CN1227545A - 3-cyanoaryl pyrazoles and use thereof as herbicides - Google Patents

3-cyanoaryl pyrazoles and use thereof as herbicides Download PDF

Info

Publication number
CN1227545A
CN1227545A CN 97197015 CN97197015A CN1227545A CN 1227545 A CN1227545 A CN 1227545A CN 97197015 CN97197015 CN 97197015 CN 97197015 A CN97197015 A CN 97197015A CN 1227545 A CN1227545 A CN 1227545A
Authority
CN
China
Prior art keywords
methyl
fluoro
chloro
phenyl
pyrazoles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 97197015
Other languages
Chinese (zh)
Inventor
O·沙尔纳
K·-H·林克
K·－J·罗伊布克
M·多林格
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of CN1227545A publication Critical patent/CN1227545A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

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, R<1> is hydrogen or possibly substituted alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkyl alkyl, R<2> is hydrogen or possibly substituted alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkyl alkyl, R<3> is hydrogen, halogen or possibly substitued alkyl, R<4> is hydrogen or halogen, and R<5> is hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen or one of the radicals -Q-R<6>, -NH-R<6>, -NH-O-R<6>, -NH-SO2-R<6>, -N(SO2-R<6>)2, -CQ<1>-R<6>, -CQ<1>-Q<2>-R<6>, -CQ<1>-NH-R<6>, -Q<2>-CQ<1>-R<6>, -NH-CQ<1>-R<6>, -N(SO2-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 Q<1> and Q<2> are oxygen or sulphur and R<6> 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-dif luoro methoxy pyrazol are excepted by disclaimer.

