and heated to 50~C. At this temperature. about 10.4 g (0.12 mol) 10 of chlorodifluoromethane are introduced over a period of 3 hours. After the reaction has ended. the predominant part of the solvent is removed under water pump vacuum and the residue is tal~en up in 50 ml of ~ater. The aqueous suspension is acidified using 2N hvdrochloric acid and extracted ~ith dichlorometllane. The organic phase is washed with water. dried over magllesium sulphate and freed from the solvent under 1~ water pump vacuum.

Tllis ~ives ~.2 g (86% of theory) of 3-(4-cyano-2.~-difluol-o-pllellyl)-~-difluoro-metll~ Imercapto- I -meth~ 1-1 1 I-pyrazole of meltillg point 1 04~C.

The compound listed in Table I as E.~;alllple 8~ can be prepal-ed tor example. as fol lo~ s:

CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries CN
F/~,F

~ Br At -5~C, a suspension of 9.9 g (40 mmol) of 70% strength 3-chloro-perbenzoic acid in 130 ml of dichloromethane is added with stirring to a solution of 5.5 g (16 mmol) of 4-bromo-3-(4-cyano-2,5-difluoro-phenyl)- 1 -methyl-S-methylmercapto- 1 H-pyrazole in 5 100 ml of dichloromethane. The reaction mixture is stirred at room temperature(approximately 20~C) for 16 hours, the precipitated solid is filtered off and the filtrate is washed successively with saturated. sodium thiosulphate solution, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulphate and freed from the solvent under water pump vacuum.

This gives S.S g (91% oftheory) of 4-bromo-3-(4-cyano-~ S-difluoro-phenyl)-l-methyl-S-methylsulphonyl-lH-pyrazole as a crystalline solid of melting point 176~C.

The compound listed in Table I as Example 83 can be prepared. for example~ as follo~s:

CN

F ~ F
N\~Br N

.
CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries At room temperature (approximately 20~C). a solution of 4.8 g (30 mmol) of bromine in 15 ml of dichloromethane is added with stirring to a solution of 5.1 g (17 mmol) of 3-(4-cyano-2,5-difluoro-phenyl)-5-difluoro-methylmercapto- I H-methyl- I H-pyrazole in 20 ml of dichloromethane. The reaction mixture is heated under reflux for 18 hours, 5 diluted with 20 ml of dichloromethane and washed successively with dilute sodium hydrogen sulphite solution, saturated sodium bicarbonate solution and sodium chloride solution, dried over magnesium sulphate and freed from the solvent under water pump vacuum.

This gives 5.8 g (90% of theory) of 4-bromo-3-(4-cyano-2,5-difluoro-phenyl)-5-10 difluoromethylmercapto-l-methyl-lH-pyrazole as a crystalline solid of melting point l OO~C.

The compound listed in Table I as Example 87 can be prepared, for example, as follo~vs:

CN

,, N~
N

At room temperature (approximatelv _0~C). 2.5 g (55 mmol) of methvlllvdrazille are added to a solution of 6.2 g (~2 mmol) of 1-(4-cyano-2.5-difluoro-pllenyl)-3.3-bis-(methyltllio)-~-propen-l-olle in 60 ml of acetonitl-ile. The reaction mixture is heated undel- reflux t'or 90 minutes and thell poured into ice-~vater. The precipitated solid is filtered of'f ~ith suctio~ ashed ~ith ~ater alld dried under reduced pressure.

This ~rives ~.0 (r (86% of theory) of 3-(4-cyallo-2.5-difluolo-pllellyl)- 1 -methyl-5-methylmercapto- I H-pvrazole of melthlg pohlt I 1 8~C.

CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries Staffin~ matenals of the formula (I~):

Example (III-I) ~ C2H5 Oq~

F~F
CN

At 10~C to 15~C, 147 g (1.46 mol) of triethylamine and 170 g (1.80 mol) of 5 magnesium chloride (anhydrous) are added successively to a mixture of 251 g (1.48 mol) of potassium monoethyl malonate in 2 litres of acetonitrile. The mixture is stirred at room temperature (approximately 20~C) for about 150 minutes. then cooled to -10~C to -5~C and, at this temperature~ admixed successively with 145 g (0.72 mol) of 4-cyano-2,5-difluoro-benzoyl chloride and 14.7 g (0.146 mol) of triethylamine. The 10 reaction mixture is then stirred at room temperature for approximately 18 hours and subsequently concentrated. The residue is admixed with 1.2 litres of toluene and then with I litre of 13% strength hydrochloric acid. The mixture is stirred at room temperature for 3 hours~ the precipitated solid is filtered off and the organic phase is separated off from the filtrate. The organic phase is washed ~vith 13% strength 15 hydrochloric acid and then ~ith ~vater~ dried ~vith magnesium sulphate and filtered. The solvent is carefully distilled off from the filtrate under ~vater pump vacuum.

This gives 173 g (95% of theory) of ethyl 3-(4-cyano-2 5-difluoro-pllenyl)-3-oxo-propiollate of melting pohlt 44~C as a bright yello\~. solid residue.

CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries Example (111-2) q~ C2H5 q~'~ CH3 F~F
CN

Using the method of Example (111-1) and potassium monoethylmethyl malonate instead of potassium monoethyl malonate, the compound ethyl 3-(4-cyano-2.5-difluoro-phenyl)-5 2-methyl-3-oxo-propionate is obtained in 93.6% yield as a yello~v liquid.

~H NMR (CDCI3, d, ppm): 1.20 (t, 311), 1.50 (d. 3H)~ 4.17 (q. 2H)~ 4.32 (q. IH), 7.48 (dd, IH), 7.73 (dd, IH).

Example (111-3) NC ~S--CH3 At -20~C. a solution of 10.9 g (0.06 mol) of 1-(4-c~ano-2 5-difluoro-phen~l)-ethanone in S0 ml of tetrahydrofuran is added drop~vise over a period of 0.5 hours to a suspension of 13.~ ~o (0.12 mol) of potassium t-butoxide in 100 ml of tetrah drofuran.
The mixture is stirred at -20~C for about 30 mhlutes and thell admixed ~ith ~.6 g (0.06 mol) of carbon disulphide (CS.). After a further 30 mhlutes. 17.0 g (0.1~ mol) of 1~ methy I iodide are added and the reactioll mixture is allo~ed to ~arm to roomtemperature over a period of ~ hours. The reaction mixture is poured into ~00 ml of ice-~ater. adjusted to pl-l I ushlg h~drocllloric acid alld extracted ~ith 1~00 ml of eth~l acetate. The organic phase is ~ashed ~ith sodium chloride solution. dried over CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries magnesium sulphate and freed from the solvent under water pump vacuum. The crudeproduct which is obtained as a residue is stirred with approximately 20 ml of acetonitrile and the precipitated solid is filtered off and dried.

This gives 6.9 g (40% of theory) of 1-(4-cyano-2,5-difluoro-phenyl)-3,3-bis-S (methylthio)-2-propen-1 -one as a crystalline bright yellow solid of melting point 1 88~C.

Staffin~F matenals of the formula (V):

Example (V-l) O~C

F~'F
CN
6.7 g (56 mmol) of thionyl chloride are added drop~vise 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-dimethyl-formamide. The reaction mixture is then heated under reflux for approximately 6 hours. After the evolution of gas has ceased the mixture is allowed to cool and filtered. The volatile components are then carefully distilled off from the filtrate under water pump vacuum.

This gives 3.6 g (95.5% of theory) of 4-cyano-7.5-difluoro-benzoyl chloride as a y ello~ liquid.

111 NMR (CDCI~ d. ppm): 7.95 (dd 111). 7.54 (dd. IH).

CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries Staffin~ maferials of the fonnula (VO:

Example (Vl-l) O~OH

F ~ F
CN

At at most 40~C, a solution of 5.74 g (29 mmol~ of 2,5-difluoro-4-nitromethyl-benzonitrile in 30 ml of acetone is added dropwise to a suspension of 8.0 g (50 mmol) of potassium permanganate (ground finely in a mortar) in 100 ml of acetone. The reaction mixture is then stirred at room temperature (approximately 20~C) for about 16 hours and subsequently acidified using 2N hydrochloric acid. The precipitated manganese dioxide is removed by filtration and tlle filtrate is concentrated under water pump vacuum. The residue is taken up in ethyl acetate, washed with water, dried with magnesium sulphate and filtered. The filtrate is concentrated and the residue is stirred with a little dichloromethane and filtered off with suction.

This gives 3.4 g (64% of theory) of 4-cyano-2.5-di~uoro-benzoic acid as a crystalline product of melthlg point 1 59~C.

'H NMR (DMSO-D6. d. ppm): 7.92 (dd. IH) 8.15 (dd IH)~ 14.10 (s broad 111).

Example (Vl-'7) O~OH

F ~ F
CN

CA 022~6~08 1998-11-30 Le A 31 691 - ~orei~n Countries Step I

A mixture of 9.5 g (50 mmol) of methyl 2,4,5-trifluoro-benzoate, 2.7 g (55 mmol) of sodium cyanide and 100 ml of N,N-dimethyl-formamide is stirred at approximately 25~C for 3 days and subsequently filtered through activated carbon. The filtrate is 5 concentrated using water pump vacuum and the residue is recrystallized from cyclohexane/ethyl acetate (Vol.: 9:1).

This gives 4.0 g (41% of theory) of methyl 4-cyano-2,5-difluoro-benzoate of melting point 60~C.

Step 2 A mixture of 0.83 g (4.4 mmol) of methyl 4-cyano-2,5-difluoro-benzoate, 0.49 g (4.4 mmol) of potassium t-butoxide, 50 ml of diethyl ether and 10 ml of water isstirred at approximately 23~C for 12 hours. The mixture is subsequently acidified using conc. hydrochloric acid. and the organic phase is separated off. dried over sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water 15 pump vacuum.

This gives 0.50 g (62% of theory) of 4-cyano-2.5-difluoro-benzoic acid as a crystalline product of melting point 1 59~C.

By the method of Example (Vl-l ) or (Vl-7). it is also possible to prepare. for example.
the compounds 5-chloro-4-cyatlo-7-~uoro-benzoic acid (melthlg point: 147~C) and 7-70 chloro-4-cyano-5-fluoro-benzoic acid (melting point: 163~C).

CA 022~6~08 1998-11-30 Le A 31 691 - Forei~n Countries Staffin~ matenals of the folmula (V~

Example (Vll-l) ~NO2 Cl ~F

CN

3.7 g (60 mmol) of nitromethane are initially charged together with 80 ml of ethyl acetate and 18.2 g (120 mmol) of diazabicycloundecene (DBU), and the mixture is cooled to -10~C. A solution of 8.7 g (50 mmol) of 5-chloro-2.4-difluoro-benzonitrile in 50 ml of ethyl acetate is then added dropwise~ and the reaction mixture is stirred in an ice bath for about 15 hours and subsequently acidified using 2N hydrochloric acid. The organic phase is separated off. shaken with saturated aqueous sodium chloride solution, dried with magnesium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vacuum.

This gives 9.7 g (73.6% pure. i.e. 67% of theory) of 5-chloro-2-fiuoro-4-nitromethyl-benzonitrile as an amorphous residue ~/hich can be emplo,ved without any furtherpurification for the next reaction step.

By the method of Example (Vll-l). it is also possible to prepare for example. the compounds 2.5-di fluoro-4-1litromethyl-benzonitrile (melting point: 1 00~C) and 2-chloro-5-fluoro-4-nitromethyl-bellzonitrile (melting pohlt: 35~C).