Description

3-cyanoaryl pyrazoles and as herbicide applications
The present invention relates to new 3-cyanoaryl pyrazoles, their preparation methods, new intermediate, and they are as the purposes of weedicide.
3-aryl-the pyrazoles of more known replacements have herbicidal properties (referring to EP 361114, EP447055, WO 92/02509, WO 92/06962, WO94/26109, WO95/33728, WO96/01255).But it is satisfied fully that the weeding activity of these compounds and farm crop security are not always made us.
Therefore, the invention provides the new 3-cyanoaryl pyrazoles of logical formula I:
Figure A9719701500061
Wherein
Q represents oxygen (O), sulphur (S), SO or SO 2,
R 1Represent the optional separately substituted alkyl of hydrogen or representative, alkenyl, the alkynes base, cycloalkyl or cycloalkylalkyl,
R 2Represent the optional separately substituted alkyl of hydrogen or representative, alkenyl, the alkynes base, cycloalkyl or cycloalkylalkyl,
R 3Represent hydrogen, halogen or optional substituted alkyl,
R 4Represent hydrogen or halogen,
R 5Represent hydrogen, hydroxyl, sulfydryl, amino, hydroxyl amino, halogen, perhaps in the residue below the representative:
-Q-R 6,-NH-R 6,-NH-O-R 6,-NH-SO 2-R 6,-N (SO 2-R 6) 2,-CQ 1-R 6,-CQ 1-Q 2-R 6,-CQ 1-NH-R 6,-Q2-CQ 1-R 6,-NH-CQ 1-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 6Or-Q 2-CQ 1-NH-R 6,
Q wherein 1And Q 2Represent oxygen or sulphur separately, and R 6The optional separately substituted alkyl of representative, alkenyl, the alkynes base, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclic radical or heterocyclic radical alkyl, but except following compounds:
1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-bromo-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-nitro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethylsulfonyl amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethoxycarbonyl methoxyl group-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-methyl sulfenyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-amino-sulfonyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles and 1-methyl-3-(4-cyano group-2-fluoro-5-fluorosulfonyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles (learning from WO96/01255), these compounds are got rid of by abstention.
If suitably in the presence of thinner, when the cyano-aryl carbonyl compound of the hydrazine or derivatives thereof of logical formula II and logical formula III and/or, if suitably, during the tautomerism precursor reactant of formula III compound, obtained the new 3-cyanoaryl pyrazoles H of logical formula I 2N-NH-R 1(II), wherein R 1As above definition,
Figure A9719701500071
Wherein
R 3, R 4And R 5As above definition separately,
Q 3Represent oxygen or sulphur and
R represents hydrogen or alkyl, preferably represents hydrogen or C 1-C 6-alkyl,
And, if suitably, the logical formula I compound that obtains is further transformed in the above-mentioned substituting group range of definition by ordinary method.
The compound of logical formula I can change into the compound of other logical formula I according to the substituting group of above-mentioned definition by ordinary method, for example by conventional alkylating, and acylation or sulfoacylation (R for example 2: H → CH 3, CHF 2, C 2H 5, CH 2CH=CH 2R 5: OH → OCH 3, OC 2H 5, OCHF 2, OCH 2CH=CH 2, OCOCH 3SH → SCH 3, SC 2H 5NH 2→ NHC 3H 7, NHCOCH 3, NHSO 2CH 3), by sulfuration (QR for example 2: OH → SH), by oxygenizement (S → SO for example, SO 2) or by close electricity or nucleophilic substitution (R for example 3: H → C1, Br; R 5: F → OH, SH, NH 2)-also is referring to preparation embodiment.
The new 3-cyanoaryl pyrazoles of logical formula I has strong weeding activity.
In definition, saturated or unsaturated alkyl, alkyl for example, alkenyl or alkynes base are straight or branched in all cases.
Halogen general proxy fluorine, chlorine, bromine or iodine is preferably represented fluorine, chlorine or bromine, special representative's fluorine or chlorine.
The present invention preferably provides the formula I compound,
Wherein
Q represents oxygen (O), sulphur (S), SO or SO 2,
R 1Represent hydrogen, representative is optional by cyano group, halogen or C 1-C 4The alkyl that-alkoxyl group replaces with 1-6 carbon atom, represent and have optional alkenyl or the alkynes base that is replaced by halogen under 2-6 carbon atom and the various situation under the various situations, perhaps represent have in the cycloalkyl under the various situations 3-6 carbon atom and, if suitably, have 1-4 carbon atom in the moieties, and optional in all cases by cyano group, halogen or C 1-C 4Cycloalkyl or cycloalkylalkyl that-alkyl replaces,
R 2Represent hydrogen, representative is optional by cyano group, halogen, C 1-C 4-alkoxyl group or C 1-C 4The alkyl that-alkylthio replaces with 1-6 carbon atom, represent and have optional alkenyl or the alkynes base that is replaced by halogen under 2-6 carbon atom and the various situation under the various situations, perhaps represent have in the cycloalkyl under the various situations 3-6 carbon atom and, if suitably, have 1-4 carbon atom in the moieties, and optional in all cases by cyano group, halogen or C 1-C 4Cycloalkyl or cycloalkylalkyl that-alkyl replaces,
R 3Represent hydrogen, halogen or optional, halogen, C by cyano group 1-C 4-alkoxyl group or C 1-C 4The alkyl that-alkylthio replaces with 1-6 carbon atom,
R 4Represent hydrogen or halogen,
R 5Represent hydrogen, hydroxyl, sulfydryl, amino, hydroxyl amino, halogen, perhaps in the residue below the representative:
-Q-R 6,-NH-R 6,-NH-O-R 6,-NH-SO 2-R 6,-N (SO 2-R 6) 2,-CQ 1-R 6,-CQ 1-Q 2-R 6,-CQ 1-NH-R 6,-Q 2-CQ 1-R 6,-NH-CQ 1-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 6Or-Q 2-CQ 1-NH-R 6,
Q wherein 1And Q 2Represent oxygen or sulphur separately, and R 6Representative is optional by cyano group, halogen, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl-carbonyl, C 1-C 4-alkoxy carbonyl or C 1-C 4The alkyl with 1-6 carbon atom that-alkyl amino-carbonyl replaces is represented to have under the various situations and is chosen by cyano group carboxyl, halogen, C under 2-6 carbon atom and the various situation wantonly 1-C 4-alkyl-carbonyl, C 1-C 4-alkoxyl group-carbonyl or C 1-C 4The alkenyl of-alkylamino-carbonyl substituted or alkynes base, represent have in the cycloalkyl under the various situations 3-6 carbon atom and, if suitably, have 1-4 carbon atom in the moieties, and choose by cyano group carboxyl, halogen, C in all cases wantonly 1-C 4-alkyl-carbonyl or C 1-C 4The cycloalkyl of-alkoxyl group-carbonyl substituted or cycloalkylalkyl; represent have in the aryl under the various situations 6 or 10 carbon atoms and, if suitably, have 1-4 carbon atom in the moieties; and it is optional in all cases by hydroxyl; sulfydryl, amino, cyano group; carboxyl; formamyl, thiocarbamoyl, C 1-C 4-alkyl, C 1-C 4-haloalkyl, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, C 1-C 4-alkylthio, C 1-C 4-halogenated alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl, C 1-C 4Aryl or arylalkyl that-alkylamino or dimethylamino replace; perhaps represent have in the heterocyclic radical 2-6 carbon atom and 1-3 nitrogen-atoms and/or 1 or 2 Sauerstoffatom and/or 1 sulphur atom and, if suitably, have 1-4 carbon atom in the moieties; and it is optional in all cases by hydroxyl; sulfydryl, amino, cyano group; carboxyl; formamyl, thiocarbamoyl, C 1-C 4-alkyl, C 1-C 4-haloalkyl, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, C 1-C 4-alkylthio, C 1-C 4-halogenated alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl, C 1-C 4Heterocyclic radical or heterocyclic radical alkyl that-alkylamino or dimethylamino replace,
Wherein except following compounds: 1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-bromo-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-nitro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethylsulfonyl amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethoxycarbonyl methoxyl group-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-methyl sulfenyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles, 1-methyl-3-(4-cyano group-2-fluoro-5-amino-sulfonyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles and 1-methyl-3-(4-cyano group-2-fluoro-5-fluorosulfonyl-phenyl)-4-chloro-5--difluoro-methoxy-pyrazoles (learning) from WO96/01255.
The present invention be more particularly directed to the formula I compound,
Wherein
Q represents oxygen (O), sulphur (S), SO or SO 2,
R 1Represent hydrogen, representative is optional separately by cyano group, fluorine, chlorine, the methyl that methoxy or ethoxy replaces, ethyl, just-or different-propyl group, just-, different-, secondary-or tert-butyl, representative is optional separately by fluorine, the propenyl that chlorine or bromine replaces, butenyl, proyl or butynyl, perhaps representative is optional separately by cyano group, fluorine, chlorine, bromine, the cyclopropyl that methyl or ethyl replace, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl or cyclohexyl methyl
R 2Represent hydrogen, representative is optional separately by cyano group, fluorine, chlorine, methoxyl group, oxyethyl group, the methyl that methylthio group or ethylmercapto group replace, ethyl, just-or different-propyl group, just-, different-, secondary-or tert-butyl, representative is optional separately by fluorine, the propenyl that chlorine or bromine replaces, butenyl, proyl or butynyl, perhaps representative is optional separately by cyano group, fluorine, chlorine, bromine, the cyclopropyl that methyl or ethyl replace, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl or cyclohexyl methyl
R 3Represent hydrogen, fluorine, chlorine, bromine, or representative is optional by cyano group, fluorine, chlorine, methoxyl group, oxyethyl group, the methyl that methylthio group or ethylmercapto group replace, ethyl, just-or different-propyl group, just-, different-, secondary-or tert-butyl,
R 4Represent hydrogen or fluorine, chlorine or bromine,
R 5Representation hydroxy, sulfydryl, amino, fluorine, chlorine, below bromine or the representative in the residue one:
-Q-R 6、-NH-R 6,-NH-O-R 6,-NH-SO 2-R 6,-N(SO 2-R 6) 2,
-CQ 1-R 6.-CQ 1-Q 2-R 6,-CQ 1-NH-R 6,-Q 2-CQ 1-R 6,-NH-CQ 1-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 6Or-Q 2-CQ 1-NH-R 6,