CA 022~6~08 1998-11-30 ~ Le A 31 691 - Foreign Countries Stain~in~ mateirials of the formula (X):

Example (X-l) Oq~CH3 F~F
CN

5.16 g (24 mmol) of 2,5-difluoro-4-(1-nitro-ethyl)-benzonitrile are dissolved in 50 ml 5 of acetic acid, and the mixture is heated under refiux for 8 hours and. after cooling, introduced into about 200 ml of water. The mixture is then extracted with dichloromethane and the organic phase is washed successively with water, saturated sodium bicarbonate solution and with saturated sodium chloride solution, dried with magnesium sulphate and filtered. The filtrate is concentrated under ~vater pump vacuum 10 and the residue is extracted repeatedly ~vith hot n-hexane. The solvent is carefully distilled off from the combined extract solutions under water pump vacuum.

This gives 2.72 g (62% of theory) of 1-(275-difluoro-4-cyano-phenyl)-ethanone as a colourless crystalline residue of melting point 42~C.

Example (X-2) O~CH3 F ~, 1~ 1 11 --F
CN

5.~ g (0.11 mol) of sodium cyanide (ground) h- 200 ml of N.N-dimethyl-f'ormamide are sth-l-ed \~ ith 17.-'7 ~7 (0.10 mol) of 2 4 5-trifiuoro-acetopllellolle at 25~C for 12 hours. The mixtul-e is filtered off ~ith suction. the filtrate is filtered throu_~71l activated carbon and the solvent is carefull~ distilled off f;-om the filtrate under ~ater pump ~acuum - Le A 31 691 - Foreign Countries This gives 10.4 g (57% of theory) of 1-(2,5-difluoro-4-cyano-phenyl)-ethanone as an amorphous residue.

IR spectrum: 1698 cm~' (CO), 2240 cm~' (CN).

CA 022~6~08 1998-11-30 - Le A 31 691 - Forei~n Countries Use Examples:

Example A

Pre-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: I part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, I part by weight of activecompound 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 preparation of active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray series is chosen so that the particular amounts of active compound desired are applied in 1000 1 of ~vater/ha.

After three ~veeks the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

The fi~ures denote:

0% = no effect (lil~e untreated control) 100% = total destruction In this test. at application rates of 60 and 125 g/lla. for example the compoullds of Prepal-atioll Examples 3. 4. 7. 8. 1 0. 11 . 1 ~. 1 3 and I 4 e.~;hibit very stromg activity agail1st ~eeds such as Dig;tar;a (80-100%). Setaria (70-100%) Amarallthus (100%)Datul-a (90-100%) and Solanum (100%) and some of thelll are tolerated ~ell by crop plants such as for example maize (5%) soya (0-30%) and cotton (0-30%).

CA 022~6~08 1998-11-30 Le A 31 691 - Foreign Countries )le B

Post-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: I part by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active compound, I 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.
Test plants which have a height of 5-15 cm are sprayed with the preparation of active compound in such a way as to apply the particular amounts of active compound desired 10 per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1000 1 of water/ha.

After three weeks? the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

The figures denote:

0% = no effect (lil;e untreated control) 100% = total destruction In this test. at application rates of ~0 and 60 <'Ala. for example the compoullds of Preparation Examples ,. ~. 7. 8. 10. I l. I'. 13 and 15 sho~ ver! strong activity agaillst ~veeds such as Abutilon (100%). Chenopodi-llll (95-100%). Solallum (100%).
~0 Digitaria (70-100%) and Setal-ia (80-100%).

Claims (10)

Claims
1. 3-Cyanoaryl-pyrazoles of the general formula (I) characterized in that Q represents oxygen (O), sulphur (S), SO or SO2, R1 represents hydrogen or represents alkyk, alkenyl, alkinyk cycloalkyl or cycloalkylalkyl, each of which is optionally substituted, R2 represents hydrogen or represents alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkylalkyl, each of which is optionally substituted.

R3 represents hydrogen halogen or optionally substituted alkyl.