Q wherein 1And Q 2Represent oxygen or sulphur separately, and R 6Representative is optional separately by cyano group, fluorine, chlorine; methoxyl group, oxyethyl group, methylthio group; ethylmercapto group, ethanoyl, propionyl; methoxycarbonyl, ethoxycarbonyl, the methyl of methylamino carbonyl or ethylamino carbonyl substituted; ethyl, just-or different-propyl group, just-; different-; secondary-or tert-butyl; representative is optional separately by cyano group, carboxyl, fluorine; chlorine, bromine, ethanoyl; propionyl, just-or different-butyryl radicals, methoxycarbonyl; ethoxycarbonyl, just-or different-third oxygen carbonyl, the methylamino carbonyl; the ethylamino carbonyl, just-propenyl that or different-propyl group aminocarboxyl replaces, butenyl; proyl or butynyl, representative are optional separately by cyano group, carboxyl; fluorine, chlorine, bromine; ethanoyl, propionyl, the cyclopropyl that methoxycarbonyl or ethoxycarbonyl replace; cyclobutyl, cyclopentyl, cyclohexyl; the cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl or cyclohexyl methyl; representative is optional separately by hydroxyl, sulfydryl, amino; cyano group, carboxyl, formamyl; thiocarbamoyl, methyl, ethyl; trifluoromethyl, methoxyl group, oxyethyl group; difluoro-methoxy, trifluoromethoxy, methylthio group; ethylmercapto group, difluoro methylthio group, trifluoromethylthio; methylsulfinyl, ethyl sulfinyl, methyl sulphonyl; methylamino, the phenyl that ethylamino or dimethylamino replace, benzyl or styroyl; perhaps representative is optional separately by hydroxyl, sulfydryl, amino; cyano group, carboxyl, formamyl; thiocarbamoyl, methyl, ethyl; just-or different-propyl group, just-; different-; secondary-or tert-butyl, difluoromethyl; dichloromethyl, trifluoromethyl, trichloromethyl; the chloro difluoromethyl; the fluoro dichloromethyl, methoxyl group, oxyethyl group; difluoro-methoxy; trifluoromethoxy, methylthio group, ethylmercapto group; the difluoro methylthio group; trifluoromethylthio, methylsulfinyl, ethyl sulfinyl; methyl sulphonyl; ethylsulfonyl, methylamino, ethylamino or dimethylamino replace is selected from Oxyranyle Evil fourth cyclic group; furyl, tetrahydrofuran base, dioxolanyl; thienyl; tetrahydro-thienyl, pyrryl, pyrazolyl; imidazolyl; triazolyl ， oxazolyl ， isoxazolyl; thiazolyl; isothiazolyl ， oxadiazole base, thiadiazolyl group; pyridyl; pyrimidyl, triazinyl, pyrazolyl methyl; furyl methyl; thienyl methyl ， oxazolyl methyl ， isoxazolyl methyl; the thiazolyl methyl; pyridylmethyl, the heterocyclic radical of Pyrimidylmethyl or heterocyclic radical alkyl
Wherein except following compounds: 1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-bromo-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-nitro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethylsulfonyl amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethoxycarbonyl methoxyl group-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-methyl sulfenyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles, 1-methyl-3-(4-cyano group-2-fluoro-5-amino-sulfonyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles and 1-methyl-3-(4-cyano group-2-fluoro-5-fluorosulfonyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles (learning) from WO96/01255.
Very particularly preferably be the 3-cyanoaryl pyrazoles of following structural formula
Figure A9719701500131
Figure A9719701500141
Figure A9719701500151
R under the wherein various situations 5As above definition.
Above-mentioned general or preferred group definition is applicable to the formula I end product and correspondingly is applicable to initiator or the intermediate that preparation needs under the various situations.The definition of these groups can be made up as required mutually, promptly comprises the combination between the preferred range of pointing out.
For example use that methyl hydrazine and 2-chloro-2-(4-cyano group-2-fluoro-5-methoxyl group-benzoyl)-ethyl acetate are initiator, then the reaction process of the inventive method (a) can illustrate by following reaction formula:
Formula II provides the General Definition that is used as the hydrazine derivative of initiator in the inventive method of preparation formula I compound.In formula II, R 1Preferably or especially have and above pointed out, formula I compound of the present invention is relevant with describing, respectively as preferably with as particularly preferred R 1Definition.
The formula II initiator is the known synthetic compound that is used for.
Formula III provides the General Definition that also is used as the cyano-aryl carbonylic acetic acid derivative of initiator in the inventive method (a).In formula III, R 3, R 4And R 5Preferably or especially have and above pointed out, formula I compound of the present invention is relevant with describing, respectively as preferably with as particularly preferred R 3, R 4And R 5Definition.
R preferably represents hydrogen or has alkyl, particularly hydrogen, methyl or the ethyl of 1-4 carbon atom.
Except compound 2-(4-cyano group-2-fluoro-benzoyl) ethyl acetate, be called 3-(4-cyano group-2-fluoro-phenyl)-3-oxo-ethyl propionate (referring to WO96/-1255) again, the formula III initiator is not disclosed in the literature up to now; Except 2-(4-cyano group-2-fluoro-benzoyl)-ethyl acetate, the formula III initiator constitutes the part of the application's theme as novel substance.
If suitably at acid acceptor for example in the presence of the triethylamine, if if suitably at reaction promoter for example in the presence of the magnesium chloride and suitably at thinner for example in the presence of the acetonitrile,-20 ℃ and+temperature between 50 ℃ under, propanedioic acid or derivatives thereof or the salt of formula IV compound and the cyano group benzoyl halogen reaction of general formula (V) when logical formula IV, and during with the ordinary method aftertreatment, obtain wherein Q 3Represent the new cyano-aryl carbonyl compound (referring to preparation embodiment) of the formula III of oxygen
Figure A9719701500161
Wherein R and R 3As above definition separately,
Figure A9719701500162
Wherein
R 4And R 5Separately as above the definition and
X 1Represent halogen.
The malonate derivative that need be used as the formula IV of intermediate is the known synthetic organic compound that is used for.
Except compound 4-cyano group-3-methoxyl group-Benzoyl chloride (referring to Arch.Pharm.323 (1990), 507-512:EP 166609) and 4-cyano group-2-fluoro-Benzoyl chloride (referring to WO96/01255) outside, also need formula (V) cyano group benzoyl halogen to be not disclosed in the literature up to now as intermediate; Except 4-cyano group-3-methoxyl group-Benzoyl chloride and 4-cyano group-2-fluoro-Benzoyl chloride, formula (V) compound constitutes the part of the application's theme as novel substance.
If suitably at reaction promoter N for example, dinethylformamide exists down, if with suitably at thinner for example in the presence of the tetracol phenixin, under the temperature between 0 ℃ and 120 ℃, when the cyanobenzoic acid of logical formula VI and halogenating agent for example when phosgene (or its dimer or tripolymer) or thionyl chloride reaction, obtain the new cyano group benzoyl halogen (referring to preparing embodiment) of formula (V)
Figure A9719701500171
Wherein
R 4And R 5As above definition separately.
The cyanobenzoic acid that need be used as the formula VI of intermediate is known and/or can prepares (referring to Arch.Pharm.323 (1990), 507-512 by known method itself; Collect.Czech.Chem.Commun.40 (1975), 3009-3019; Chem.Pharm.Bull., 27 (1979), 3039-3048; J.Chem.Soc., PerkinTrans, I, 1994,1679-1684; Tetrahedron Lett.31 (1990), 7223-7226; EP166609; EP 351856; WO93/15078).
Be not disclosed in the literature up to now, as novel substance formation the application theme part is that (VI is compound a) for general formula
Wherein
R 5As above definition,
X 2Represent halogen, special representative's fluorine or chlorine.
If suitably at thinner for example in the presence of the acetone, under the temperature between 0 ℃ and 50 ℃, when the nitro methyl benzonitrile of general formula (VII) and oxygenant for example during the potassium permanganate reaction, (VI new cyanobenzoic acid a) is (referring to preparation embodiment to obtain formula, also can be referring to J.Chem.Soc.1949,3374)
Figure A9719701500181
Wherein
R 5And X 2As above definition separately.
The nitro methyl benzonitrile of formula (VII) is not disclosed in the literature up to now, and they constitute the application's theme part as novel substance.
At acid acceptor for example 1,8-diazabicyclo [5.4.0] 11-7-alkene (DBU) exists down, with, if suitably at thinner for example in the presence of the ethyl acetate,-20 ℃ and+temperature between 40 ℃ under, when the halogenated benzyl nitrile of general formula (VIII) and Nitromethane 99Min. reaction, obtain the new compound (referring to preparation embodiment) of formula (VII)
Figure A9719701500182
Wherein
R 5And X 2Separately as above the definition and
X 3Represent halogen, special representative's fluorine or chlorine.
The intermediate of formula (VIII) is known and/or can be by the preparation of known method (referring to EP 191185, EP 433124, and EP 431373, and EP 497239, and EP 557949, EP566268, EP 635486).
(VI cyanobenzoic acid a) can be according to following reaction formula (R: alkyl, particularly methyl or ethyl for formula; X 3: halogen, particularly fluorine or chlorine) from the halogenated benzoic ether preparation of known formula (IX) (referring to J.Chem.Eng.Datal3 (1968), 587-588; C.A.69:106150 draws record):
At acid acceptor for example in the presence of the potassium tert.-butoxide with at thinner for example in the presence of the tetrahydrofuran (THF), as the cyano-aryl ketone and the dithiocarbonic anhydride (CS of general formula (X) 2) reaction, and, if suitably, then-preferably do not separate intermediate-and alkylating reagent for example methyl iodide-30 ℃ and+when reacting under the temperature between 30 ℃, obtain wherein Q 3Represent the new cyano-aryl carbonyl compound (referring to preparation embodiment) of the formula III of sulphur
Wherein
R 3, R 4And R 5As above definition separately.
If the formula III initiator that obtains with this method can-suitably do not separate intermediate-, obtain the formula I active compound according to the inventive method and the reaction of formula II hydrazine derivative yet.
Formula (X) intermediate be known and/or can by the preparation of known method (referring to Chem.Pharm.Bull, 33 (1985), 1360-1366; EP 166609; EP 628550; WO94/05153; Preparation embodiment).
The inventive method suitable diluent that is prepared the new compound of formula I is inert organic solvents particularly.Particularly including aliphatics, alicyclic or aromatic, any halogenated hydrocarbon, gasoline for example, benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin; Ethers, ether for example, Di Iso Propyl Ether ， diox, tetrahydrofuran (THF) or ethylene glycol dimethyl ether or ethylene glycol bisthioglycolate ethyl ether; Ketone, acetone for example, butanone or methyl iso-butyl ketone (MIBK); Carboxylic-acid, for example acetate or propionic acid; Nitrile, acetonitrile for example, propionitrile or benzonitrile; Amides, N for example, dinethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or HMPA; Ester class, for example methyl acetate or ethyl acetate; Sulfoxide class, for example methyl-sulphoxide; Alcohols, methyl alcohol for example, ethanol, just-or different-propyl alcohol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diglycol monotertiary methyl ether, carbiphene.
When carrying out the inventive method, temperature of reaction can change in quite wide scope.Generally speaking, be reflected under the temperature between 0 ℃ and 150 ℃ and carry out, preferably under the temperature between 20 ℃ and 120 ℃, carry out.
The inventive method is generally under atmospheric pressure carried out.But also can carry out the inventive method-generally under high pressure or the low pressure between 0.1 to 10 crust.
When implementing the inventive method, generally use initiator with about equimolar amount.But, also can be with one of them initiator component of big relatively excessive use.Reaction is generally carried out in suitable diluent, and the general stirred for several hour under the temperature of needs of reaction mixture.Carry out aftertreatment (referring to preparation embodiment) by ordinary method.
Active compound of the present invention can be used as defoliating agent, and siccative kills straw agent and particularly conduct and kills the weeds agent.In a broad sense, so-called weeds are all plants of the place growth do not expected at it by understanding.Material of the present invention is the amount that depends primarily on use as total weedicide or selective herbicide.
Relevant with the plant for example, can use active compound of the present invention:
The broadleaf weed kind: mustard belongs to (Sinapis), separate row Vegetable spp (Lepidium), Bedstraw (Galium), Stellaria (Stellaria), Matricaria (Matricaria), Anthemis (Anthemis), Herba galinsogae parviflorae (Galinsoga), Chenopodium (Chenopodium), Urtica (Urtica), Senecio (Senecio), Amaranthus (Amaranthus), Portulaca (Portulaca), Xanthium (Xanthium), japanese bearbind belongs to (Convolvulus), sweet potato genus (Ipomoea), Polygonum (Polygonum), sesbania (Sesbania), Ambrosia (Ambrosia), Cirsium (Cirsium), bristlethistle (Carduus), sonchus L (Sonchus), Solanum (Solanum), weldering Lepidium (Rorippa), Leaf of Chinese Deciduous Cypress belongs to (Rotala), Vandellia (Lindernia), wild awns fiber crops belong to (Lamium), Veronica (Veronica), abutilon (Abutilon), bur (Emex), Datura (Datura), Viola (Viola), the weasel hemp nettle belongs to (Galeopsis), papaver (Papaver), bachelor's-button (Centaurea), Clover (Trifolium), Ranunculus (Ranunculus) and Dandelion (Taraxacum).
Dicotyledonous crops kind: Gossypium (Gossypium), Glycine (Glycine), Beta, Daucus (Daucus), Phaseolus (Phaseolus), Pisum (Pisum), Solanum (Solanum), linum (Linum), sweet potato genus (Ipomoea), vetch (Vicia), Nicotiana (Nicotiana), tomato belongs to (Lycopersicon), peanut (Arachis), mustard belongs to (Brassica), Lactuca (Lactuca), Cucumis (Cucumis), and buffalo gourd (Cucurbita).
Monocotyledon weed kind: Echinochloa (Echinochloa), setaria (Setaria), Panicum (Panicum), knotgrass (Digitaria), ladder are herded genus (Phleum), annual bluegrass belongs to (Poa), festuca (Festuca), cricket Lepidium (Eleusine), Brachiaria (Brachiaria), lolium (Lolium), Brome (Bromus), Avena (Avena), Cyperus (Cyperus), Sorghum (Sorghum), Agropyron (Agropyron), Cynodon, Monochoria (Monchoria), genus fimbristylis (Fimbristylis), arrowhead (Sagittaria), Eleocharis (Eleocharis), bit of a bridle grass (Scirpus), Dallis grass (Paspalum), Ischaemum, cusp Pittosporum (Sphenoclea), talon eria (Dactyloctenium), cut gang Ying and belong to (Agrostis), amur foxtail belongs to (Alopecurus) and Apera.
Monocot crops kind: Oryza (Oryza), Zea (Zea), Triticum (Triticum), Hordeum (Hordeum), Avena (Avena), Secale (Secale), Sorghum (Sorghum), Panicum (Panicum), sugarcane (Saccharum), pineapple (Ananas), Asparagus (Asparagus) and allium (Allium).
But the purposes of active compound of the present invention is not subjected to the restriction of these kinds, but expands to other plant in an identical manner.
According to concentration, The compounds of this invention for example is suitable at industrial site and railway, is with or without on the roads of trees or the square all control weeds.These compounds also are used in perennial plantation plant place, lawn, playground and pasture control weeds, described perennial plantation plant place is the woods for example, the tree of ornamental plantation, orchard, the vineyard, lemon garden, nut garden, banana plantation, cafetal, tea plantation, rubber plantation, oil palm plantation, cocoa plantation, mushy fruit plantation plant and hop field, and be used in year non-hibernating eggs plant place selective control weeds.
Formula I compound of the present invention be specially adapted to before bud and bud after in unifacial leaf and dicotyledonous farm crop selective control unifacial leaf and broadleaf weed.
Active compound can be mixed with conventional formulation, for example solution, emulsion, wettable powder, suspension agent, pulvis, pulvis subtilis, paste, soluble powder, granule, suspendible missible oil and be soaked with the natural and synthetic materials of active compound material, and be wrapped in the trickle capsule in the polymkeric substance.
These type agent are produced in a known manner, for example, are that liquid solvent and/or solid carrier mix with active compound with expanding agent, and optional tensio-active agent, i.e. emulsifying agent and/or dispersion agent and/or the pore forming material of using.
Use water as under the situation that expands agent, also can use-case such as organic solvent make solubility promoter.Suitable liquid solvent mainly contains: aromatic substance, and as dimethylbenzene, toluene or alkylnaphthalene; Chloro aromatic substance and chlorinated aliphatic hydrocarbon are as chlorinated benzene class, polyvinyl chloride-base or methylene dichloride; Aliphatic hydrocarbon, as hexanaphthene or paraffin, mineral oil fraction for example, mineral oil and vegetables oil; Alcohols, as butanols or ethylene glycol with and ether and ester; Ketone is as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone; Intensive polar solvent is as dimethyl formamide and methyl-sulphoxide; And water.
Suitable solid carrier is: ammonium salt for example, and ground natural mineral matter such as kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite and ground synthetic mineral matter are as high dispersive silicon-dioxide, alumina and silicate; The solid carrier that is fit to that is used for granule has: for example crushing and broken natural mineral matter such as calcite, marble, float stone, sepiolite and rhombspar, and the synthetic particle of organic and inorganic powder and following organic particle: for example wood sawdust, coconut husk, corn cob and tobacco stem; The emulsifying agent and/or the pore forming material that are fit to have: for example nonionic and anionic emulsifier, as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, for example, alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and protein hydrolysate; The dispersion agent that is fit to has: for example, and lignin sulfite waste liquor and methylcellulose gum.
Can use the natural and synthetic polymer of tackiness agent such as carboxymethyl cellulose and powdery, particle or latex form in the preparation, as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, as kephalin and Yelkin TTS, and synthetic phospholipid.Other possible additive is mineral oil and vegetables oil.
Also can use tinting material, as mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic dye are as the salt of alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff and micro-nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Generally speaking, preparation contains the active compound of 0.1-95% weight, preferred 0.5-90%.
For the control weeds, active compound of the present invention or its dosage form also can be used as the mixture use with known weedicide, can be final preparation or container mixture.
What be applicable to described mixture is known weedicide, acetochlor for example, acifluorfen (sodium salt), aclonifen, alachlor, alloxydim (sodium salt), ametryn, amidochlor, amidosulfuron, the spirit of sulphur grass, atrazine, azimsulfuron, herbicide, benfuresate, the phonetic grass of benzyl swell (methyl esters), bentazone, benzofenap, benzoylpropethyl (ethyl ester), bilanafos, bifenox, bromobutide, bromofenoxim, bromoxynil, Butachlor technical 92, the fourth grass is special, and cafenstrole blocks careless amine, chlomethoxyfen, weed eradication is flat, pyrazon, chlorimuron (ethyl ester), chlornitrofen, chlorsulfuron, the chlorine wheat is grand, cinmethylin, and the ether grass is grand, clethodim, clodinafop (propargyl) ， clomazone, clopyralid, clopyrasulfuron, cloransulam are (methyl), cumyluron, cyanazine, weed eradication spy, cyclosulfamuron, cycloxydim, cyhalofop are (butyl), 2,4-drips, and 2, the 4-Embutox, 2,4-drips propionic acid, desmedipham, di_allate, dicamba 98, diclofop-methyl (methyl esters), two benzene azoles are fast, diflufenican, fourth is disliked grand, dimepiperate, dimethachlor, diformazan third second is clean, dimethenamid, the spirit of amino second fluorine, diphenamide, diquat, dithiopyr, Diuron Tech, daimuron, EPTC, esprocarb, ethalfluralin, ethametsulfuron are (methyl), ethofumesate, ethoxyfen, etobenzanid oxazole diclofop-methyl, wheat straw volt (isopropyl ester), the wheat straw volt (isopropyl ester-L), wheat straw volt (methyl esters), pyridine ethyl methyl, fluazifop (butyl ester), flumetsulam, flumiclorac (pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofenethyl (ethyl ester), amine grass azoles, flupropacil, the fluorenes butyric acid, fluorine is decided ketone, fluroxypyr, flurprimidol, flurtamone, Fomesafen, grass ammonium phosphine (ammonium salt), glyphosate (sec.-propyl ammonium salt), halosafen, pyrrole fluorine chlorine standing grain spirit (ethoxy ethyl ester), hexazinone, miaow grass ester (methyl esters), imazamethapyr, imazamox, weed eradication cigarette, the weed eradication quinoline, Imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole ， Evil grass ether, lactofen, lenacil, methoxydiuron, MCPA, MCPP, mefenacet, metamitron, pyrrole grass peace, methabenzthiazuron, metobenzuron, metobromuron, Bing Caoan, metosulam, metoxuron, metsulfuron-methyl (methyl esters), the piperazine humulone, Hydram, monolinuron, naproanilide, napropamide, neburon, nicoculsfuron, norflurazon, orbencarb, oryzalin ， Evil humulone, oxyfluorfen, Paraquat, pendimethalin, phenmedipham, piperophos, Bing Caoan, Fluoropyrimidinesulfuron (methyl esters), prometryn, propachlor, Stam F-34, propaquizafop, pentyne grass amine, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (ethyl ester), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac are (sodium), quinclorac, quinmerac, quizalofop (ethyl ester), quizalofop (tetrahydro furfuryl ester), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, ethyl methyl (methyl esters), glyphosate, tebutam, terbufos benzthiazuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thiophene methyl (methyl esters), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron-methyl (methyl esters), TRICLOPYR ACID, tridiphane, trifluralin and triflusulfuron.
Also may be the mixture with other known activity compound, described other active compound be a mycocide for example, insecticide, miticide, nematocides, bird repellent, plant nutrient agent and improve the reagent of Soil structure.
These active compounds can use itself, use with its dosage form, perhaps use with the type of service that therefrom prepares by further diluting, for example instant solution, suspensoid, emulsion, pulvis, paste and granule.They can use in a usual manner, for example by pouring, and spraying, atomizing or sow.
Active compound of the present invention can be used before plant sprout or behind the bud.It also can be admixed in the soil prior to seeding.