R1 represents hydrogen or halogen and R3 represents hydrogen, hydroxyl, mercapto, amino, hydroxyamino, halogen, or represents one of the radicals -Q-R6, -NH-R6, -NH-O-R6, -NH-SO2-R6--N(SO2-R6)2, -CQ1-R6, -CQ1-Q2-R6, -CQ1-NH-R6, -Q2-CQ1-R6, -NH-CQ1-R6, -N(SO2-R6)(CQ1-R6), -Q2-CQ1-Q2-R6, -NH-CQ1-Q2-R6 or -Q2-CQ1-NH-R6.

where Q1 and Q2 each represent oxygen or sulphur and R6 represents alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, each of which is optionally substituted, except for the compounds 1-methyl-3-(4-cyano-2-fluoro-phenyl)-4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-phenyl)-4-bromo-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-5-nitro-phenyl)-4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-5-ethylsulphonylamino-phenyl)-4-chloro-5-difluoromethoxy-pyrazole,1-methyl-3-(4-cyano-2-fluoro-5-ethoxycarbonylmethoxy-phenyl)-4-chloro-5-difluoro-methoxy-pyrazole, 1-methyl-3-(4-cyano-2-chloro-phenyl)-4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-5-methylthio-phenyl)-4-chloro-5-difluoromethoxy-pyrazole, 1-methyl-3-(4-cyano-2-fluoro-5-amino-phenyl)-4-chloro-5-difluoromethoxy-pyrazole, 1-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, 1-methyl-3-(4-cyano-2-fluoro-5-aminosulphonyl-phenyl)-4-chloro-5-difluoromethoxy-pyrazole and 1-methyl-3-(4-cyano-2-fluoro-5-fluorosulphonyl-phenyl)-4-chloro-5-difluoromethoxy-pyrazole.
2. Process for preparing 3-cyanoaryl-pyrazoles of the general formula (I) in which R1, R2, R3, R4, R5 and Q are each as defined in Claim 1.

characterized in that hydrazine or derivatives thereof of the general formula (II) H2N-NH-R1 (II), in which R1 is as defined above, are reacted with cyanoarylcarbonyl compounds of the general formula (III) in which R3, R4 and R5 are each as defined above.

Q3 represents oxygen or sulphur and R represents hydrogen or alkyl.

- and/or, if appropriate, tautomers of the compounds of the formula (III) -and, if appropriate, further conversions within the scope of the above definition of the substituents are carried out by customary methods on the resulting compounds of the formula (I).
3. Cyanoaryl compounds of the general formula (III) in which R3, R4 and R5 are each as defined in Claim 1 and Q3 represents oxygen or sulphur and R represents hydrogen or alkyl.
4. Cyanobenzoyl halides of the general formula (V) in which R4 and R5 are each as defined in Claim 1 and X1 represents halogen.
5. 4-Cyanobenzoic acids of the general formula (VIa) in which R4 and R5 are each as defined in Claim 1,
6. Nitromethylbenzonitriles of the general formula (VII) in which R5 is as defined in Claim 1 and X2 represents halogen.
7. Herbicidal compositions, characterized in that they contain at least one 3-cyanoarylpyrazole of the general formula (I) according to Claim 1.
8. Method for controlling undesirable plants, characterized in that 3-cyanoarylpyrazoles of the general formula (I) according to Claim 1 are allowed to act on undesirable plants and/or their habitat.
9. Use of 3-cyanoarylpyrazoles of the general formula (I) according to Claim 1 for controlling undesirable plants.
10. Process for preparing 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.
CA002256508A 1996-06-03 1997-05-21 3-cyanoaryl pyrazoles and use thereof as herbicides Abandoned CA2256508A1 (en)

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DE1996122189 DE19622189A1 (en) 1996-06-03 1996-06-03 3-cyanaryl pyrazole
DE19622189.7 1996-06-03
PCT/EP1997/002580 WO1997046535A1 (en) 1996-06-03 1997-05-21 3-cyanoaryl pyrazoles and use thereof as herbicides

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DE19838706A1 (en) 1998-08-26 2000-03-02 Bayer Ag Substituted 3-aryl-pyrazoles
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US6897322B2 (en) * 2001-01-16 2005-05-24 Basf Aktiengesellschaft Method of producing 1-alkyl-3-aryl-5-difluoromethoxy-1H-pyrazoles
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US5624601A (en) * 1994-10-20 1997-04-29 Shin-Etsu Chemical Co., Ltd. Silacyclohexane compounds, a liquid crystal composition comprising the same and a liquid crystal device comprising the composition
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