The amount of the active compound that uses can change in a quite wide scope.This depends primarily on the character of desired effects.Generally speaking, the amount of use is used the 1g-10kg active compound at per hectare soil area, and preferred per hectare soil area uses the 5g-5kg active compound.
The preparation and the application of active compound of the present invention can be described according to the following examples.
Preparation embodiment
Embodiment 1
Figure A9719701500241
At first 171g (0.676mol) 2-(4-cyano group-2,5-two fluoro-benzoyls)-ethyl acetate is joined in the 300ml acetate, and be under about 40 ℃, drip with 36.3g (0.80mol) methyl hydrazine and mix at internal temperature.Then mixture is settled out the aureus solid about 90 minutes of 90 ℃-100 ℃ heating.Mixture is slowly poured in about 2 liters of frozen water after the cooling.Suction strainer separate solid product washes with water, and water pump vacuumizes drying.Stir with the 600ml methylene dichloride then, suction strainer, and water pump vacuumizes drying again.
Obtain 125g (theoretical amount 79%) 3-(4-cyano group-2,5-two fluoro-phenyl)-5-hydroxyl-1-methyl isophthalic acid H-pyrazoles, 198 ℃ of fusing points.
Embodiment 2
Figure A9719701500251
47g (0.20mol) 3-(4-cyano group-2,5-two fluoro-phenyl)-5-hydroxyl-1-methyl isophthalic acid H-pyrazoles and 350mlN, the mixture of dinethylformamide mixes with 55g salt of wormwood, and about 60 minutes of 50 ℃ of heating.Under the internal temperature between 60 ℃ and 70 ℃, added 100g (1.16mol) chloro methylene fluoride through about 6 hours.Then mixture vacuumizes down at water pump and concentrates, and resistates is dissolved in 500ml water.Aqeous suspension 2N hcl acidifying, and use dichloromethane extraction.Organic phase washes with water, and dried over mgso is also filtered.Filtrate concentrates under pump vacuum, and resistates is used 500ml with hot hexane lixiviate 4 times at every turn.The following carefully distilling off solvent from the hexane fraction that merges of pump vacuum.
Obtain 24.6g (theoretical amount 43%) 3-(4-cyano group-2,5-two fluoro-phenyl)-5-difluoro-methoxy-1-methyl isophthalic acid H-pyrazoles, 80 ℃ of fusing points.
By column chromatography (with methylene dichloride eluting silica gel post) can be from the extracted residues that in fact is not dissolved in hexane separating isomerism body compound 3-(4-cyano group-2,5-two fluoro-phenyl)-2-difluoromethyl-1-methyl-pyrazoles-5-ketone, 128 ℃ of fusing points.
Embodiment 3
Under the room temperature (about 20 ℃), stir the solution that in the 20ml methylene dichloride, adds 1.9g (12mmol) bromine in the 5ml methylene dichloride down in the solution of 2.85g (10mmol) 3-(4-cyano group-2,5-two fluoro-phenyl)-2-difluoromethyl-1-methyl-pyrazoles-5-ketone.Mixture stirred 3 hours down at about 20 ℃, with the dilution of 20ml methylene dichloride, washed with saturated sodium bicarbonate aqueous solution with saturated sodium chloride aqueous solution, and dried over mgso is also filtered.Careful distilling off solvent from filtrate under the pump vacuum.
Obtain 3.5g (theoretical amount 96%) 4-bromo-3-(4-cyano group-2,5-two fluoro-phenyl)-5-difluoro-methoxy-1-methyl isophthalic acid H-pyrazoles, 79 ℃ of fusing points.
Embodiment 4
Figure A9719701500261
Add 1.5g (4mmol) 4-bromo-3-(4-cyano group-2,5-two fluoro-phenyl)-1-methyl-5-difluoro-methoxy-1H-pyrazoles in the solution of 0.5g in the 40ml acetonitrile (6mmol) sodium methylate.Mixture stirred 16 hours down in room temperature (about 20 ℃), poured in the water, and was using hcl acidifying, filtered out precipitated solid, wash with water, and pump vacuum was dry down.
Obtain 1.1g (theoretical amount 75%) 4-bromo-3-(4-cyano group-2-fluoro-5-methoxyl group-phenyl)-1-methyl-5-two-fluorine methoxyl group-1H-pyrazoles, 155 ℃ of fusing points.
Embodiment 5
Under the room temperature (about 20 ℃), add the dichloromethane solution of 150ml (0.15mol) 1M boron tribromide in the solution of 18.8g in the 100ml methylene dichloride (0.05mol) 4-bromo-3-(4-cyano group-2-fluoro-5-methoxyl group-phenyl)-1-methyl-5-difluoro-methoxy-1H-pyrazoles.Reaction mixture at room temperature stirs after 16 hours and mixes with water and methylene dichloride.Separate organic phase, and water successively, saturated sodium hydrogen carbonate solution and sodium chloride solution washing, dried over mgso, and pump vacuum goes down to desolventize.The crude product that obtains is moving phase by the column chromatography purifying with diamino methane.
Obtain 8.3g (theoretical amount 46%) 4-bromo-3-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-1-methyl-5-difluoro-methoxy-1H-pyrazoles, 129 ℃ of fusing points.
Embodiment 6
Add 2.8g (20mmol) salt of wormwood and 1.0g (8mmol) bromoacetonitrile in the solution of 1.9g in the 50ml acetonitrile (6.0mmol) 4-chloro-3-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-5-difluoro-methoxy-1-methyl isophthalic acid H-pyrazoles.Reaction mixture concentrates under the pump vacuum after room temperature (about 20 ℃) stirs about 16 hours down.Resistates mixes with 50ml water, uses the 2N hcl acidifying, and uses dichloromethane extraction.Organic phase is washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, and dried over mgso is also filtered concentrated filtrate under the pump vacuum.The resistates crude product that obtains is by column chromatography purifying (methylene dichloride, silica gel).
Obtain 1.0g (theoretical amount 47%) 5-(4-chloro-5-difluoro-methoxy-1-methyl isophthalic acid H-pyrazole-3-yl)-2-cyano group-4-fluoro-phenoxy group acetonitrile, 104 ℃ of fusing points.
By preparing the method for embodiment 1-6, and the general remark of method produced according to the present invention, can preparation example such as following table 1 in the formula I compound listed.The 3-cyanoaryl pyrazoles
Figure A9719701500281
Table 1: the embodiment of formula I compound
Figure A9719701500282
Figure A9719701500301
Figure A9719701500311
Figure A9719701500321
Figure A9719701500331
Figure A9719701500341
Figure A9719701500361
Figure A9719701500381
Figure A9719701500411
For example can be prepared as follows the compound of embodiment 47 in the table 1:
Under the room temperature (about 20 ℃), in the 80ml methylene dichloride, add 4.2g (26mmol) bromine solutions in the 10ml methylene dichloride in the solution of 6.0g (23mmol) 3-(4-cyano group-2,5-two fluoro-phenyl)-1-methyl-5-methyl sulfenyl-1H-pyrazoles under stirring.Reaction mixture at room temperature stirred about 60 minutes, also used rare sodium sulfite solution successively with the dilution of 20ml methylene dichloride, saturated sodium hydrogen carbonate solution and sodium chloride solution washing, and dried over mgso, and water pump vacuumizes the removal solvent.
Obtain 7.0g (theoretical amount 88.5%) 4-bromo-3-(4-cyano group-2,5-two fluoro-phenyl)-1-methyl-5-methyl sulfenyl-1H-pyrazoles, be crystalline solid, 100 ℃ of fusing points.
For example can be prepared as follows the compound of embodiment 79 in the table 1:
With 2.4g (10mmol) 3-(4-cyano group-2,5-two fluoro-phenyl)-5-hydroxyl-1-methyl isophthalic acid H-pyrazoles, the mixture of 6.7g (30mmol) phosphoric sulfide (V) and 50ml dimethylbenzene heated 9 hours under refluxing.Then mixture concentrates under pump vacuum, and resistates and 50ml 2N aqueous sodium hydroxide solution stir.Filtering mixt then, filtrate is used the 2N hcl acidifying.Suction strainer separates the crystallized product that obtains.
Obtain 1.6g (theoretical amount 64%) 3-(4-cyano group-2,5-two fluoro-phenyl)-1-methyl-5-sulfydryl-1H-pyrazoles, 137 ℃ of fusing points.
For example can be prepared as follows the compound of embodiment 79 in the table 1:
Figure A9719701500431
Under-20 ℃, through about 30 minutes, the solution of 10.9g (0.06mol) 1-(2,5-two fluoro-4-cyano group-phenyl)-ethyl ketone in the Dropwise 5 0ml tetrahydrofuran (THF) in the suspension of 13.5g in the 100ml tetrahydrofuran (THF) (0.12mol) potassium tert.-butoxide.Mixture-20 ℃ down stir about 30 minutes after with 4.6g (0.06mol) dithiocarbonic anhydride (CS 2) mix.Through after 30 minutes, add 7.3g (0.12mol) acetate and 5.6g (0.12mol) methyl hydrazine successively again, make reaction mixture be warmed to room temperature through 2 hours.Then reaction mixture is poured in the 250ml frozen water and used washed with dichloromethane.With hydrochloric acid water is adjusted to pH1, and extracts repeatedly with methylene dichloride.Extraction liquid from hydrochloric acid soln washs with sodium chloride solution, dried over mgso, and pump vacuum goes down to desolventize.
Obtain 5.6g (theoretical amount 37%) 3-(4-cyano group-2,5-two fluoro-phenyl)-1-methyl-5-sulfydryl-1H-pyrazoles, be the yellow solid crystallization, 137 ℃ of fusing points.
For example can be prepared as follows the compound of embodiment 80 in the table 1:
Figure A9719701500432
80mlN, the solution of 5g in the dinethylformamide (0.02mol) 3-(4-cyano group-2,5-two fluoro-phenyl)-5-sulfydryl-1-methyl isophthalic acid H-pyrazoles mixes with 8.3g (0.06mol) salt of wormwood, and is heated to 50 ℃.Under this temperature, added about 10.4g (0.12mol) chloro methylene fluoride through 3 hours.After reaction finished, water pump vacuumizes removed most of solvent, and resistates is dissolved in 50ml water.Water comes together with the 2N hcl acidifying and with methylene dichloride, and organic phase washes with water, dried over mgso, and pump vacuum goes down to desolventize.
Obtain 5.2g (theoretical amount 86%) 3-(4-cyano group-2,5-two fluoro-phenyl)-5-difluoromethyl sulfenyl-1-methyl isophthalic acid H-pyrazoles, 104 ℃ of fusing points.
For example can be prepared as follows the compound of embodiment 82 in the table 1:
Figure A9719701500441
Under-5 ℃, the suspension that adds 9.9g (40mmol) 70% intensity 3-chloro peroxybenzoic acid in the 130ml methylene dichloride in the solution of 5.5g (16mmol) 4-bromo-3-(4-cyano group-2,5-two fluoro-the phenyl)-1-methyl-5-methyl sulfenyl-1H-pyrazoles under stirring in the 100ml methylene dichloride.Reaction mixture stirred 16 hours down in room temperature (about 20 ℃), the solid of filtering-depositing, filtrate are used saturated hypo solution successively, saturated sodium hydrogen carbonate solution and the washing of saturated sodium chloride solution, dried over mgso, and pump vacuum goes down to desolventize.
Obtain 5.5g (theoretical amount 91%) 4-bromo-3-(4-cyano group-2,5-two fluoro-phenyl)-1-methyl-5-methyl sulphonyl-1H-pyrazoles, be crystalline solid, 176 ℃ of fusing points.
For example can be prepared as follows the compound of embodiment 83 in the table 1:
Figure A9719701500442
Under the room temperature (about 20 ℃), the solution that adds 4.8g (30mmol) bromine in the 15ml methylene dichloride in the solution of 5.1g (17mmol) 3-(4-cyano group-2,5-22 fluoro-the phenyl)-5-difluoromethyl sulfenyl-1H-methyl isophthalic acid H-pyrazoles under stirring in the 20ml methylene dichloride.Reaction mixture heated 18 hours under refluxing, and with the dilution of 20ml methylene dichloride, and used rare sodium sulfite solution successively, saturated sodium hydrogen carbonate solution and sodium chloride solution washing, and dried over mgso, and pump vacuum goes down to desolventize.
Obtain 5.8g (theoretical amount 90%) 4-bromo-3-(4-cyano group-2,5-two fluoro-phenyl)-5-difluoromethyl sulfenyl-1-methyl isophthalic acid H-pyrazoles, be crystalline solid, 100 ℃ of fusing points.
For example can be prepared as follows the compound of embodiment 87 in the table 1:
Figure A9719701500451
Under the room temperature (about 20 ℃), the 6.2g in the 60ml acetonitrile (22mmol) 1-(4-cyano group-2,5-two fluoro-phenyl)-3 adds 2.5g (55mmol) methyl hydrazine in the solution of 3-pair-(methyl sulfenyl)-2-propylene-1-ketone.Heating was poured in the frozen water after 90 minutes under the reaction mixture refluxed.The suction strainer precipitated solid washes with water and drying under reduced pressure.
Obtain 5.0g (theoretical amount 86%) 3-(4-cyano group-2,5-two fluoro-phenyl)-1-methyl-5-methyl sulfenyl-1H-pyrazoles, 118 ℃ of fusing points.
The formula III initiator:
Embodiment (III-1)
Figure A9719701500452
Under 10 ℃-15 ℃, in 2 liters of acetonitriles, add 147g (1.46mol) triethylamine and 170g (1.80mol) magnesium chloride (anhydrous) in the mixture of 251g (1.48mol) monoethyl malonate potassium successively.Mixture stirs about 150 minutes postcooling down to-10 ℃ to-5 ℃ in room temperature (about 20 ℃), and under this temperature, successively with 145g (0.72mol) 4-cyano group-2,5-difluoro benzoyl chloride and 14.7g (0.146mol) triethylamine mixes.Reaction mixture at room temperature stirred about 18 hours then, and then concentrated.Resistates mixes the mixed in hydrochloric acid of back and 1 liter of 13% intensity with 1.2 liters of toluene.Mixture at room temperature stirred 3 hours, the solid of filtering-depositing, and from filtrate, separate organic phase.Wash with water behind the salt acid elution of organic phase with 13% intensity, dried over mgso is also filtered.Careful distilling off solvent from filtrate under the pump vacuum.
Obtain 173g (theoretical amount 95%) 3-(4-cyano group-2,5-two fluoro-phenyl)-3-oxo-ethyl propionate, 44 ℃ of fusing points are the aureus solid residue.
Embodiment (III-2)
Figure A9719701500461
The method of Application Example (III-1), and with Methylpropanedioic acid list ethyl ester potassio for monoethyl malonate potassium, the productive rate with 93.6% obtains compound 3-(4-cyano group-2,5-two-phenyl)-2-methyl-3-oxo-ethyl propionate, is yellow liquid. 1H?NMR(CDCl 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).
Embodiment (III-3)
Under-20 ℃, through 0.5 hour, the solution of 10.9g (0.06mol) 1-(4-cyano group-2,5-difluorophenyl)-ethyl ketone in the Dropwise 5 0ml tetrahydrofuran (THF) in the suspension of 13.5g in the 100ml tetrahydrofuran (THF) (0.12mol) potassium tert.-butoxide.Mixture-20 ℃ down stir about 30 minutes after with 4.6g (0.06mol) dithiocarbonic anhydride (CS 2) mix.After 30 minutes, add 17.0g (0.12mol) methyl iodide, and make reaction mixture be warmed to room temperature through 2 hours again.Reaction mixture is poured in the 500ml frozen water, be adjusted to pH1, and use the 1500ml ethyl acetate extraction with hydrochloric acid.Organic phase is washed with sodium chloride solution, dried over mgso, and water pump vacuumizes the removal solvent.Resistates solid that obtains and approximately 20ml acetonitrile stirring, and the solid of filtering-depositing, drying.
Obtaining 6.9g (theoretical amount 40%) 1-(4-cyano group-2,5-two fluoro-phenyl)-3,3-is two-(methyl sulfenyl)-2-propylene-1-ketone, be aureus crystalline solid, 188 ℃ of fusing points.
Formula (V) initiator
Embodiment (V-1)
To 3.4g (19mmol) 4-cyano group-2,5-two fluoro-phenylformic acid, 30ml tetracol phenixin and a N drip 6.7g (56mmol) thionyl chloride in the mixture of dinethylformamide.Reaction mixture heated about 6 hours under refluxing.No longer behind the evolving gas, make mixture cooling and filtration.Carefully from filtrate, distill out volatile component then under the pump vacuum.
Obtain 3.6g (theoretical amount 95.5%) 4-cyano group-2,5-two fluoro-Benzoyl chlorides are yellow liquid. 1H NMR (CDCl 3.d, ppm): 7.95 (dd, 1H), 7.54 (dd, 1H) formula VI initiator embodiment (VI-1)
Figure A9719701500472
Under the highest 40 ℃ of temperature, drip 5.74g (29mmol) 2 in the 30ml acetone, the solution of 5-two fluoro-4-nitro methyl-benzonitriles in the suspension of the 8.0g in 100ml acetone (50mmol) potassium permanganate (levigate in mortar).Reaction mixture stirred about 16 hours down in room temperature (about 20 ℃) then, and then used the 2N hcl acidifying.Filter and remove sedimentary Manganse Dioxide, concentrated filtrate under the pump vacuum.Resistates is dissolved in ethyl acetate, washes with water, and dried over mgso is also filtered.Concentrated filtrate, resistates stirs suction strainer with a small amount of methylene dichloride.
Obtain 3.4g (theoretical amount 64%) 4-cyano group-2,5-two fluoro-phenylformic acid are crystallized product, 159 ℃ of fusing points. 1H NMR (DMSO-D 6.d.ppm): 7.92 (dd.1H) .8.15 (dd.1H) .14.10 (s broad peak 1H). embodiment (VI-2) Step 1
9.5g (50mmol) 2,4,5-three fluoro-methyl benzoate, 2.7g (55mmol) sodium cyanide and 100mlN, the mixture of dinethylformamide stirred 3 days at about 25 ℃, passed through activated carbon filtration then.Water pump vacuumizes concentrated filtrate, and resistates cyclohexane/ethyl acetate (volume ratio 9: 1) recrystallization.
Obtain 4.0g (theoretical amount 41%) 4-cyano group-2,5-two fluoro-methyl benzoate, 60 ℃ of fusing points.Step 2
0.83g (4.4mmol) 4-cyano group-2,5-two fluoro-methyl benzoate, the mixture of 0.49g (4.4mmol) potassium tert.-butoxide, 50ml ether and 10ml water stirred 12 hours at about 23 ℃, used the concentrated hydrochloric acid acidifying mixture then, separate organic phase, dried over sodium sulfate is also filtered.Careful distilling off solvent from filtrate under the pump vacuum.
Obtain 0.50g (theoretical amount 62%) 4-cyano group-2,5-two fluoro-phenylformic acid are crystallized product, 159 ℃ of fusing points.
By the method for embodiment (VI-1) or (VI-2), also can preparation example such as compound 5-chloro-4-cyano group-2-fluoro-phenylformic acid (fusing point: 147 ℃) and 2-chloro-4-cyano group-5-fluoro-phenylformic acid (fusing point: 163 ℃).
Formula (VII) initiator
Embodiment (VII-1)
Figure A9719701500491
At first add 3.7g (60mmol) Nitromethane 99Min. and 80ml ethyl acetate and 18.2g (120mmol) diazabicyclo hendecene (DBU), mixture is cooled to-10 ℃.8.7g (50mmol) 5-chloro-2 in the Dropwise 5 0ml ethyl acetate then, the solution of 4-two fluoro-benzonitriles, reaction mixture stirred in ice bath 15 hours, and then used the 2N hcl acidifying.Separate organic phase, with saturated sodium chloride aqueous solution one oscillates, with dried over mgso and filtration.Careful distilling off solvent from filtrate under the pump vacuum.
Obtain 9.7g (purity 73.6%, promptly 67% of theoretical amount) 5-chloro-2-fluoro-4-nitro methyl benzonitrile, be amorphous resistates, need not anyly be further purified and promptly can be used for next step reaction.
By the method for embodiment (VII-1), also can preparation example such as compound 2,5-two fluoro-4-nitro methyl benzonitriles (fusing point: 100 ℃) and 2-chloro-5-fluoro-4-cyano methyl-benzonitrile (fusing point: 35 ℃).
Formula (X) initiator
Embodiment (X-1)
Figure A9719701500492
With 5.16g (24mmol) 2,5-two fluoro-4-(1-nitro-ethyl)-benzonitrile is dissolved in the 50ml acetate, and mixture heated 8 hours under refluxing, and after the cooling, joined in about 200ml water.Use the dichloromethane extraction mixture then, organic phase is water successively, saturated sodium hydrogen carbonate solution and the washing of saturated sodium chloride solution, and dried over mgso is also filtered.Concentrated filtrate under the pump vacuum, resistates extracts repeatedly with hot normal hexane.The following carefully distilling off solvent from the extraction liquid that merges of pump vacuum.
Obtain 2.72g (theoretical amount 62%) 1-(2,5-two fluoro-4-cyano group-phenyl)-ethyl ketone, be the colourless crystallization product, 42 ℃ of fusing points.
Embodiment (X-2)
Figure A9719701500501
200mlN, 5.4g in the dinethylformamide (0.11mol) sodium cyanide (grinding) and 17.4g (0.10mol) 2,4,5-three fluoro-methyl phenyl ketones stirred 12 hours at 25 ℃.Suction strainer mixture, filtrate be by activated carbon filtration, and careful distilling off solvent from filtrate under the pump vacuum.
Obtain 10.4g (theoretical amount 57%) 1-(2,5-two fluoro-4-cyano group-phenyl)-ethyl ketone, be amorphous resistates.
IR spectrum: 1698cm -1(CO), 2240cm -1(CN).
Application Example
Embodiment A
Test before the bud
Solvent: 5 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
In order to prepare the active compound appropriate formulation, with 1 part of weight active compound and described amount solvent, add described amount emulsifying agent, water is diluted to missible oil the concentration that needs.
The seed of sowing test plant in normal soil.After 24 hours, use the mode of active compound of the expectation of specified quantitative with per unit area, soil is sprayed with active agent preparations.Select the concentration of spraying series, make and use the active compound of the expectation of specified quantitative with 1000 premium on currency/ha.
The Samsung after date is to measure degree of damage to plant with untreated control thing growth phase infringement percentage relatively.
Data declaration:
0%=does not have effect (as the untreated control thing)
The 100%=completely destroy
In this test, with 60 with during the applicating ratio of 125g/ha, for example prepare embodiment 3,4,7,8,10,11,12,13 and 15 compound exhibits goes out very strong for example to cut weeds knotgrass (Digitaria) (80-100%), setaria (Setaria) (70-100%), Amaranthus (Amaranthus) (100%), Datura (Datura) (90-100%) and the weeding activity of Solanum (Solanum) (100%), and farm crop have good tolerance for example corn (5%), soybean (0-30%) and cotton (0-30%) in them some.
Embodiment B
Test behind the bud
Solvent: 5 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
In order to prepare the active compound appropriate formulation, with 1 part of weight active compound and described amount solvent, add described amount emulsifying agent, water is diluted to missible oil the concentration that needs.
With the test plant spraying of active agent preparations, make the active compound of per unit area being used the expectation of specified quantitative to high 5-15cm.Select the concentration of spraying fluid, make with 1000L water/hectare and use the active compound of the expectation of specified quantitative.
The Samsung after date is to measure degree of damage to plant with untreated control thing growth phase infringement percentage relatively.
Data declaration:
0%=does not have effect (as the untreated control thing)
The 100%=completely destroy
In this test,, for example prepare embodiment 3 with 20 with during the applicating ratio of 60g/ha, 4,7,8,10,11,12,13 and 15 compound exhibits goes out the very strong for example abutilon (Abutilon) (100%) of cutting weeds, and Chenopodium (Chenopodium) (95-100%), Solanum (Solanum) (100%), knotgrass (Digitaria) (70-100%) and setaria (Setaria) (80-100%).

Claims (10)

1. the 3-cyanoaryl pyrazoles that leads to formula I:
Figure A9719701500021
Be characterised in that
Q represents oxygen (O), sulphur (S), SO or S0 2,
R 1Represent the optional separately substituted alkyl of hydrogen or representative, alkenyl, the alkynes base, cycloalkyl or cycloalkylalkyl,
R 2Represent the optional separately substituted alkyl of hydrogen or representative, alkenyl, the alkynes base, cycloalkyl or cycloalkylalkyl,
R 3Represent hydrogen, halogen or optional substituted alkyl,
R 4Represent hydrogen or halogen,
R 5Represent hydrogen, hydroxyl, sulfydryl, amino, hydroxyl amino, halogen, perhaps in the group below the representative:
-Q-R 6.-NH-R 6.-NH-O-R 6.-NH-SO 2-R 6.-N (SO 2-R 6) 2.-CQ 1-R 6.-CQ 1-Q 2-R 6.-CQ 1-NH-R 6.-Q 2-CO 1-R 6.-NH-CQ 1-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 6Or-Q 2-CQ 1-NH-R 6, Q wherein 1And Q 2Represent oxygen or sulphur separately, and R 6The optional separately substituted alkyl of representative, alkenyl, the alkynes base, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclic radical or heterocyclic radical alkyl,
Except compound: 1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-phenyl)-4-bromo-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-nitro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethylsulfonyl amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-ethoxycarbonyl methoxyl group-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-methyl sulfenyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-amino-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles; 1-methyl-3-(4-cyano group-2-fluoro-5-chloro-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles, 1-methyl-3-(4-cyano group-2-fluoro-5-amino-sulfonyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles and 1-methyl-3-(4-cyano group-2-fluoro-5-fluorosulfonyl-phenyl)-4-chloro-5-difluoro-methoxy-pyrazoles.
2. the preparation method of leading to the 3-cyanoaryl pyrazoles of formula I:
Figure A9719701500031
Wherein
R 1, R 2, R 3, R 4, R 5With each claim 1 definition freely of Q, be characterised in that
The hydrazine or derivatives thereof of logical formula II and the cyano-aryl carbonyl compound of logical formula III and/or, if suitable, the tautomerism precursor reactant of formula III compound, H 2N-NH-R 1(II), wherein R 1As above definition,
Figure A9719701500032
R wherein 3, R 4And R 5As above definition separately, Q 3Represent oxygen or sulphur and R to represent hydrogen or alkyl,
And, if suitably, the logical formula I compound that obtains is carried out further conversion in the above-mentioned substituting group range of definition by ordinary method.
3. the cyano-aryl compound that leads to formula III R wherein 3, R 4And R 5Respectively claim 1 defines freely, and Q 3Represent oxygen or sulphur and R to represent hydrogen or alkyl.
4. the cyano group benzoyl halogen of general formula (V) R wherein 4And R 5Respectively claim 1 defines freely, and X 1Represent halogen.
5. general formula (VI 4-cyanobenzoic acid a)
Figure A9719701500043
R wherein 4And R 5Respectively claim 1 defines freely.
6. the nitro methyl benzonitrile of general formula (VII)
Wherein
R 5Such as claim 1 definition and
X 2Represent halogen.
7. herbicidal composition is characterised in that, it contains the 3-cyano-aryl pyrazoles of the logical formula I of at least a claim 1.
8. control is not expected to be characterised in that the method for plant, the 3-cyano-aryl pyrazoles of the logical formula I of claim 1 is acted on do not expect plant and/or its growth region.
9. the purposes of plant is not expected in the control of the 3-cyano-aryl pyrazoles of the logical formula I of claim 1.
10. prepare the method for herbicidal composition, be characterised in that, with the 3-cyano-aryl pyrazoles of the logical formula I of claim 1 with expand agent and/or tensio-active agent and mix.
CN 97197015 1996-06-03 1997-05-21 3-cyanoaryl pyrazoles and use thereof as herbicides Pending CN1227545A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996122189 DE19622189A1 (en) 1996-06-03 1996-06-03 3-cyanaryl pyrazole
DE19622189.7 1996-06-03

Publications (1)

Publication Number Publication Date
CN1227545A true CN1227545A (en) 1999-09-01

Family

ID=7795979

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 97197015 Pending CN1227545A (en) 1996-06-03 1997-05-21 3-cyanoaryl pyrazoles and use thereof as herbicides

Country Status (8)

Country Link
EP (1) EP0906285A1 (en)
JP (1) JP2000512275A (en)
CN (1) CN1227545A (en)
AU (1) AU2958597A (en)
BR (1) BR9709521A (en)
CA (1) CA2256508A1 (en)
DE (1) DE19622189A1 (en)
WO (1) WO1997046535A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870677A (en) * 2010-06-28 2010-10-27 大连理工大学 5-arylmethoxy radical phenyl pyrazol compound and preparation method thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19838706A1 (en) 1998-08-26 2000-03-02 Bayer Ag Substituted 3-aryl-pyrazoles
IT1313601B1 (en) * 1999-08-05 2002-09-09 Isagro Ricerca Srl HERBICIDE ACTIVITY PHENYLPIRAZOLI
DE19937772A1 (en) 1999-08-10 2001-02-15 Bayer Ag Substituted heterocyclyl-2GH-chromenes
DE10032633A1 (en) * 2000-07-05 2002-01-17 Bayer Ag Method for finding protoporphyrinogen oxidase inhibitors
GB0016787D0 (en) 2000-07-07 2000-08-30 Pfizer Ltd Compounds useful in therapy
JP2004519456A (en) * 2001-01-16 2004-07-02 ビーエーエスエフ アクチェンゲゼルシャフト Method for producing 1-alkyl-3-aryl-5-difluoromethoxy-1H-pyrazole

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2537047A1 (en) * 1975-08-20 1977-03-03 Bayer Ag VINYLTHIONOPHOSPHORIC ACID ESTERS, THE METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDES
US4546113A (en) * 1983-04-14 1985-10-08 Pfizer Inc. Antiprotozoal diamidines
GB8703975D0 (en) * 1987-02-20 1987-03-25 Wellcome Found Pesticidal compounds
ATE192430T1 (en) * 1993-12-03 2000-05-15 Hoffmann La Roche ACETIC ACID DERIVATIVES AS MEDICINAL PRODUCTS
DE4417837A1 (en) * 1994-05-20 1995-11-23 Basf Ag Substituted 3-phenylpyrazoles
GB9413237D0 (en) * 1994-07-01 1994-08-24 Zeneca Ltd Herbicides
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
GB9422667D0 (en) * 1994-11-10 1995-01-04 Zeneca Ltd Herbicides
WO1997000246A1 (en) * 1995-06-15 1997-01-03 Novartis Ag Novel herbicides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870677A (en) * 2010-06-28 2010-10-27 大连理工大学 5-arylmethoxy radical phenyl pyrazol compound and preparation method thereof

Also Published As

Publication number Publication date
EP0906285A1 (en) 1999-04-07
WO1997046535A1 (en) 1997-12-11
JP2000512275A (en) 2000-09-19
CA2256508A1 (en) 1997-12-11
BR9709521A (en) 1999-08-10
DE19622189A1 (en) 1997-12-04
AU2958597A (en) 1998-01-05

Similar Documents

Publication Publication Date Title
CN1113060C (en) Substituting 2-amino-4-alkylamino-1,3,5-triazine as herbicide
CN1038129C (en) Substituted triazolinones
CN1233242A (en) Substituted 2,4-diamino-1,3,5-triazines as herbicides
CN1526704A (en) Substituted triazolformamide compound
CN1239956A (en) Substituted 2-amino-4-alkylamino-1,3,5-triazines as herbicides
CN1229355C (en) Substituted fluoroalcoxyphenylsulfonylurea
CN1305466A (en) Substituted phenyl pyridazinones
CN1314894A (en) Substituted phenyl uracils compound
CN1088705C (en) Thienylsulfonylamino (THIO) carbonyl compounds
CN1227545A (en) 3-cyanoaryl pyrazoles and use thereof as herbicides
CN1257490A (en) Substituted pyridylpyrazoles as herbicides, insecticides and acaricides
CN1255126A (en) Heterocyclically substituted aromatic amino compounds with herbicidal effect
CN1216538A (en) Substituted 2-aryl-1,2,4-triazine-3,5-di(thi) ones as herbicides
CN1293060C (en) Substituted aryl sulphonyl(thio)ureas used as herbicides
CN1121392C (en) Substituted pyrimidine (thi) ones
CN1057765C (en) 4-cyano-phenyl-imino-heterocyclic compound
CN1370160A (en) Substituted heterocyclyl-2h-chromenes
CN1130360C (en) Substituted thienocycloalk (en)ylamino-1,3,5-triazine
CN1227548A (en) Substituted p-trifluoromethylphenyluracils
CN1113063C (en) Heterocyclyluracil
CN1227546A (en) Substituted 1-(3-pyrazolyl)-pyrazoles with herbicide activity and intermediate for its preparation
CN1216533A (en) 3-cyanoaryl pyrazoles and their use as herbicides
CN1311783A (en) Sulfonyl amino (thio) carbonyl triazoline (thi) one having alkenyl substitutents
CN1256329C (en) Herbicidal substituted benzoylpyrazoles
CN1329602A (en) Substituted 1,3,5-triazines as herbicides

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication