CN1305466A - Substituted phenyl pyridazinones - Google Patents

Substituted phenyl pyridazinones Download PDF

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CN1305466A
CN1305466A CN99807143A CN99807143A CN1305466A CN 1305466 A CN1305466 A CN 1305466A CN 99807143 A CN99807143 A CN 99807143A CN 99807143 A CN99807143 A CN 99807143A CN 1305466 A CN1305466 A CN 1305466A
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group
alkyl
bases
fluoro
amino
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K·H·林克尔
A·胡珀茨
M·W·德鲁斯
M·多林格
I·维特肖洛夫斯基
C·埃尔德伦
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Bayer AG
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Bayer AG
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    • 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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
    • C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/08—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having 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
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having 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
    • C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
    • C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • 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
    • C07D405/10—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 carbon chain containing aromatic rings

Abstract

The invention relates to novel substituted phenyl pyridazinones of formula (I), wherein R<1>, R<2>, R<3>, R<4>, R<5> and R<6> have the meanings cited in the description. The invention also relates to the production and use thereof as herbicides. The invention further relates to novel intermediate products.

Description

The phenyl pyridazinones that replaces
The present invention relates to the Phenylpyridazinones class of new replacement, relate to their preparation method and they are as the crop protection agent, in particular as weedicide with as the purposes of sterilant.
The Phenylpyridazinones of more known replacements has herbicidal performance (referring to DE-A-1105232, DE-A-1670309, DE-A-1670315, DE-A-1695840, DE-A-2526643, DE-A-2706700, DE-A-2808193, DE-A-2821809, DE-A-19754348, US-A-5298502, WO-A-96/39392, WO-A-97/07104).The weeding activity of these compounds is not exclusively satisfactory.
Therefore, the invention provides the Phenylpyridazinones class of the new replacement of logical formula I:
Wherein
R 1Represent hydrogen, fluorine, chlorine or bromine,
R 2Represent cyano group, formamyl, thiocarbamoyl, fluorine, chlorine, bromine, perhaps representative is optional separately by the alkyl that has 1 or 2 carbon atom separately of fluoro-and/or chloro-replacement, alkoxyl group or alkylthio,
R 3Represent group-A 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 3-C 4-alkenyl, C 3-C 4-alkynes base, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 1Also representative is optional separately by fluoro-, the C that chloro-or bromo-replace 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 2Also representative is optional separately by fluoro-, chloro-, bromo-or C 1-C 4The C of-alkoxyl group-replacement 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 3Represent hydrogen, hydroxyl, amino, cyano group, isocyano-, thiocyano, nitro, formyl radical, carboxyl, formamyl, thiocarbamoyl, sulfo group, chlorosulfonyl, fluorine, chlorine, bromine, representative optional separately by hydroxyl-, fluoro-, chloro-, C 1-C 4-alkoxyl group-, C 1-C 4-alkyl-ketonic oxygen base-or C 1-C 4The alkyl that has 1-6 carbon atom in each comfortable alkyl of-alkoxyl group-ketonic oxygen base-replacement, alkoxyl group, alkylthio; alkyl sulphinyl, alkyl sulphonyl, alkylamino; dialkyl amido, carbalkoxy, alkyl amino-carbonyl; dialkyl amino carbonyl or dialkoxy (sulfo-) phosphoryl, representative optional separately by fluoro-or chloro-replace at alkenyl, have the alkenyl of 2-6 carbon atom in alkylidene group or the alkynes base separately; alkenyl oxy; alkenyl amino, alkylidene amino, alkenyl oxy carbonyl; the alkynes base; alkynes base oxygen base, alkynes base amino or alkynes base oxygen base carbonyl, representative is optional separately by fluoro-; chloro-; cyano group-, carboxyl-, C 1-C 4-alkyl-and/or C 1-C 4Have 3-6 carbon atom in each comfortable cycloalkyl of-alkoxyl group-carbonyl-replacement and randomly in alkyl, have the cycloalkyl of 1-4 carbon atom, cycloalkyl oxy, cycloalkyl amino, cycloalkylalkyl, cycloalkyl alkoxy, cycloalkyl alkyl amino, the ring alkylidene amino, cycloalkyl oxy carbonyl or cycloalkyl alkoxy carbonyl, perhaps representative optional separately by nitro-, cyano group-, carboxyl-, fluoro-, chloro-, bromo-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-and/or C 1-C 4The phenyl of-carbalkoxy-replacement, phenoxy group, phenyl-C 1-C 4-alkyl, phenyl-C 1-C 4-alkoxyl group, carbobenzoxy or phenyl-C 1-C 4-carbalkoxy,
A 3Also quilt hydrogenant pyrryl wholly or in part, pyrazolyl, imidazolyl, triazolyl are chosen in representative separately wantonly, furyl, Oxyranyle, oxetanyl, dioxolanyl alkyl dioxin, thienyl ， oxazolyl isoxazolyl, thiazolyl, isothiazolyl oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl-C 1-C 4-alkyl, furyl-C 1-C 4-alkyl, thienyl-C 1-C 4-alkyl ， oxazolyl-C 1-C 4-alkyl ， isoxazolyl-C 1-C 4-alkyl, thiazolyl-C 1-C 4-alkyl, pyridyl-C 1-C 4-alkyl, pyrimidyl-C 1-C 4-alkyl, the pyrazolyl methoxyl group, the furyl methoxyl group is represented perhydro pyranyl methoxyl group or pyridyl methoxyl group,
R 4Represent hydrogen, carboxyl, cyano group; formamyl, thiocarbamoyl, nitro; hydroxyl, sulfydryl, amino; fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl that has 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement, alkoxyl group, alkylthio; alkylamino, dialkyl amido or carbalkoxy
R 5Represent hydrogen, carboxyl, cyano group; formamyl, thiocarbamoyl, nitro; hydroxyl, sulfydryl, amino; fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl that has 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement, alkoxyl group, alkylthio; alkylamino, dialkyl amido or carbalkoxy and
R 6Represent hydrogen, carboxyl, cyano group; formamyl, thiocarbamoyl, nitro; hydroxyl, sulfydryl, amino; fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl that has 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement, alkoxyl group, alkylthio; alkylamino, dialkyl amido or carbalkoxy.
The Phenylpyridazinones of the new replacement of logical formula I has interesting biological property, particularly strong weeding and insecticidal activity.
In definition, saturated or unsaturated hydrocarbon chain, alkyl for example, each straight or branched naturally of alkenyl or alkynes base.
Halogen general proxy fluorine, chlorine, bromine or iodine, preferred fluorine, chlorine or bromine, particularly fluorine or chlorine.
R 1Preferably represent hydrogen, fluorine or chlorine,
R 2Preferably represent cyano group, formamyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl or trifluoromethyl,
R 3Preferred group-the A that represents 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, methyl, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group, just-or different-propoxy-, methyl sulphonyl or ethylsulfonyl,
A 1Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases, propylene-1,3-two bases, acetylene-1,2-two bases, propine-1,2-two bases or propine-1,3-two bases
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, methyl, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group, just-or different-propoxy-, methyl sulphonyl, ethylsulfonyl, just-or different-sulfonyl propyl base or phenyl sulfonyl,
A 2Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases, propylene-1,3-two bases, acetylene-1,2-two bases, propine-1,2-two bases or propine-1,3-two bases
A 3Represent hydrogen, hydroxyl, amino; cyano group, nitro, formyl radical; carboxyl, formamyl, sulfo group; fluorine, chlorine, bromine; representative is optional separately by fluoro-, chloro-, and methoxyl group-or the methyl of oxyethyl group-replacement; ethyl, just-or different-propyl group, just-; different-, secondary-or tert-butyl, just-; different-, secondary-or uncle-amyl group, methoxyl group; oxyethyl group, just-or different-propoxy-, just-; different-, secondary-or uncle-butoxy, just-; different-, secondary-or uncle-pentyloxy, methylthio group; ethylmercapto group, just-or different-rosickyite base, just-; different-, secondary-or uncle-butylthio, methylsulfinyl; the ethyl sulfinyl, just-or different-propyl group sulfinyl, methyl sulphonyl; ethylsulfonyl, just-or different-sulfonyl propyl base, methylamino; ethylamino, just-or different-propyl group amino, just-; different-, secondary-or tert-butyl amino, dimethylamino; diethylamino, methoxycarbonyl, ethoxycarbonyl; just-or different-third oxygen carbonyl, dimethoxy phosphoryl, diethoxy phosphoryl or dipropoxy phosphoryl; diisopropoxy phosphoryl, representative are optional separately by the vinyl of fluoro-or chloro-replacement, propenyl; butenyl, propenyl oxygen base, butenyl oxygen base; propenyl amino, butenyl amino, propylidene amino; butylidene amino, propenyl oxygen base carbonyl, butenyl oxygen base carbonyl; ethynyl, proyl, butynyl; proyl oxygen base, butynyl oxygen base, proyl amino; butynyl amino, proyl oxygen base carbonyl or butynyl oxygen base carbonyl, representative is optional separately by fluoro-; chloro-, cyano group-, carboxyl-; methyl-, ethyl-, just-or different-propyl group-; methoxycarbonyl-or the cyclopropyl of ethoxycarbonyl-replacement; cyclobutyl, cyclopentyl, cyclohexyl; cyclopropyl oxygen base; cyclobutyl oxygen base, cyclopentyloxy, cyclohexyl oxygen base; the cyclopropyl methyl; cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl; cyclo propyl methoxy; cyclobutyl methoxy base, cyclopentyl methoxyl group, cyclohexyl methoxyl group; ring pentylidene amino; cyclohexylene amino, cyclopentyloxy carbonyl, cyclohexyl oxygen base carbonyl; cyclopentyl methoxycarbonyl or cyclohexyl methoxycarbonyl; perhaps representative optional separately by nitro-, cyano group-, carboxyl-; fluoro-; chloro-, bromo-, methyl-; ethyl-; just-or different-propyl group-, trifluoromethyl-, methoxyl group-; oxyethyl group-; just-or different-propoxy--, difluoro-methoxy-, trifluoromethoxy-; methoxycarbonyl-and/or the phenyl of ethoxycarbonyl-replacement; phenoxy group, benzyl, styroyl; benzyl oxygen base; carbobenzoxy, benzyl oxygen base carbonyl
A 3Also representative (optional separately quilt is hydrogenant wholly or in part) dioxolanyl ， alkyl dioxin, pyrryl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl ， oxazolyl ， isoxazolyl, thiazolyl, isothiazolyl ， oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl methyl, furyl methyl, thienyl methyl oxazolyl methyl ， isoxazolyl methyl, thiazolyl methyl, pyridylmethyl, Pyrimidylmethyl, pyrazolyl methoxyl group, furyl methoxyl group or pyridyl methoxyl group
R 4Preferably represent hydrogen, carboxyl, cyano group, formamyl, thiocarbamoyl; nitro, hydroxyl, sulfydryl, amino, fluorine; chlorine, bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl, just-or different-propyl group; just-, different-, secondary-or tert-butyl, methoxyl group; oxyethyl group, methylthio group, ethylmercapto group, methylamino; ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl
R 5Preferably represent hydrogen, carboxyl, cyano group, formamyl, thiocarbamoyl; nitro, hydroxyl, sulfydryl, amino, fluorine; chlorine, bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl, just-or different-propyl group; just-, different-, secondary-or tert-butyl, methoxyl group; oxyethyl group, methylthio group, ethylmercapto group, methylamino; ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl and
R 6Preferably represent hydrogen, carboxyl, cyano group, formamyl, thiocarbamoyl; nitro, hydroxyl, sulfydryl, amino, fluorine; chlorine, bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl; just-or different-propyl group, just-, different-, secondary-or tert-butyl; methoxyl group, oxyethyl group, methylthio group, ethylmercapto group; methylamino, ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl.
R 1Especially preferably represent hydrogen, fluorine or chlorine,
R 2Especially preferably represent cyano group or thiocarbamoyl,
R 3Especially preferably represent group-A 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, methyl, ethyl, just-or different-propyl group, methyl sulphonyl or ethylsulfonyl,
A 1Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases or propylene-1,3-two bases,
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, methyl, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group, just-or different-propoxy-, methyl sulphonyl, ethylsulfonyl, just-or different-sulfonyl propyl base or phenyl sulfonyl,
A 2Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases or propylene-1,3-two bases,
A 3Represent hydrogen, hydroxyl, amino; cyano group, nitro, carboxyl; formamyl, sulfo group, fluorine; chlorine, bromine, representative is optional separately by fluoro-; chloro-, methoxyl group-or the methyl of oxyethyl group-replacement, ethyl; just-or different-propyl group, just-, different-; secondary-or tert-butyl, just-, different-; secondary-or uncle-amyl group, methoxyl group, oxyethyl group; just-or different-propoxy-, just-, different-; secondary-or uncle-butoxy, just-, different-; secondary-or uncle-pentyloxy, methylthio group, ethylmercapto group; just-or different-rosickyite base, just-, different-; secondary-or uncle-butylthio, methylsulfinyl, ethyl sulfinyl; just-or different-propyl group sulfinyl, methyl sulphonyl, ethylsulfonyl; just-or different-sulfonyl propyl base, methylamino, ethylamino; just-or different-propyl group amino, just-, different-; secondary-or tert-butyl amino, dimethylamino, diethylamino; methoxycarbonyl, ethoxycarbonyl, just-or different-third oxygen carbonyl; representative is optional separately by the propenyl of fluoro-or chloro-replacement, butenyl, propenyl oxygen base; butenyl oxygen base, propenyl amino, butenyl amino; propylidene amino, butylidene amino, propenyl oxygen base carbonyl; butenyl oxygen base carbonyl, proyl, butynyl; proyl oxygen base, butynyl oxygen base, proyl amino; butynyl amino, proyl oxygen base carbonyl or butynyl oxygen base carbonyl, representative is optional separately by fluoro-; chloro-, cyano group-, carboxyl-; methyl-, ethyl-, just-or different-propyl group-; methoxycarbonyl-or the cyclopropyl of ethoxycarbonyl-replacement, cyclobutyl, cyclopentyl; cyclohexyl, cyclopropyl oxygen base, cyclobutyl oxygen base; cyclopentyloxy, cyclohexyl oxygen base, cyclopropyl methyl; cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl; cyclo propyl methoxy, cyclobutyl methoxy base, cyclopentyl methoxyl group; the cyclohexyl methoxyl group, ring pentylidene amino, cyclohexylene amino; the cyclopentyloxy carbonyl; cyclohexyl oxygen base carbonyl, cyclopentyl methoxycarbonyl or cyclohexyl methoxycarbonyl, perhaps representative optional separately by nitro-; cyano group-; carboxyl-, fluoro-, chloro-; bromo-; methyl-, ethyl-, just-or different-propyl group-; trifluoromethyl-; methoxyl group-, oxyethyl group-, just-or different-propoxy--; difluoro-methoxy-; trifluoromethoxy-, methoxycarbonyl-and/or the phenyl of ethoxycarbonyl-replacement, phenoxy group; benzyl; styroyl, benzyl oxygen base, carbobenzoxy; benzyl oxygen base carbonyl
A 3Also represent pyrazolyl, imidazolyl, triazolyl, furyl, thienyl oxazolyl ， isoxazolyl, thiazolyl, isothiazolyl oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl methyl, furyl methyl, thienyl methyl oxazolyl methyl ， isoxazolyl methyl, thiazolyl methyl, pyridylmethyl, Pyrimidylmethyl, pyrazolyl methoxyl group, furyl methoxyl group or pyridyl methoxyl group
R 4Especially preferably represent hydrogen, cyano group, thiocarbamoyl, nitro, fluorine, chlorine; bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group; methylthio group, ethylmercapto group, methylamino, ethylamino or dimethylamino
R 5The methyl that preferred especially representative is replaced by fluoro-and/or chloro-separately, ethyl, just-or different-propyl group and
R 6Especially preferably represent hydrogen, cyano group, thiocarbamoyl; nitro, fluorine, chlorine; bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl; just-or different-propyl group, methoxyl group, oxyethyl group; methylthio group, ethylmercapto group, methylamino; ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl.
Above-mentioned general or preferred group definition is applicable to the end product of formula I and correspondingly is applicable to and is used to prepare needed initiator or intermediate separately.These group definition can make up as required mutually, promptly comprise the combination between the given preferable range.
Preferably provide above comprising compound as the formula I of the combination of the definition of preferably listing according to the present invention.
Especially preferably provide above comprising compound as the formula I of the combination of the definition of especially preferably listing according to the present invention.
List the compound of formula I very particularly preferably in the following group.The 1st group
Figure A9980714300191
Ar for example has following definition here:
4-cyano group-phenyl; 2-fluoro-4-cyano group-phenyl; 2-chloro-4-cyano group-phenyl; 3-fluoro-4-cyano group-phenyl; 3-chloro-4-cyano group-phenyl; 2-fluoro-5-chloro-4-cyano group-phenyl; 2; 5-two chloro-4-cyano group-phenyl; 2-chloro-5-fluoro-4-cyano group-phenyl; 2-chloro-4; 5-dicyano-phenyl; 2-chloro-4-fluoro-5-cyano group-phenyl; 2; 5-two fluoro-4-cyano group-phenyl, 2-chloro-4-cyano group-5-methyl-phenyl, 2-fluoro-4-cyano group-5-methyl-phenyl; 2-chloro-4-cyano group-5-trifluoromethyl-phenyl; 2-fluoro-4-cyano group-5-trifluoromethyl, 2,5-two fluoro-4-thiocarbamoyl-phenyl; 2-fluoro-4-cyano group-5-methoxyl group-phenyl; 2-fluoro-4-cyano group-5-isopropoxy-phenyl, 2-chloro-4-cyano group-5-(2-propynyl oxygen base)-phenyl, 2-fluoro-4-cyano group-5-(1-methyl-2-propynyl oxygen base)-phenyl; 2-chloro-4-thiocarbamoyl-5-isopropoxy-phenyl; 2-fluoro-4-cyano group-5-(2-propenyl oxygen base)-phenyl, 2-chloro-4-cyano group-5-methyl sulphonyl-amino-phenyl, 2-fluoro-4-cyano group-5-ethylsulfonyl amino-phenyl; 2-fluoro-4-thiocarbamoyl-5-methyl sulphonyl amino-phenyl; 2-chloro-4-cyano group-5-ethylsulfonyl-amino-phenyl, 2-fluoro-4-cyano group-5-cyclopropyl sulfuryl amino-phenyl, 2-fluoro-4-cyano group-5-sec.-propyl sulfuryl amino-phenyl; 2-chloro-4-thiocarbamoyl-5-ethyl-sulfuryl amino-phenyl; 2-chloro-4-cyano group-5-cyano group amino-phenyl, 2-fluoro-4-cyano group-5-trifluoromethyl sulfonyl amino-phenyl, 2-fluoro-4-cyano group-5-(2; 2-two fluoro ethyls-sulfuryl amino)-phenyl; 2-fluoro-4-cyano group-5-phenyl sulfonyl amino-phenyl, 2-fluoro-4-cyano group-5-tertiary butyl sulfuryl amino-phenyl, 2-chloro-4-cyano group-5-methoxyl group-carbonyl-phenyl; 2-fluoro-4-cyano group-5-ethoxycarbonyl-phenyl; 2-fluoro-4-thiocarbamoyl-5-methoxycarbonyl-phenyl, 2-fluoro-4-cyano group-5-(1-methyl-2-propynyl-sulfenyl)-phenyl, 2-fluoro-4-cyano group-5-methylamino-phenyl; 2-chloro-4-thiocarbamoyl-5-methoxycarbonyl methyl-phenyl; 2-chloro-4-cyano group-5-(N-methyl-ethylsulfonyl-amino)-phenyl, 2-chloro-4-cyano group-5-isopropoxy carbonyl-phenyl, 2-fluoro-4-cyano group-5-(two-ethylsulfonyl-amino)-phenyl; 2-fluoro-4-cyano group-5-(N-methyl sulphonyl-N-ethylsulfonyl amino)-phenyl; 2-fluoro-4-cyano group-5-(1-methoxycarbonyl-oxyethyl group)-phenyl, 2-fluoro-4-cyano group-5-cyclopropyl oxygen base-phenyl, 2-chloro-4-cyano group-5-dimethylamino-phenyl; 2-fluoro-4-cyano group-5-tetrahydrofuran (THF) ylmethoxy-phenyl; 2-fluoro-4-cyano group-5-amino-phenyl, 2-fluoro-4-cyano group-5-methylamino carbonyl-phenyl, 2-fluoro-4-cyano group-5-methyl sulphonyl oxygen base-phenyl; 2-chloro-4-cyano group-5-difluoro-methoxy-phenyl; 2-fluoro-4-cyano group-5-ethoxycarbonyl methoxyl group-phenyl, 2-fluoro-4-cyano group-5-dimethylamino carbonyl-phenyl, 2-fluoro-4-cyano group-5-cyano group methoxyl group-phenyl; 2-fluoro-4-cyano group-5-(2-chloro-2-propenyl oxygen base)-phenyl; 2-fluoro-4-cyano group-5-hydroxyl-phenyl, 2-fluoro-4-cyano group-5-nitro-phenyl, 2-fluoro-4-cyano group-5-diethoxy phosphoryl amino-phenyl; 2-fluoro-4-cyano group-5-chloro alkylsulfonyl-phenyl; 2-fluoro-4-cyano group-5-formyl radical amino-phenyl, 2-chloro-4-cyano group-5-ethoxycarbonyl-oxygen base-phenyl, 2-fluoro-4-cyano group-5-diethoxy phosphoryl methoxy base-phenyl; 2-chloro-4-cyano group-5-hydroxyl-phenyl; 2-fluoro-4-cyano group-5-(N, N-diacetyl-amino)-phenyl, 2-fluoro-4-cyano group-5-acetylamino-phenyl; 2-chloro-4-cyano group-5-thiocyano-phenyl; 2-fluoro-4-cyano group-5-diethylamino oxygen base-phenyl, 2-fluoro-4-cyano group-5-tetrahydrofuran base oxygen base-phenyl, 2-fluoro-4-cyano group-5-urea groups-phenyl; 2-fluoro-4-cyano group-5-dimethoxy methene amido-phenyl; 2-chloro-4-cyano group-5-oxyethyl group methene amido-phenyl, 2-fluoro-4-cyano group-5-(2-chloro-ethoxycarbonyl-oxygen base)-phenyl, 2-chloro-4-cyano group-5-dimethylamino methene amido-phenyl; 2-chloro-4-cyano group-5-(perhydro pyrans-4-base oxygen base)-phenyl; 2-fluoro-4-cyano group-5-(2-methoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano group-5-(2-carboxyl-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano group-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl; 2-fluoro-4-cyano group-5-(2-chloro-2-secondary butoxy carbonyl)-phenyl; 2-fluoro-4-cyano group-5-(2-chloro-2-formamyl-ethyl)-phenyl, 2-fluoro-4-cyano group-5-(2-chloro-2-methoxycarbonyl-1-methyl-ethyl)-phenyl, 2-fluoro-4-cyano group-5-(1; 2-two bromo-2-methoxycarbonyl-ethyls)-phenyl; 2-chloro-4-cyano group-5-(2-chloro-2-isopropoxy-carbonyl-ethyl)-phenyl, 2-fluoro-4-cyano group-5-(2-carboxyl-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano group-5-(2-chloro-2-ethylamino carbonyl-ethyl)-phenyl; 2-fluoro-4-cyano group-5-(2-allyl amino carbonyl-2-chloro-ethyl)-phenyl; 2-fluoro-4-cyano group-5-(2-ethoxycarbonyl-vinyl)-phenyl, 2-fluoro-4-cyano group-5-(2-chloro-2-cyclopropyl aminocarboxyl-ethyl)-phenyl, 2-fluoro-4-cyano group-5-(2-chloro-2-dimethylamino carbonyl-ethyl)-phenyl; 2-chloro-4-cyano group-5-(2-chloro-2-ethylsulfonyl aminocarboxyl-ethyl)-phenyl; 2-fluoro-4-thiocarbamoyl-5-(2-ethylamino carbonyl-vinyl)-phenyl, 2-fluoro-4-cyano group-5-(1-ethoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano group-5-(1-ethoxy carbonyl ethyl)-phenyl; 2-chloro-4-cyano group-5-carboxyl-phenyl; 2-fluoro-4-cyano group-5-isobutoxy-phenyl, 2-chloro-4-cyano group-5-isobutoxy-phenyl, 2-chloro-4-cyano group-5-(2-methoxyl group-oxyethyl group)-phenyl; 2-fluoro-4-cyano group-5-(N-ethanoyl-N-methyl sulphonyl-amino)-phenyl; 2-fluoro-4-cyano group-5-(N-propionyl-N-methyl sulphonyl-amino)-phenyl, 2-fluoro-4-cyano group-5-(N-isobutyryl-N-methyl sulphonyl-amino)-phenyl, 2-fluoro-4-cyano group-5-(N-valeryl-N-methyl sulphonyl-amino)-phenyl; 2-fluoro-4-cyano group-5-(N-benzoyl-N-methyl sulphonyl-amino)-phenyl; 2-fluoro-4-cyano group-5-(N-(4-methoxyl group-benzoyl)-N-methyl-alkylsulfonyl-amino)-phenyl, 2-fluoro-4-cyano group-5-(N-ethanoyl-N-ethylsulfonyl-amino)-phenyl, 2-fluoro-4-cyano group-5-(N-propionyl-N-ethylsulfonyl-amino)-phenyl; 2-fluoro-4-cyano group-5-(N-isobutyryl-N-ethylsulfonyl-amino)-phenyl; 2-fluoro-4-cyano group-5-(N-valeryl-N-ethylsulfonyl-amino)-phenyl, 2-fluoro-4-cyano group-5-(N-benzoyl-N-ethylsulfonyl-amino)-phenyl, 2-fluoro-4-cyano group-5-(N-(4-methoxyl group-benzoyl)-N-ethyl-alkylsulfonyl-amino)-phenyl; 2-fluoro-4-thiocarbamoyl-5-(N-ethanoyl-N-methyl sulphonyl-amino)-phenyl; 2-fluoro-4-thiocarbamoyl-5-(N-propionyl-N-methyl sulphonyl-amino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-isobutyryl-N-methyl sulphonyl-amino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-valeryl-N-methyl sulphonyl-amino)-phenyl; 2-fluoro-4-thiocarbamoyl-5-(N-benzoyl-N-methyl sulphonyl-amino)-phenyl; 2-fluoro-4-thiocarbamoyl-5-(N-(4-methoxyl group-benzoyl)-N-methyl sulphonyl-amino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-ethanoyl-N-ethylsulfonyl-amino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-propionyl-N-ethylsulfonyl-amino)-phenyl; 2-fluoro-4-thiocarbamoyl-5-(N-isobutyryl-N-ethylsulfonyl-amino)-phenyl; 2-fluoro-4-thiocarbamoyl-5-(N-valeryl-N-ethylsulfonyl-amino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-benzoyl-N-ethylsulfonyl-amino)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(N-(4-methoxyl group-benzoyl)-N-ethylsulfonyl-amino)-phenyl.
The 2nd group
Figure A9980714300221
Ar for example has the definition of listing in top the 1st group here.
The 3rd group
Figure A9980714300222
Ar for example has the definition of listing in top the 1st group here.
The 4th group
Figure A9980714300223
Ar for example has the definition of listing in top the 1st group here.
The 5th group
Figure A9980714300224
Ar for example has the definition of listing in top the 1st group here.
The 6th group
Figure A9980714300231
Ar for example has the definition of listing in top the 1st group here.
The 7th group
Ar for example has the definition of listing in top the 1st group here.
The 8th group
Figure A9980714300233
Ar for example has the definition of listing in top the 1st group here.
The 9th group
Figure A9980714300234
Ar for example has the definition of listing in top the 1st group here.
The 10th group
Ar for example has the definition of listing in top the 1st group here.
The 11st group
Figure A9980714300241
Ar for example has the definition of listing in top the 1st group here.
The 12nd group
Figure A9980714300242
Ar for example has the definition of listing in top the 1st group here.
The 13rd group
Figure A9980714300243
Ar for example has the definition of listing in top the 1st group here.
The 14th group
Figure A9980714300244
Ar for example has the definition of listing in top the 1st group here.
The 15th group
Figure A9980714300245
Ar for example has the definition of listing in top the 1st group here.
The 16th group
Figure A9980714300251
Ar for example has the definition of listing in top the 1st group here.
The 17th group
Ar for example has the definition of listing in top the 1st group here.
The 18th group
Ar for example has the definition of listing in top the 1st group here.
The 19th group
Figure A9980714300254
Ar for example has the definition of listing in top the 1st group here.
The 20th group
Figure A9980714300255
Ar for example has the definition of listing in top the 1st group here.
The 21st group
Figure A9980714300261
Ar for example has the definition of listing in top the 1st group here.
The 22nd group
Figure A9980714300262
Ar for example has the definition of listing in top the 1st group here.
The 23rd group
Ar for example has the definition of listing in top the 1st group here.
The 24th group
Figure A9980714300264
Ar for example has the definition of listing in top the 1st group here.
The 25th group
Ar for example has the definition of listing in top the 1st group here.
The 26th group
Ar for example has the definition of listing in top the 1st group here.
The 27th group
Figure A9980714300272
Ar for example has the definition of listing in top the 1st group here.
The 28th group
Ar for example has the definition of listing in top the 1st group here.
The 29th group
Ar for example has the definition of listing in top the 1st group here.
The 30th group
Figure A9980714300275
Ar for example has the definition of listing in top the 1st group here.
The 31st group
Ar for example has the definition of listing in top the 1st group here.
The 32nd group
Ar for example has the definition of listing in top the 1st group here.
When the reaction below carrying out, obtain the Phenylpyridazinones of the new replacement of logical formula I:
(a) if if suitably in the presence of reaction promoter and suitably in the presence of thinner, the halogenated aryl hydrocarbon of logical formula II reacts with the pyridazinone of logical formula III or reacts with the sour affixture or an alkali metal salt of logical formula III compound:
Figure A9980714300283
Wherein
R 1, R 2And R 3As above the definition and
X 1Represent halogen,
Figure A9980714300284
Wherein
R 4, R 5And R 6As above definition,
Perhaps
(b) if if suitably in the presence of reaction promoter and suitably in the presence of thinner, the aryl hydrazine of logical formula IV and the β-trihalogenmethyl of general formula (V)-ketenes react:
Wherein
R 1, R 2And R 3As above the definition and
Figure A9980714300292
Wherein
R 4, R 5And R 6As above definition,
X 2Represent halogen,
Perhaps
(c) the hydrazone carboxylic acid of logical formula VI carries out the closed loop condensation, promptly reacts with dewatering agent:
Figure A9980714300293
Wherein
R 1, R 2, R 3, R 4, R 5And R 6As above definition,
Perhaps
(d) nitrated general formula (I a) 2, the dibasic Phenylpyridazinones of 4-, promptly react with nitrating agent:
Figure A9980714300301
Wherein
R 1, R 2, R 4, R 5And R 6As above definition,
Perhaps
(e) separately randomly in the presence of reaction promoter and randomly in the presence of thinner, the positive phosphine reaction of carbalkoxy methylene radical of the hydrazone carbonyl compound of general formula (VII) and general formula (VIII) or with the phosphono-carboxylic acids trialkyl ester reaction of general formula (IX):
Figure A9980714300302
Wherein
R 1, R 2, R 3, R 5And R 6As above definition,
Wherein
R 4As above the definition and
The R representative has the alkyl of 1-6 carbon atom,
Wherein
R 4As above the definition and
The R representative has the alkyl of 1-6 carbon atom.
The compound of logical formula I also can be converted into compound according to other logical formula I of above-mentioned definition by other ordinary method, for example by nucleophilic substitution (R for example 3: F → OH, SH, NH 2, OCH 3, NHSO 2CH 3) or (R for example of the further conversion by functional group 2: F/Cl/Br → CN, CONH 2→ CN, CN → CSNH 2, NO 2→ NH 2R 3: NO 2→ NH 2, NH 2→ F, Cl, Br, CN, NHSO 2CH 3, SO 2Cl, OCH 3→ OH, OH → OCH 2CH=CH 2)-also is referring to preparation embodiment.
Use, 4-fluoro-6-methyl-5-trifluoromethyl-pyridazin-3-one and 4 for example, 5-difluoro-2-methoxyl-benzonitrile is an initiator, then the reaction process of the method according to this invention (a) can be represented by following reaction formula:
Figure A9980714300311
Use, for example 4,4,4-three chloro-3-Methyl-2-difluoromethyl-crotonaldehydes and 4-cyano group-2-fluoro-5-propargyloxy-phenyl hydrazine is an initiator, then the reaction process of the method according to this invention (b) can be represented by following reaction formula:
Figure A9980714300312
Use, for example 2-chloro-3-chlorodifluoramethyl--4-oxo-(4-cyano group-2-fluoro-5-methyl sulphonyl amino-phenyl)-hydrazone is an initiator to 2-butylene acid N-, and then the reaction process of the method according to this invention (c) can be represented by following reaction formula:
Use, 2-(2-chloro-4-cyano group-phenyl)-4 for example, 6-two chloro-5-pentafluoroethyl group pyridazin-3-ones and nitric acid are initiator, then the reaction process of the method according to this invention (d) can be represented by following reaction formula:
Figure A9980714300322
Use, for example 3,3,3-three fluoro-2-oxo-propionic aldehyde 1-(4-cyano group-2,5-difluorophenyl-hydrazone) and triphenyl Asia phosphine ethyl acetate are initiator, then the reaction process of the method according to this invention (e) can be represented by following reaction formula:
Figure A9980714300323
Formula II provides will be as the General Definition of the halogenated aryl hydrocarbon of initiator in the method according to this invention (a) of the compound that is used for preparing formula I.In formula II, R 1, R 2And R 3Above preferably or especially having in the description of the compound of the formula I that will prepare according to the present invention already mentioned conduct preferred or as particularly preferred R 1, R 2And R 3Definition; X 1Preferably represent fluorine, chlorine or bromine, particularly fluorine.
The initiator of formula II be known and/or can by known method preparation itself (referring to EP191181, EP370332, EP431373, EP441004).
Formula III provides the General Definition that also will be used as the pyridazinone of initiator in the method according to this invention (a).In formula III, R 4, R 5And R 6Above preferably having in the description of the compound of the formula I that will prepare according to the present invention already mentioned conduct preferred, particularly preferred or R very particularly preferably 4, R 5And R 6Definition.
The initiator of formula III be known and/or can by known method preparation itself (referring to J.Chem.Soc.1947,239; Angew.Chem.77 (1965), 282; Monatsh.Chem.120 (1989), 329).
Formula IV provides will be as the General Definition of the aryl hydrazine of initiator in the method according to this invention (b) of the compound that is used for preparing formula I.In formula IV, R 1, R 2And R 3Above preferably having in the description of the compound of the formula I that will prepare according to the present invention already mentioned conduct preferred, particularly preferred or R very particularly preferably 1, R 2And R 3Definition.
The initiator of formula IV is known and/or can be by known method preparation (referring to EP370332) itself.
Formula (V) provides the General Definition that also will be used as the β-trihalogenmethyl-ketenes of initiator in the method according to this invention (b).In formula (V), R 4, R 5And R 6Above preferably having in the description of the compound of the formula I that will prepare according to the present invention already mentioned conduct preferred, particularly preferred or R very particularly preferably 4, R 5And R 6Definition; X 2Preferably represent fluorine, chlorine or bromine, particularly chlorine.
The initiator of formula (V) is known and/or can be by known method preparation (referring to DE2706700) itself.
Formula VI provides will be as the General Definition of the hydrazone carboxylic acid of initiator in the method according to this invention (c) of the compound that is used for preparing formula I.In formula VI, R 1, R 2, R 3, R 4, R 5Above preferably having with R6 in the description of the compound of the formula I that will prepare according to the present invention already mentioned conduct preferred, particularly preferred or R very particularly preferably 1, R 2, R 3, R 4, R 5Definition with R6.
The initiator of formula VI is known and/or can be by known method preparation (referring to WO9639392) itself.
If when suitably at thinner for example in the presence of the alcoholic acid, if with suitably reaction promoter for example tosic acid in the presence of, under the temperature between 0 ℃ and 100 ℃, when the aryl hydrazine of logical formula IV and the β-carboxyl of general formula (X)-ketenes react, obtain the hydrazone carboxylic acid of logical formula IV:
Figure A9980714300341
Wherein
R 1, R 2And R 3As above definition,
Figure A9980714300342
Wherein
R 4, R 5And R 6As above definition.
(I a) provides will be as 2 of initiator, the General Definition of the dibasic Phenylpyridazinones of 4-in the method according to this invention (d) of the compound that is used for preparing formula I for formula.Formula (I a) in, R 1, R 2, R 4, R 5And R 6Above preferably having in the description of the compound of the formula I that will prepare according to the present invention already mentioned conduct preferred, particularly preferred or R very particularly preferably 1, R 2, R 4, R 5And R 6Definition.
(I initiator a) is known and/or can be by known method preparation (referring to the method according to this invention (a)-(c)) itself formula.
Formula (VII) provides will be as the General Definition of the hydrazone carbonyl compound of initiator in the method according to this invention (e) of the compound that is used for preparing formula I.In formula (VII), R 1, R 2, R 3, R 5And R 6Already mentioned conduct relevant with the description of the compound of the formula I that will prepare according to the present invention above preferably or especially having is preferred, particularly preferred or R very particularly preferably 1, R 2, R 3, R 5And R 6Definition.
The initiator of formula (VII) is known and/or can be by known method preparation (referring to according to WO9707104) itself.
As the new compound of the part of theme of the present invention, also do not disclose in the document be general formula (VII hydrazone carbonyl compound a):
Figure A9980714300351
Wherein
R 1Represent fluorine, chlorine or bromine,
R 2-1Represent cyano group, formamyl, thiocarbamoyl, perhaps representative is optional separately by the alkyl that has 1 or 2 carbon atom separately of fluoro-and/or chloro-replacement, alkoxyl group or alkylthio,
R 3Represent group-A 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 3-C 4-alkenyl, C 3-C 4-alkynes base, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 1Also representative is optional separately by fluoro-, the C that chloro-or bromo-replace 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 2Also representative is optional separately by fluoro-, the C that chloro-or bromo-replace 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 3Represent hydrogen, hydroxyl, amino, cyano group, isocyano-, thiocyano, nitro, carboxyl, formamyl, thiocarbamoyl, sulfo group, chlorosulfonyl, fluorine, chlorine, bromine, representative is optional separately by fluoro-, chloro-or C 1-C 4The alkyl that has 1-6 carbon atom in the comfortable alkyl of each of-alkoxyl group-replacement, alkoxyl group, alkylthio; alkyl sulphinyl, alkyl sulphonyl, alkylamino; dialkyl amido; carbalkoxy or dialkoxy (sulfo-) phosphoryl, representative optional separately by fluoro-or chloro-replace at alkenyl, have the alkenyl of 2-6 carbon atom in alkylidene group or the alkynes base separately; alkenyl oxy; alkenyl amino, alkylidene amino, alkenyl oxy carbonyl; the alkynes base; alkynes base oxygen base, alkynes base amino or alkynes base oxygen base carbonyl, representative is optional separately by fluoro-; chloro-; cyano group-, carboxyl-, C 1-C 4-alkyl-and/or C 1-C 4Have 3-6 carbon atom in each comfortable cycloalkyl of-alkoxyl group-carbonyl-replacement and randomly in alkyl, have the cycloalkyl of 1-4 carbon atom, cycloalkyl oxy, cycloalkylalkyl, cycloalkyl alkoxy, the ring alkylidene amino, cycloalkyl oxy carbonyl or cycloalkyl alkoxy carbonyl, perhaps representative optional separately by nitro-, cyano group-, carboxyl-, fluoro-, chloro-, bromo-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-and/or C 1-C 4The phenyl of-carbalkoxy-replacement, phenoxy group, phenyl-C 1-C 4-alkyl, phenyl-C 1-C 4-alkoxyl group, carbobenzoxy or phenyl-C 1-C 4-carbalkoxy,
A 3Also quilt hydrogenant pyrryl wholly or in part, pyrazolyl, imidazolyl, triazolyl are chosen in representative separately wantonly, furyl, Oxyranyle, oxetanyl, dioxolanyl, thienyl ， oxazolyl isoxazolyl, thiazolyl, isothiazolyl oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl-C 1-C 4-alkyl, furyl-C 1-C 4-alkyl, thienyl-C 1-C 4-alkyl ， oxazolyl-C 1-C 4-alkyl ， isoxazolyl-C 1-C 4-alkyl, thiazolyl-C 1-C 4-alkyl, pyridyl-C 1-C 4-alkyl, pyrimidyl-C 1-C 4-alkyl, the pyrazolyl methoxyl group, the furyl methoxyl group is represented perhydro pyranyl methoxyl group or pyridyl methoxyl group,
R 5Represent hydrogen, cyano group, thiocarbamoyl, nitro, hydroxyl; sulfydryl, amino, fluorine, chlorine, bromine; the perhaps optional separately alkyl that in alkyl, has 1-4 carbon atom separately that is replaced by fluoro-and/or chloro-of representative, alkoxyl group, alkylthio, alkylamino or dialkyl amido and
R 6Represent hydrogen, cyano group, thiocarbamoyl, nitro, hydroxyl; sulfydryl, amino, fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl, alkoxyl group, alkylthio, alkylamino or the dialkyl amido that have 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement.
When the reaction below carrying out, obtain general formula (VII new hydrazone carbonyl compound a):
If if (α) suitably thinner for example water in the presence of and suitably reaction promoter for example sodium acetate in the presence of, under the temperature between 0 ℃ and 100 ℃, formula (IV aryl hydrazine a) and the α-dihalo of general formula (XI)-carbonyl compound reacts:
Figure A9980714300371
Wherein
R 1, R 2-1And R 3As above definition,
Wherein
R 5And R 6As above the definition and
X 3Represent halogen (particularly chlorine or bromine)
(referring to preparation embodiment),
Perhaps at R 6Represent under the situation of hydrogen-
(β) with the arylamines diazotization of ordinary method (for example by with Sodium Nitrite and hydrochloric acid and/or acetic acidreaction) with general formula (XII):
Wherein
R 1, R 2-1And R 3As above definition, the diazonium salt that obtains in a usual manner with 1 of general formula (X III), 3-dicarbonyl compound reaction:
Figure A9980714300374
Wherein
R 5As above the definition and
R represents alkyl (preferable methyl or ethyl),
The compound and the decarboxylize of the general formula (X IV) that obtains of hydrolysis in a usual manner:
Wherein
R, R 1, R 2-1, R 3And R 5As above definition.
Formula (VIII) and (IX) provide respectively also will be as the carbalkoxy methylene radical phosphorane of initiator and the General Definition of phosphono-carboxylic acids trialkyl ester in the method according to this invention (e) of the compound that is used for preparing formula I.In formula (VIII) and (IX), R 4Above preferably having separately with preferred according to the relevant already mentioned conduct of the description of the compound of formula I of the present invention, particularly preferred or R very particularly preferably 4Definition; R preferably represents alkyl, particularly methyl or the ethyl with 1-4 carbon atom separately.
The initiator of formula (VIII) and (IX) is the known synthetic compound that is used for.
Be used to prepare the method according to this invention (a) of the compound of formula I, (b), (c), (d) He (e) preferably in the presence of suitable diluent, carry out.Suitable diluent generally is conventional organic solvent.These preferably include aliphatics, and are alicyclic and aromatic, optional by halogenated hydrocarbon, for example pentane, hexane, heptane, sherwood oil, volatile oil, gasoline, benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, hexanaphthene, methylcyclohexane, methylene dichloride, trichloromethane (chloroform) or tetracol phenixin, dialkyl ether, ether for example, isopropyl ether, methyl tertiary butyl ether, tert amyl methyl ether(TAME) (MTBE), Ethyl Tertisry Butyl Ether, tertiary amyl ethyl ether, tetrahydrofuran (THF) (THF), 1, the 4-diox, ethylene glycol dimethyl ether or ethylene glycol bisthioglycolate ethyl ether, diethylene glycol dimethyl ether or diethylene glycol diethyl ether; The dialkyl group ketone, acetone for example, butanone (methyl ethyl ketone), methyl isopropyl Ketone or methyl iso-butyl ketone (MIBK); Nitrile, acetonitrile for example, propionitrile, butyronitrile or benzonitrile; Amides, N for example, dinethylformamide (DMF), N,N-dimethylacetamide, N-methyl formyl aniline, N-Methyl pyrrolidone or hexamethyl phosphoric triamide; The ester class, methyl acetate for example, ethyl acetate, acetate just-or different-propyl ester, acetate just-, the exclusive OR second month in a season-butyl ester; Sulfoxide class, for example methyl-sulphoxide; The alkane alcohols, methyl alcohol for example, ethanol, just-or different-propyl alcohol, just-, different-, secondary-or the trimethyl carbinol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, glycol ether monomethyl ether or glycol ether monoethyl ether; The perhaps mixture or the pure water of they and water.In the method according to this invention (b), advantageously can use acetate as thinner.
Be used to prepare the method according to this invention (a) of the compound of formula I, (b) He (e) preferably in the presence of suitable reaction promoter, carry out.Suitable reaction promoter generally is conventional inorganic or organic bases or acid acceptor.These preferably include the acetate of basic metal or alkaline-earth metal, amide, carbonate, supercarbonate, hydride, oxyhydroxide or alkoxide, sodium acetate for example, potassium acetate or lime acetate, lithamide, ammonification sodium, ammonification potassium or ammonification calcium, yellow soda ash, salt of wormwood or lime carbonate, sodium bicarbonate, saleratus or Calcium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride KH or hydrolith, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methylate, sodium ethylate, just-or different-sodium propylate, just-, different-, secondary-or sodium tert-butoxide or potassium methylate, potassium ethylate, just-or different-potassium propylate, just-, different-, secondary-or potassium tert.-butoxide; Also has alkaline organic nitrogen compound, Trimethylamine for example, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclo-hexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, accelerine, N, N-dimethyl benzyl amine, pyridine, the 2-methyl-, the 3-methyl-, the 4-methyl-, 2, the 4-dimethyl-, 2, the 6-dimethyl-, 3, the 4-dimethyl-and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidines, 1,4-diazabicyclo [2,2,2]-octane (DABCO), 1,5-diazabicyclo [4,3,0]-ninth of the ten Heavenly Stems-5-alkene (DBN) or 1,8-diazabicyclo [5,4,0]-11-7-alkene (DBU).
The method according to this invention (c) that is used to prepare the compound of formula I is carried out in the presence of dewatering agent.Suitable dewatering agent is conventional dewatering agent, sulfuric acid for example, methylsulfonic acid, Phenylsulfonic acid, tosic acid, diacetyl oxide and phosphorus oxide (V).
The method according to this invention (d) that is used to prepare the compound of formula I uses nitrating agent to carry out.Suitable nitrating agent is conventional nitrating agent, for example nitric acid and itself and nitrated auxiliary agent vitriolic mixture for example.
Carry out the inventive method (a), (b), (c), in the time of (d) and (e), temperature of reaction can change in quite wide scope.Generally speaking, this method-20 ℃ and+carry out under the temperature between 200 ℃, preferably between 0 ℃ and 150 ℃, particularly under the temperature between 10 ℃ and 120 ℃, carry out.
The method according to this invention is generally under atmospheric pressure carried out.But also can carry out under pressurization or the decompression the inventive method-generally at 0.1 crust between 10 crust.
Carrying out the inventive method (a), (b), (c), in the time of (d) and (e), generally using initiator with about equimolar amount.But, also can be with big relatively one of them composition of excessive use.Reaction is generally in suitable diluent, if suitably, carry out in the presence of reaction promoter, and general reaction mixture stirred for several hour under the temperature of needs.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 the straw agent, and particularly as killing 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 steriland herbicide or selective herbicide.For example relevant with following plant, 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 (Arachjs), mustard belongs to (Brassica), Lactuca (Lactuca), Cucumis (Cucumis), and buffalo gourd (Cucurbita).
Monocotyledon weed kind: Echinochloa (Echinochloa), setaria (Setaria), Panicum (Panicum), knotgrass (Digitaria), ladder is 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), 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 road of arboreal growth or the square all control weeds.These compounds are used to equally 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.
The compound of formula I of the present invention has strong weeding activity and broad spectrum of activity when being administered to soil and be administered to the over-ground part of plant.
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, and be wrapped in the trickle capsule in the polymkeric substance.
These type agent are produced in a known manner, for example, and by active compound be that is to say that with expanding agent liquid solvent and/or solid carrier mix, and optional use tensio-active agent, that is to say emulsifying agent and/or dispersion agent and/or pore forming material.
If employed expansion agent is a water, then also can use-case such as organic solvent make solubility promoter.Main suitable liquid solvent has: aromatics, and as dimethylbenzene, toluene or alkylnaphthalene, chlorinated aromatic compound or 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, as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, as dimethyl formamide and methyl-sulphoxide, and water.
Suitable solid carrier is: for example ammonium salt and ground natural mineral matter, as kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite and ground synthetic mineral matter, as high dispersive silicon-dioxide, rock soil 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 tackiness agent in the preparation, as the natural and synthetic polymer of carboxymethyl cellulose and powdery, particle or latex form, 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 dyestuff, as mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic dye, as alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff, and micro-nutrients, as the salt of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Generally speaking, preparation contains the active compound between 0.1 to 95% weight percent, preferred 0.5-90%.
For the control weeds, active compound of the present invention, with itself or its dosage form, the mixture that also can be used as with known weedicide uses, and can be whole preparation or the mixed thing of bucket.
The possible composition that is applicable to described mixture is known weedicide, for example:
Acetochlor, acifluorfen (sodium salt), aclonifen, alachlor, alloxydim (sodium salt), ametryn, amidochlor, amidosulfuron, anilofos, the spirit of sulphur grass, atrazine, azafenidin, azimsulfuron, herbicide (ethyl ester), benfuresate, the phonetic grass of benzyl swells (methyl esters), bentazone, benzofenap, benzoylpropethyl (ethyl ester), bilanafos, bifenox, bispyribac (sodium salt), bromobutide, bromofenoxim, bromoxynil, Butachlor technical 92, butroxydim, the fourth grass is special, cafenstrole, caloxydim, block careless amine, carfentrazone (ethyl ester), chlomethoxyfen, weed eradication is flat, pyrazon, chlorimuron (ethyl ester), chlornitrofen, chlorsufuron, the chlorine wheat is grand, cinidon (ethyl ester), cinmethylin, the ether grass is grand, clethodim, clodinafop (propargyl) ， clomazone, clomeprop, clopyralid, clopyrasulfuron (methyl esters), cloransulam (methyl), cumyluron, cyanazine, cybutryne, weed eradication spy, cyclosulfamuron, cycloxydim, cyhalofop (butyl), 2,4-drips, and 2, the 4-Embutox, 2,4-drips propionic acid, desmedipham, di_allate, dicamba 98, diclofop-methyl (methyl esters), diclosulam, acetyl alachlor (ethyl ester), two benzene azoles are fast, diflufenican, diflufenzopyr ， Ding Evil is grand, dimepiperate, dimethachlor, diformazan third second is clean, dimethenamid, dimexyflam, the spirit of amino second fluorine, diphenamide, diquat, dithiopyr, Diuron Tech, daimuron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid ， oxazole diclofop-methyl (P-ethyl ester), wheat straw volt (isopropyl ester), and the wheat straw volt (isopropyl ester-L), wheat straw volt (methyl esters), the pyridine ethyl methyl, fluazifop (P-butyl ester), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac (pentyl ester), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofenethyl (ethyl ester), amine grass azoles, flupropacil, flurpyrsulfuron (methyl esters,-sodium salt), fluorenes butyric acid (butyl ester), fluorine is decided ketone, fluroxypyr (meptyl), flurprimidol, flurtamone, fluthiacet (methyl esters), fluthiamide, Fomesafen, careless ammonium phosphine (ammonium salt), glyphosate (sec.-propyl ammonium salt), halosafen, pyrrole fluorine chlorine standing grain spirit (ethoxy ethyl ester), pyrrole fluorine chlorine standing grain spirit (P-methyl esters), hexazinone, miaow grass ester (methyl esters), imazamethapyr, imazamox, imazapic, the weed eradication cigarette, the weed eradication quinoline, Imazethapyr, imazosulfuron, iodosulfuron, ioxynil, isopropalin, isoproturon Yi Evil is grand, isoxaben, isoxachlortole, isoxaflutole Evil grass ether, lactofen, lenacil, methoxydiuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, pyrrole grass peace, methabenzthiazuron, metobenzuron, metobromuron, (α-) Bing Caoan, metosulam, metoxuron, the piperazine humulone, metsulfuron-methyl (methyl esters), Hydram, monolinuron, naproanilide, napropamide, neburon, nicoculsfuron, norflurazon, orbencarb, oryzalin, oxadiargyl Evil humulone, oxasulfuron, oxaziclomefone, oxyfluorfen, Paraquat, perlagon acid, pendimethalin, pentoxazone, phenmedipham, piperophos, Bing Caoan, Fluoropyrimidinesulfuron (methyl esters), prometryn, propachlor, Stam F-34, propaquizafop, propisochlor, pentyne grass amine, prosulfocarb, prosulfuron, pyraflufen (ethyl ester), pyrazolate, pyrazosulfuron (ethyl ester), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac (methyl esters), pyrithiobac (sodium salt), quinclorac, quinmerac, quinoclamine, quizalofop (P-ethyl ester), quizalofop (p-tetrahydro furfuryl ester), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulphentrazone, ethyl methyl (methyl esters), glyphosate, sulphosulfuron, tebutam, terbufos benzthiazuron, tepraloxydim, 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 can be the mixture with other known activity compound, described other active compound be a mycocide for example, insecticide, miticide, nematocides, bird repellent, the reagent of the plant nutrient agent and the structure of improving the soil.
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 be used in a usual manner, for example by pouring, and spraying, atomizing or sow.
Active compound of the present invention can be used after plant emerges preceding or emerges.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 using is that per hectare soil area uses the 1g-10kg active compound, and preferred per hectare soil area uses the 5g-5kg active compound.
The following examples can illustrate the preparation and the application of active compound of the present invention.Preparation EXAMPLE Example 1
Figure A9980714300451
3 of 5.0 grams (18 mmole) in 150 milliliters of toluene, 3,3-three fluoro-2-oxo-propionic aldehyde-1-(2,5-two fluoro-4-cyano group-phenyl-hydrazones) mix with (the inferior phosphoranyl of triphenyl) methyl acetate of 8.7 grams (26 mmole), and this mixture stirred 3 hours under reflux temperature.Use rotatory evaporator to concentrate this mixture, resistates Virahol recrystallization.
Obtain 2-(2,5-two fluoro-4-cyano group-phenyl)-5-trifluoromethyl-pyridazin-3-one of 1.3 grams (theoretical amount 24%), 143 ℃ of fusing points.
Embodiment 2
Figure A9980714300461
3 of 5.0 grams (18 mmole) in 150 milliliters of toluene, 3,3-three fluoro-2-oxopropanal-1-(2,5-two fluoro-4-cyano group-phenyl-hydrazones) mix with (1-oxyethyl group-carbonyl ethylidene) triphenyl phosphorane of 9.4 grams (26 mmole), and this mixture stirred 3 hours under reflux temperature.Use rotatory evaporator to concentrate this mixture, resistates Virahol recrystallization.
Obtain 2-(2,5-two fluoro-4-cyano group-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 2.41 grams (theoretical amount 42.5%), 135 ℃ of fusing points.
Be similar to embodiment 1 and 2, and the general description of method produced according to the present invention, also can prepare the compound of the formula I of listing in the following table 1.
Figure A9980714300462
Table 1: the embodiment of the compound of formula I
The embodiment sequence number ????R 1 ????R 2 ????R 3 ?R 4 ?R 5 ????R 6
????3 ????F ????CN ????NO 2 ?H ?CF 3 ????H
????4 ????Cl ????CN ????NO 2 ?H ?CF 3 ????H
????5 ????F ????CN ????NO 2 ?H ?CF 3 ????CH 3
????6 ????Cl ????CN ????NO 2 ?H ?CF 3 ????CH 3
????7 ????F ????CN ????NO 2 ?CH 3 ?CF 3 ????H
????8 ????Cl ????CN ????NO 2 ?CH 3 ?CF 3 ????H
????9 ????Cl ????CN ????OH ?H ?CF 3 ????H
???10 ????F ????CN ????OH ?CH 3 ?CF 3 ????H
???11 ????F ????CN ????OCH 3 ?CH 3 ?CF 3 ????H
???12 ????F ????CN ????OC 2H 5 ?CH 3 ?CF 3 ????H
???13 ????F ????CN ????OCH(CH 3) 2 ?CH 3 ?CF 3 ????H
The embodiment sequence number ?R 1 ?R 2 ????????R 3 ?R 4 ?R 5 ????R 6
?14 ?F ?CN ????OCH 2CH=CH 2 ?CH 3 ?CF 3 ????H
?15 ?F ?CN ????OCH 2C≡CH ?CH 3 ?CF 3 ????H
?16 ?F ?CN ????OCH(CH 3)C≡CH ?CH 3 ?CF 3 ????H
?17 ?F ?CN ????OCH 2COOCH 3 ?CH 3 ?CF 3 ????H
?18 ?F ?CN ????OCH 2COOC 2H 5 ?CH 3 ?CF 3 ????H
?19 ?F ?CN ??OCH 2COOCH(CH 3) 2 ?CH 3 ?CF 3 ????H
?20 ?F ?CN ????OCH 2COOC 5H 11 ?CH 3 ?CF 3 ????H
?21 ?F ?CN ??OCH(CH 3)COOC 2H 5 ?CH 3 ?CF 3 ????H
?22 ?F ?CN ????OH ?H ?CF 3 ????H
?23 ?F ?CN ????OCH 3 ?H ?CF 3 ????H
?24 ?F ?CN ????OC 2H 5 ?H ?CF 3 ????H
?25 ?F ?CN ????OCH(CH 3) 2 ?H ?CF 3 ????H
?26 ?F ?CN ????OCH 2CH=CH 2 ?H ?CF 3 ????H
?27 ?F ?CN ????OCH 2C≡CH ?H ?CF 3 ????H
?28 ?F ?CN ????OCH(CH 3)C≡CH ?H ?CF 3 ????H
?29 ?F ?CN ????OCH 2COOCH 3 ?H ?CF 3 ????H
?30 ?F ?CN ????OCH 2COOC 2H 5 ?H ?CF 3 ????H
?31 ?F ?CN ????OCH 2COOCH(CH 3) 2 ?H ?CF 3 ????H
?32 ?F ?CN ????OCH 2COOC 5H 11 ?H ?CF 3 ????H
?33 ?F ?CN ????OCH(CH 3)COOC 2H 5 ?H ?CF 3 ????H
?34 ?F ?CN ????COOC 2H 5 ?CH 3 ?CF 3 ????H
?35 ?F ?CN ????COOC 2H 5 ?H ?CF 3 ????H
?36 ?F ?CN ????CONHCH 3 ?CH 3 ?CF 3 ????H
?37 ?F ?CN ????CON(CH 3) 2 ?CH 3 ?CF 3 ????H
?38 ?F ?CN ????NH 2 ?CH 3 ?CF 3 ????H
?39 ?F ?CN ????NH 2 ?H ?CF 3 ????H
?40 ?F ?CN ????NHSO 2CH 3 ?CH 3 ?CF 3 ????H
The embodiment sequence number ?R 1 ?R 2 ????R 3 ?R 4 ?R 5 ????R 6
??41 ?F ?CN ????NHSO 2C 2H 5 ?CH 3 ?CF 3 ????H
??42 ?F ?CN ????NHSO 2CH 2Cl ?CH 3 ?CF 3 ????H
??43 ?F ?CN ????NHSO 2CF 3 ?CH 3 ?CF 3 ????H
??44 ?F ?CN ????NHSO 2Cyclopropyl ?CH 3 ?CF 3 ????H
??45 ?F ?CN ????NHSO 2CH 3 ?H ?CF 3 ????H
??46 ?F ?CN ????NHSO 2C 2H 5 ?H ?CF 3 ????H
??47 ?F ?CN ????NHSO 2CH 2Cl ?H ?CF 3 ????H
??48 ?F ?CN ????NHSO 2CF 3 ?H ?CF 3 ????H
??49 ?F ?CN ????NHsO 2Cyclopropyl ?H ?CF 3 ????H
??50 ?Cl ?CN ????NH 2 ?H ?CF 3 ????H
??51 ?Cl ?CN ????OCH 2C≡CH ?H ?CF 3 ????H
??52 ?C1 ?CN ????OCH(CH 3)C≡CH ?H ?CF 3 ????H
??53 ?Cl ?CN ????OCH 2COOCH 3 ?H ?CF 3 ????H
??54 ?Cl ?CN ????OCH 2COOC 2H 5 ?H ?CF 3 ????H
??55 ?Cl ?CN ????OCH 2COOCH(CH 3) 2 ?H ?CF 3 ????H
??56 ?Cl ?CN ????OCH 2COOC 5H 11 ?H ?CF 3 ????H
??57 ?Cl ?CN ????NHSO 2CH 3 ?CH 3 ?CF 3 ????H
??58 ?Cl ?CN ????NHSO 2C 2H 5 ?CH 3 ?CF 3 ????H
??59 ?Cl ?CN ????OCH 2C≡CH ?CH 3 ?CF 3 ????H
??60 ?C1 ?CN ????OCH(CH 3)C≡CH ?CH 3 ?CF 3 ????H
??61 ?Cl ?CN ????OCH 2COOCH 3 ?CH 3 ?CF 3 ????H
??62 ?Cl ?CN ????OCH 2COOC 2H 5 ?CH 3 ?CF 3 ????H
??63 ?C1 ?CN ?OCH 2COOCH(CH 3) 2 ?CH 3 ?CF 3 ????H
??64 ?Cl ?CN ????OCH 2COOC 5H 11 ?CH 3 ?CF 3 ????H
??65 ?F ?CSNH 2 ????NHSO 2CH 3 ?CH 3 ?CF 3 ????H
??66 ?F ?CSNH 2 ????NHSO 2C 2H 5 ?CH 3 ?CF 3 ????H
??67 ?F ?CSNH 2 ????NHSO 2CH 3 ?H ?CF 3 ????H
The embodiment sequence number ?R 1 ???R 2 ???????R 3 ?R 4 ?R 5 ????R 6
??68 ?F ?CSNH 2 ????NHSO 2C 2H 5 ?H ?CF 3 ????H
??69 ?Cl ?CSNH 2 ????OCH(CH 3)C≡CH ?CH 3 ?CF 3 ????H
??70 ?Cl ?CSNH 2 ????OCH 2COOC 5H 11 ?CH 3 ?CF 3 ????H
??71 ?F ?CSNH 2 ????OCH 2CH=CH2 ?H ?CF 3 ????H
??72 ?F ?CSNH 2 ????OCH 2C≡CH ?H ?CF 3 ????H
??73 ?F ?CSNH 2 ????OCH(CH 3)C≡CH ?H ?CF 3 ????H
??74 ?Cl ?CSNH 2 ????NHSO 2CH 3 ?H ?CF 3 ????H
??75 ?Cl ?CSNH 2 ????NHSO 2C 2H 5 ?H ?CF 3 ????H
??76 ?F ?CSNH 2 ????OCH 2CH=CH 2 ?CH 3 ?CF 3 ????H
??77 ?F ?CSNH 2 ????OCH 2C≡CH ?CH 3 ?CF 3 ????H
??78 ?F ?CSNH 2 ????OCH(CH 3)C≡CH ?CH 3 ?CF 3 ????H
??79 ?Cl ?CSNH 2 ????NHSO 2CH 3 ?CH 3 ?CF 3 ????H
??80 ?Cl ?CSNH 2 ????NHSO 2C 2H 5 ?CH 3 ?CF 3 ????H
??81 ?F ?CN ????N(SO 2CH 3) 2 ?CH 3 ?CF 3 ????H
??82 ?F ?CN ????N(SO 2C 2H 5) 2 ?CH 3 ?CF 3 ????H
??83 ?F ?CN ????N(CH 3)SO 2CH 3 ?CH 3 ?CF 3 ????H
??84 ?F ?CN ????N(CH 3)SO 2C 2H 5 ?CH 3 ?CF 3 ????H
??85 ?F ?CSNH 2 ????N(SO 2CH 3) 2 ?CH 3 ?CF 3 ????H
??86 ?F ?CSNH 2 ????N(SO 2C 2H 5) 2 ?CH 3 ?CF 3 ????H
??87 ?F ?CN ????SCH 2COOCH 3 ?CH 3 ?CF 3 ????H
??88 ?F ?CN ????SCH 2COOC 2H 5 ?CH 3 ?CF 3 ????H
??89 ?F ?CF 3 ????NHSO 2CH 3 ?CH 3 ?CF 3 ????H
??90 ?F ?CF 3 ????NHSO 2C 2H 5 ?CH 3 ?CF 3 ????H
??91 ?F ?CF 3 ????OCH 2CH=CH 2 ?CH 3 ?CF 3 ????H
??92 ?F ?CF 3 ????OCH 2C≡CH ?CH 3 ?CF 3 ????H
??93 ?F ?CF 3 ????OCH 2COOC 5H 11 ?CH 3 ?CF 3 ????H
??94 ?F ?CSNH 2 ????N(CH 3)SO 2CH 3 ?CH 3 ?CF 3 ????H
The embodiment sequence number ?R 1 ??R 2 ????????R 3 ??R 4 ?R 5 ????R 6
??95 ?F ?CSNH 2 ????N(CH 3)SO 2C 2H 5 ?CH 3 ?CF 3 ????H
??96 ?F ?CSNH 2 ????N(SO 2CH 3) 2 ?CH 3 ?CF 3 ????H
??97 ?F ?CSNH 2 ????N(SO 2C 2H 5) 2 ?CH 3 ?CF 3 ????H
??98 ?F ?CN ????OCH 2CH=CH 2 ?H ?CF 3 ????CH 3
??99 ?F ?CN ????OCH 2C≡CH ?H ?CF 3 ????CH 3
?100 ?F ?CN ????OCH(CH 3)C≡CH ?H ?CF 3 ????CH 3
?101 ?F ?CN ????OCH 2COOCH 3 ?H ?CF 3 ????CH 3
?102 ?F ?CN ????OCH 2COOC 2H 5 ?H ?CF 3 ????CH 3
?103 ?F ?CN ?OCH 2COOCH(CH 3) 2 ?H ?CF 3 ????CH 3
?104 ?F ?CN ????OCH 2COOC 5H 11 ?H ?CF 3 ????CH 3
?105 ?F ?CN ?OCH(CH 3)COOC 2H 5 ?H ?CF 3 ????CH 3
?106 ?F ?CN ????NHSO 2CH 3 ?H ?CF 3 ????CH 3
?107 ?F ?CN ????NHSO 2C 2H 5 ?H ?CF 3 ????CH 3
?108 ?F ?CN ????NHSO 2CH 2Cl ?H ?CF 3 ????CH 3
?109 ?F ?CN ????NHSO 2CF 3 ?H ?CF 3 ????CH 3
?110 ?F ?CSNH 2 ????NHSO 2CH 3 ?H ?CF 3 ????CH 3
?111 ?F ?CSNH 2 ????NHSO 2C 2H 5 ?H ?CF 3 ????CH 3
?112 ?F ?CN ????H ?H ?CF 3 ????H
?113 ?F ?CSNH 2 ????H ?H ?CF 3 ????H
?114 ?F ?CN ????H ?CH 3 ?CF 3 ????H
?115 ?F ?CSNH 2 ????H ?CH 3 ?CF 3 ????H
?116 ?H ?CN ????F ?H ?CF 3 ????H
?117 ?H ?CSNH 2 ????F ?H ?CF 3 ????H
?118 ?H ?CN ????F ?CH 3 ?CF 3 ????H
?119 ?H ?CSNH 2 ????F ?CH 3 ?CF 3 ????H
?120 ?F ?CSNH 2 ????F ?CH 3 ?CF 3 ????H
Figure A9980714300521
Figure A9980714300551
Figure A9980714300581
Figure A9980714300601
Figure A9980714300631
Above the compound listed as embodiment 10 in the table 1 can for example be prepared as follows:
2-(4-cyano group-2-fluoro-5-methoxyl group-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-ones of 2.0 grams (6.1 mmole) in 100 milliliters of methylene dichloride mix with the boron tribromides (1 mole of dichloromethane solution) of 18.4 grams (18.3 mmole), this mixture 25 ℃ stir 16 hours down after slow adding 150 ml waters and with dried over sodium sulfate organic phase and concentrated with rotatory evaporator.
Obtain 2-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 1.8 grams (theoretical amount 94%), 189 ℃ of fusing points.
Above the compound listed as embodiment 11 in the table 1 can for example be prepared as follows:
3 of 3.9 grams (13.5 mmole) in 150 milliliters of toluene, 3,3-three fluoro-2-oxopropanal-1-(4-cyano group-2-fluoro-5-methoxyl group-phenyl hydrazones) mix with (1-ethoxy carbonyl-ethylidene)-triphenyl phosphorane of 7.0 grams (19.3 mmole), and this mixture stirred 2 hours under reflux temperature under argon gas.After using rotatory evaporator to concentrate, resistates Virahol recrystallization.
Obtain 2-(4-cyano group-2-fluoro-5-methoxyl group-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 2.2 grams (theoretical amount 50%), 178 ℃ of fusing points.
Above the compound listed as embodiment 13 in the table 1 can for example be prepared as follows:
Figure A9980714300661
3.8 2-(4-bromo-2-fluoro-5-isopropoxy-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of gram (8 mmole) is dissolved in 10 milliliters of N-methyl-pyrrolidone, mix and (0.1 millibar) heating under 90 ℃ under reduced pressure with the cupric cyanide (I) of 0.9 gram (9.6 mmole), 2 milliliters of solvents are removed in distillation.Then under atmospheric pressure (under the argon gas) stirred 6 hours with this mixture heating up to 170 ℃ and under this temperature.After being cooled to 20 ℃, mixture adds 100 milliliters of ethyl acetate and stirs, and mixes with the ammoniacal liquor of 10% concentration and filters.The filtrate water washing, dried over sodium sulfate also carefully concentrates under pump vacuum.
Obtain 2-(4-cyano group-2-fluoro-5-isopropoxy-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 3.0 grams (theoretical amount 89%), be crude product (content: be determined as 85%) according to HPLC.
In order to be further purified, use methylene dichloride to restrain these crude products through silica gel chromatography with 2, obtain pure product (0.7 gram, content: be determined as 97%), 121 ℃ of fusing points according to HPLC.
Above the compound listed as embodiment 15 in the table 1 can for example be prepared as follows:
Under 25 ℃, 30 milliliters of N, 2-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-4-methyl-5-trifluoromethyl of the gram of 0.6 in the dinethylformamide (1.9 mmole)-pyridazin-3-one stirs down and mixed 60 minutes with the salt of wormwood of 0.4 gram (3 mmole) and the propargyl bromide (80% is pure) of 0.31 gram (2.1 mmole), this mixture mixes with water then and is adjusted to pH6 with concentrated hydrochloric acid, suction strainer goes out sedimentary product, washes with water and drying.Use the Virahol recrystallized product during purifying.
Obtain 2-(4-cyano group-2-fluoro-5-propargyloxy-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 0.3 gram (theoretical amount 44%), 145 ℃ of fusing points.
Above the compound listed as embodiment 18 in the table 1 can for example be prepared as follows:
Figure A9980714300671
Under 25 ℃, 30 milliliters of N, 2-(4-cyano group-2-fluoro-5-hydroxyl-phenyl)-4-methyl-5-trifluoromethyl of the gram of 0.7 in the dinethylformamide (2.24 mmole)-pyridazin-3-one stirs down and mixed 60 minutes with the salt of wormwood of 0.48 gram (3.5 mmole) and the ethyl bromoacetate of 0.42 gram (2.5 mmole), this mixture mixes with water then and is adjusted to pH6 with concentrated hydrochloric acid, suction strainer goes out sedimentary product, washes with water and drying.
Obtain 2-(4-cyano group-2-fluoro-5-(ethoxycarbonyl methoxyl group)-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 0.64 gram (theoretical amount 71%), 95 ℃ of fusing points.
Above the compound listed as embodiment 41 in the table 1 can for example be prepared as follows:
3 of 5.5 grams (15 mmole) in 100 milliliters of toluene; 3; 3-three fluoro-2-oxo-propionic aldehyde-1-(4-cyano group-5-ethylsulfonyl-amino-2-fluoro-phenyl-hydrazone) mix with (1-ethoxycarbonyl-ethylidene)-triphenyl phosphorane of 8.2 grams (22.5 mmole), and this mixture stirred 2 hours under reflux temperature under argon gas.After using rotatory evaporator to concentrate, use toluene/ethyl acetate 3: 1 with resistates through silica gel chromatography.
Obtain 2-(4-cyano group-5-ethylsulfonylamino-2-fluoro-the phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 3.6 grams (theoretical amount 59.5%), 198 ℃ of fusing points.
Above the compound listed as embodiment 66 in the table 1 can for example be prepared as follows:
2-(4-cyano group-5-ethylsulfonylamino-2-fluoro-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one and the 12 milliliters of triethylamines that at first in 30 milliliters of pyridines, add 1.6 grams (4 mmole), and, under liquid level, fed hydrogen sulfide 90 minutes at 60-70 ℃.After reacting completely, by mixture 60 minutes, be cooled to 25 ℃ and stir with frozen water with nitrogen, suction strainer goes out sedimentary product, and resistates washes with water and be dry.
Obtain 2-(2-fluoro-5-ethylsulfonylamino-4-thiocarbamoyl-phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one of 0.9 gram (theoretical amount 51%), 88 ℃ of fusing points.
Above the compound listed as embodiment 122 in the table 1 can for example be prepared as follows:
Figure A9980714300682
The 3-chloro-propionyl chloride of the triethylamine of 2-(4-cyano group-5-ethylsulfonylamino-2-fluoro-the phenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-ones of 1.2 grams (3 mmole) and 0.6 gram (6 mmole) and 0.77 gram (6 mmole) mixes in 50 milliliters of acetonitriles, and this mixture stirred 12 hours down at 25 ℃.After using rotatory evaporator to concentrate, resistates and water stir and use the concentrated hydrochloric acid acidifying, and suction strainer goes out sedimentary product, wash with water and drying.
Obtain 1.1 the gram (2-[5-(N-vinyl carbonyl-N-ethylsulfonyl amino)-4-cyano group-2-fluoro-phenyl]-4-methyl-5-trifluoromethyl-pyridazin-3-one, 96 ℃ of fusing points.
Above the compound listed as embodiment 129 in the table 1 can for example be prepared as follows:
Figure A9980714300691
1-[(4-cyano group-5-methyl sulphonyl amino-2-fluoro-the phenyl of 1.22 grams (3.2 mmole) in 50 milliliters of toluene)-hydrazone]-3-ethoxycarbonyl-1-chloro-1; 1-two fluoro-third-2-ketone mixes with (1-ethoxycarbonyl-ethylidene)-triphenyl phosphorane of 1.74 grams (4.8 mmole), and this mixture stirred 2 hours under reflux temperature under argon gas.After using rotatory evaporator to concentrate, use toluene/ethyl acetate 3: 1 with resistates through silica gel chromatography.
Obtain the 2-(4-cyano group-5-ethylsulfonylamino-2-fluoro-phenyl)-4 of 0.2 gram (theoretical amount 15%), 6-dimethyl-5-trifluoromethyl-pyridazin-3-one, 191 ℃ of fusing points.
Above the compound listed as embodiment 107 in the table 1 can for example be prepared as follows:
Figure A9980714300692
1-[(4-cyano group-5-methyl sulphonyl amino-2-fluoro-the phenyl of 1.22 grams (3.2 mmole) in 50 milliliters of toluene)-hydrazone]-3-ethoxycarbonyl-1-chloro-1; 1-two fluoro-third-2-ketone mixes with (1-ethoxycarbonyl-methylene radical)-triphenyl phosphorane of 1.7 grams (4.8 mmole), and this mixture stirred 2 hours under reflux temperature under argon gas.After using rotatory evaporator to concentrate, use toluene/ethyl acetate 3: 1 with resistates through silica gel chromatography.
Obtain 2-(4-cyano group-5-ethylsulfonylamino-2-fluoro-the phenyl)-6-methyl-5-trifluoromethyl-pyridazin-3-one of 0.2 gram (theoretical amount 15.5%), 143 ℃ of fusing points.
Listed the physical data of the compound of listing in the table 1 among the following table 1a
Table 1a:
The embodiment sequence number Physical data
????10 ????m.p.:189℃ ????1og.P=2.27 a)
????11 ????m.p.:178℃ ????log.P=2.76 a)
????12 ????log.P=3.12 a)
????13 ????m.p.:121℃ ????log.P=3.40 a)
????14 ????log.P=3.24 a)NMR(CDCl 3):2.44-2.45；4.65-4.68；7.46-7.49；8.03ppm
????15 ????m.p.:145℃ ????log.P=2.92 a)
????18 ????m.p.:95℃ ????log.P=3.04 a)
????21 ????m.p.:118℃
????23 ????m.p.:174℃ ????log.P=2.41 a)
????24 ????m.p.:140℃ ????log.P=2.76 a)
????40 ????m.p.:202℃ ????log.P=2.91 a)
????41 ????m.p.:198℃ ????log.P=2.42 a)
????46 ????m.p.:174℃
????66 ????m.p.:88℃ ????log.P=2.44 a)
????84 ????m.p.:98℃ ????log.P=2.68 a)
The embodiment sequence number Physical data
????107 ????m.p.:143℃ ????log.P=2.31 a)
????112 ????m.p.:160℃
????120 ????m.p.:183℃ ????log.P=2.43 a)
????121 ????m.p.:149℃ ????log.P=2.70 a)
????122 ????m.p.:95℃ ????log.P=2.89 a)
????123 ????m.p.:220℃
????124 ????m.p.:135℃ ????log.P=3.39 a)
????125 ????log.P=3.03 a)
????126 ????m.p.:165℃ ????log.P=3.29 a)
????127 ????m.p.:116℃ ????log.P=2.97 a)
????128 ????m.p.:131℃
????129 ????m.p.:189℃ ????log.P=2.65 a)
????130 ????m.p.:142℃ ????log.P=1.94 a)
????131 ????log.P=3.62 a)????NMR(CDCl 3):1.17-1.19；1.25-1.27；1.70-1.72；2.43； ????4.72-4.78；6.94-6.96；7.99ppm
????132 ????log.P=3.93 a)????NMR(CDCl 3):1.13-1.26；2.04-2.13；2.43；4.56-4.60； ????7.46-7.49ppm
The embodiment sequence number Physical data
????133 ????m.p.:134℃
????134 ????m.p.:60℃
????135 ?NMR(CDCl 3):2.43-2.44；3.77；4.61-4.63；8.01ppm
????136 ?NMR(CDCl 3):2.07-2.12；2.43-2.44；4.19-4.24；7.46- ??????????????????7.49；8.00ppm
????137 ?NMR(CDCl 3):1.72-1.74；2.36；4.77-4.82；7.47-7.50； ?????????????????????8.01ppm
????138 ????NMR(CDCl 3):2.44-2.46；4.93；7.55-7.58；8.05ppm
????158 ???????????????????log.P=3.51 ????NMR(CDCl 3):2.44-2.54；5.03；7.26；8.03ppm
????161 ???????????????????m.p.:83℃ ???????????????????log.P=3.65
????256 ???????????????????m.p.:97℃
????257 ???????????????????m.p.:221℃ ???????????????????log.P=4.17
????258 ???????????????????log.P=4.64 ????NMR(CDCl 3):1.54-1.55；1.99-2.09； ????2.42-2.44；4.25-4.26；6.91-6.93ppm
????259 ????????????????????m.p.:161℃ ????????????????????log.P=3.10
????260 ????????????????????log.P=2.93 ????NMR(CDCl 3):1.49-1.54；2.01；2.44-2.46； ????4.51-4.52；7.60-7.63；8.05ppm
????261 ????????????????????m.p.: ????????????????????log.P=2.91
Use reversed-phase column (C18) to measure the 1ogP value that provides in the top table 1 according to EECDirective79/831AnnexV.A8 by HPLC (high performance liquid chromatography).Temperature: 43 ℃.
(a) moving phase of mensuration usefulness in acid range: 0.1% phosphate aqueous solution, acetonitrile; Linear gradient corresponding results in 10% acetonitrile to 90% acetonitrile-table 1 is labeled as A)
(b) moving phase of mensuration usefulness in neutral range: the 0.01 mole of phosphoric acid salt buffer aqueous solution, acetonitrile; Linear gradient corresponding results in 10% acetonitrile to 90% acetonitrile-table 1 is labeled as b).
Use has the alkane that the does not have side chain-2-ketone (having 3-16 carbon atom) of known logP value (using the linear interpolation between two alkane ketones in succession to measure the logP value by the residence time) and proofreaies and correct.
Use the UV spectrum of 200nm-400nm in the chromatographic signal of maximum, to measure the λ maximum value.The initiator embodiment of formula IV (IV-1)
4-cyano group-2-fluoro-5-ethylsulfonyl amino-the aniline (known from DE-A-4414568) of 15 gram (50 mmole) 81% purity that will be in 100 milliliters of acetate and 20 milliliters of vitriol oils are cooled to 5 ℃ and more once mixes with the nitrosyl-sulfuric acids of 12.7 grams (100 mmole), and this mixture stirred down under 5 ℃ to 10 ℃ stirring 6 hours; Then at 15 milliliters of concentrated hydrochloric acids of 10 ℃ of solution that drip down 33.6 gram (140 mmole) tin chloride (II) dihydrates-be dissolved in.This mixture stirs with frozen water after down stirring 12 hours and with the strong aqua alkalize that alkalizes at 25 ℃.Suction strainer goes out sedimentary salt, uses concentrated hydrochloric acid to make filtrate be the acid ethyl acetate extraction of also using a little, and extraction liquid is with dried over sodium sulfate and use rotatory evaporator to concentrate.Resistates Virahol recrystallization.
Obtain the 4-cyano group-5-ethylsulfonyl amino-2-fluorophenyl hydrazine of 12.9 grams (theoretical amount 33%).Embodiment (IV-1)
Figure A9980714300741
Step 1
Figure A9980714300742
9.2 gram (0.4 mole) sodium Metal 99.5 is dissolved in 200 ml methanol, 2 of this solution and 30.8 grams (0.2 mole), and 5-two fluoro-4-cyano group-aniline mixes.Stir and still head is installed on the instrument and is heated to 90-95 ℃, distill out about 4/5 methyl alcohol.95 ℃ down stir extra 30 minutes after, remove heating, the inclusion of flask is mixed with water, is cooled to 25 ℃ and use concentrated hydrochloric acid to be adjusted to pH5, suction strainer goes out sedimentary product, washes also drying with water.
Obtain the 4-cyano group-2-fluoro-5-methoxyl group-aniline of 31.2 grams (theoretical amount 94%), 99 ℃ of fusing points, purity (method) (HPLC, logP1.34).
Step 2-changing method a
4.7 the 4-cyano group-2-fluoro-5-methoxyl group-aniline of gram (2.8 mmole) mixes with 100 milliliters of concentrated hydrochloric acids and 30 ml waters, this mixture quickly heats up to 40 ℃ of postcooling to 0 ℃.Drip 2.6 gram sodium nitrite solutions-be dissolved in, 30 ml waters then, this mixture stirred 60 minutes down at 5 ℃ to 10 ℃.The filtrate of filtering mixt and 0 ℃ is added drop-wise in the solution of the gram of 18 in 100 milliliters of concentrated hydrochloric acids (8 mmole) tin chloride (II) dihydrate.(20 ℃) stirring at room temperature of this suspension is 60 minutes then, extracts repeatedly with 45% aqueous sodium hydroxide solution alkalization alkalize and with ethyl acetate.Organic phase is with dried over sodium sulfate and use rotatory evaporator to concentrate under pump vacuum.
Obtain the 4-cyano group-2-fluoro-5-methoxyl group-phenyl hydrazine of 3 grams (theoretical amount 60%), 160 ℃ of fusing points.Step 2-changing method b
20 gram (0.5 mole) sodium Metal 99.5s are dissolved in 400 ml methanol, 2 of this solution and 68 grams (0.4 mole), and 5-two fluoro-4-cyano group-phenyl hydrazine is mixed.Stir and still head is installed on the instrument and, is distilled out about 80% methyl alcohol 80 ℃ to 85 ℃ heating down.Stirring is after extra 3 hours down at 85 ℃, and removal is heated, and the inclusion of flask is mixed with water, is cooled to 25 ℃ and the neutralization of use concentrated hydrochloric acid, and suction strainer goes out sedimentary product, washes also drying with water.Use ethyl alcohol recrystallization during purifying.
Obtain the 4-cyano group-2-fluoro-5-methoxyl group-phenyl hydrazine of 39 grams (theoretical amount 54%), 163 ℃ of fusing points.The initiator embodiment of formula (VII) (VII-1)
Figure A9980714300752
The sodium acetate that at first in 200 ml waters, adds 30 grams (370 mmole).Under ice-cooled, drip 1 of 25 grams (93 mmole), 1-two bromo-3,3,3-trifluoroacetone, this mixture at room temperature (about 20 ℃) stirred 30 minutes.With 2 of reaction mixture and 12 grams (72 mmole), 5-two fluoro-4-cyano group-phenyl hydrazine is mixed and was stirred 2 hours down at 40 ℃ to 50 ℃ then.Suction strainer goes out the sedimentary product of refrigerative, washes with water and drying.
Obtain 3,3 of 19 grams (theoretical amount 95.4%), 3-three fluoro-2-oxopropanal-1-(2,5-two fluoro-4-cyano group-phenyl hydrazones), 181 ℃ of fusing points.
Embodiment (VII-2)
In 100 ml waters sodium acetates of 7 grams (87 mmole) and 5.94 restrain (22 mmole) 1,1-two bromo-3,3, the 3-trifluoroacetone mixes, this mixture at room temperature (about 20 ℃) stirred 30 minutes, mix with the 4-cyano group-2-fluoro-5-methoxyl group-phenyl hydrazine of 3.0 grams (17 mmole), and stirred 60 minutes and stirred 10 minutes down at 95 ℃ at 40 ℃ to 50 ℃.Suction strainer goes out sedimentary product after being cooled to 20 ℃, washes with water and drying.
Obtain 3,3 of 4.1 grams (theoretical amount 83%), 3-three fluoro-2-oxo-propionic aldehyde-1-(4-cyano group-2-fluoro-5-methoxyl group-phenyl hydrazones), 168 ℃ of fusing points.
Embodiment (VII-3)
The sodium acetate of 4.1 grams (50 mmole) restrains 1 with 3.6 down at 80 ℃ in 50 ml waters; 1-two bromo-3; 3; 3-three fluoro-acetone stirred 30 minutes; this mixture mixes with the 4-cyano group-5-ethylsulfonyl amino-2-fluoro-phenyl hydrazine of 2.58 grams (10 mmole) down at 25 ℃; descended stirring 90 minutes and be cooled to 10 ℃ at 40 ℃ to 50 ℃, suction strainer goes out sedimentary product, washes with water and drying.
Obtain 3,3 of 3.03 grams (theoretical amount 83%), 3-three fluoro-2-oxo-propionic aldehyde-1-(4-cyano group-5-ethylsulfonyl amino-2-fluoro-phenyl hydrazones), 127 ℃ of fusing points.
Embodiment (VII-4)
Figure A9980714300771
The sodium acetate of 4.1 grams (50 mmole) restrains 3 with 3.6 down at 80 ℃ in 50 ml waters; 3-two bromo-1; 1; 1-three fluoro-2-butanone stirred 30 minutes; this mixture mixes with the 4-cyano group-5-ethylsulfonyl amino-2-fluoro-phenyl hydrazine of 2.58 grams (10 mmole) down at 25 ℃; descended stirring 2 hours and be cooled to 10 ℃ at 40 ℃ to 50 ℃, suction strainer goes out sedimentary product, washes with water and drying.
Obtain 1,1 of 3.2 grams (theoretical amount 84.2%), 1-three fluoro-2-oxo-butyraldehyde-3-(4-cyano group-5-ethylsulfonyl amino-2-fluoro-phenyl hydrazones), 211 ℃ of fusing points.The parent embodiment (X IV-1) of formula (X IV)
Figure A9980714300772
At first in 100 milliliters of acetate, add 6.87 gram (30 mmole) 4-cyano group-5-methyl sulphonyl amino-2-fluoro-aniline; ice-cooled 20 ℃ of 1 nitrosyl-sulfuric acids (92% concentration) that add 4.7 grams (34 mmole) next time, this mixture stirred 2 hours down at 25 ℃.Then under 5-10 ℃, drip this mixture in the suspension of the sodium acetate of five fluorine proyl ethyl acetate of 10.6 grams (45 mmole) in 200 milliliters of ethanol and 16.4 grams (200 mmole), under 25 ℃ were stirred 12 hours and stirred down, add in the entry.Suction strainer goes out sedimentary product, washes with water and drying.During purifying, product Virahol recrystallization.
Obtain the 1-[(4-cyano group-5-methyl sulphonyl amino-2-fluoro-phenyl of 8.6 grams (theoretical amount 60.5%)) hydrazono-]-4-ethoxycarbonyl-1,1,1,2,2-five fluorine fourth-3-ketone, 165 ℃ of fusing points.Embodiment (X IV-2)
Figure A9980714300781
At first in 100 milliliters of acetate, add 10.7 gram (47 mmole) 4-cyano group-5-methyl sulphonyl amino-2-fluoro-aniline; ice-cooled 20 ℃ of 1 nitrosyl-sulfuric acids (92% concentration) that add 7.3 grams (53 mmole) next time, this mixture stirred 2 hours down at 25 ℃.Then at 1 of 14.2 grams (71 mmole) in 200 milliliters of ethanol under 5-10 ℃; 1; drip this mixture in the suspension of the sodium acetate of 1-difluoro chloro ethanoyl ethyl acetate and 26 grams (313 mmole), under 25 ℃ were stirred 12 hours and stirred down, add in the entry.Suction strainer goes out sedimentary product, washes with water and drying.
Obtain the 1-[(4-cyano group-5-methyl sulphonyl amino-2-fluoro-phenyl of 13.7 grams (theoretical amount 66%)) hydrazono-]-4-ethoxycarbonyl-1,1-two fluoro-1-chloro-third-2-ketone, 175 ℃ of fusing points.
Application Example
In Application Example, compound known is in contrast below using:
Figure A9980714300782
2-(5-amino-2,4-two chloro-phenyl)-5-methyl-3 (2H)-pyridazinone-known from WO9639392.
Figure A9980714300791
4-bromo-2-(2,4-two chloro-5-nitro-phenyl)-5-methyl-3 (2H)-pyridazinone-known from WO9639392.
Figure A9980714300792
2-(5-amino-2,4-two chloro-phenyl)-4-bromo-5-methyl-3 (2H)-pyridazinone-known from WO9639392. 2-(2,4-two chloro-5-nitro-phenyl)-5-methyl-3 (2H)-pyridazinone-known from WO9639392.
Figure A9980714300794
2,5-two fluoro-4-(4-methyl-6-oxo-1 (6H)-pyridazinyl)-benzonitrile-known from WO9639392.Embodiment A
The preceding test of emerging
Solvent: the acetone of 5 parts of weight
Emulsifying agent: the alkylaryl polyglycol ether of 1 part of weight
In order to prepare the appropriate formulation of active compound, active compound and described amount solvent with 1 part of weight add described amount emulsifying agent, and water is diluted to enriched material the concentration of expectation.
The seed of sowing test plant in normal soil.After 24 hours,, make unit surface is used the active compound of the expectation of specified quantitative with the active agent preparations soil of spraying.Select the concentration of spraying fluid, make and use the active compound of the expectation of specified quantitative with 1000 premium on currency/hectares.
The Samsung after date is to estimate degree to plant injury with the growth phase of untreated control thing injury 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 1,2,12,13,24,40,41,46,66,84,107,112,120,121,122,123,124,125,126,127,128,129 and 133 compound shows than known compound (A), (B), (C), (D) with (E) the much better than activity of cutting weeds.Test after Embodiment B is emerged
Solvent: the acetone of 5 parts of weight
Emulsifying agent: the alkylaryl polyglycol ether of 1 part of weight
In order to prepare the appropriate formulation of active compound, active compound and described amount solvent with 1 part of weight add described amount emulsifying agent, and water is diluted to enriched material the concentration of expectation.
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 1000 premium on currency/hectares and use the active compound of the expectation of specified quantitative.
The Samsung after date is to estimate extent of injury to plant with the growth phase of untreated control thing injury 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 1,2,12,13,24,40,41,46,66,84,107,112,120,121,122,123,124,125,126,127,128,129 and 1 33 compound shows than known compound (A), (B), (C), (D) with (E) the much better than activity of cutting weeds.
Embodiment C
The test of ape chrysomelid (Phaedon) larva
Solvent: 7 parts of weight dimethyl formamides
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
In order to prepare the appropriate formulation of active compound, with the emulsifier mix of 1 part of weight active compound and described amount solvent and described amount, water is diluted to enriched material the concentration that needs.
By handling cabbage leaves (Brassica oleracea) in the preparation of active compound that is immersed in expectation concentration, and standby horseradish ape chrysomelid (Phaedon cochleariae) larva is infected when leaf is also moistening.
Behind the certain hour, measure and kill and wound percentage.The all mealworms of 100% expression all are killed; A mealworm is not killed in 0% expression.
In this test, for example prepare the activity that the compound of embodiment 1 and 2 shows.

Claims (14)

1. the phenyl pyridazinones that leads to the replacement of formula I:
Figure A9980714300021
Wherein
R 1Represent hydrogen, fluorine, chlorine or bromine,
R 2Represent cyano group, formamyl, thiocarbamoyl, fluorine, chlorine, bromine, perhaps representative is optional separately by the alkyl that has 1 or 2 carbon atom separately of fluoro-and/or chloro-replacement, alkoxyl group or alkylthio,
R 3Represent group-A 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 3-C 4-alkenyl, C 3-C 4-alkynes base, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 1Also representative is optional separately by fluoro-, the C that chloro-or bromo-replace 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 2Also representative is optional separately by fluoro-, chloro-, bromo-or C 1-C 4The C of-alkoxyl group-replacement 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 3Represent hydrogen, hydroxyl, amino, cyano group, isocyano-, thiocyano, nitro, formyl radical, carboxyl, formamyl, thiocarbamoyl, sulfo group, chlorosulfonyl, fluorine, chlorine, bromine, representative optional separately by hydroxyl-, fluoro-, chloro-, C 1-C 4-alkoxyl group-, C 1-C 4-alkyl-ketonic oxygen base-or C 1-C 4The alkyl that has 1-6 carbon atom in each comfortable alkyl of-alkoxyl group-ketonic oxygen base-replacement, alkoxyl group, alkylthio; alkyl sulphinyl, alkyl sulphonyl, alkylamino; dialkyl amido, carbalkoxy, alkyl amino-carbonyl; dialkyl amino carbonyl or dialkoxy (sulfo-) phosphoryl, representative optional separately by fluoro-or chloro-replace at alkenyl, have the alkenyl of 2-6 carbon atom in alkylidene group or the alkynes base separately; alkenyl oxy; alkenyl amino, alkylidene amino, alkenyl oxy carbonyl; the alkynes base; alkynes base oxygen base, alkynes base amino or alkynes base oxygen base carbonyl, representative is optional separately by fluoro-; chloro-; cyano group-, carboxyl-, C 1-C 4-alkyl-and/or C 1-C 4Have 3-6 carbon atom in each comfortable cycloalkyl of-alkoxyl group-carbonyl-replacement and randomly in alkyl, have the cycloalkyl of 1-4 carbon atom, cycloalkyl oxy, cycloalkyl amino, cycloalkylalkyl, cycloalkyl alkoxy, cycloalkyl alkyl amino, the ring alkylidene amino, cycloalkyl oxy carbonyl or cycloalkyl alkoxy carbonyl, perhaps representative optional separately by nitro-, cyano group-, carboxyl-, fluoro-, chloro-, bromo-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-and/or C 1-C 4The phenyl of-carbalkoxy-replacement, phenoxy group, phenyl-C 1-C 4-alkyl, phenyl-C 1-C 4-alkoxyl group, carbobenzoxy or phenyl-C 1-C 4-carbalkoxy,
A 3Also quilt hydrogenant pyrryl wholly or in part, pyrazolyl, imidazolyl, triazolyl are chosen in representative separately wantonly, furyl, Oxyranyle, oxetanyl, dioxolanyl alkyl dioxin, thienyl ， oxazolyl isoxazolyl, thiazolyl, isothiazolyl oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl-C 1-C 4-alkyl, furyl-C 1-C 4-alkyl, thienyl-C 1-C 4-alkyl ， oxazolyl-C 1-C 4-alkyl ， isoxazolyl-C 1-C 4-alkyl, thiazolyl-C 1-C 4-alkyl, pyridyl-C 1-C 4-alkyl, pyrimidyl-C 1-C 4-alkyl, the pyrazolyl methoxyl group, the furyl methoxyl group is represented perhydro pyranyl methoxyl group or pyridyl methoxyl group,
R 4Represent hydrogen, carboxyl, cyano group; formamyl, thiocarbamoyl, nitro; hydroxyl, sulfydryl, amino; fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl that has 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement, alkoxyl group, alkylthio; alkylamino, dialkyl amido or carbalkoxy
R 5Represent hydrogen, carboxyl, cyano group; formamyl, thiocarbamoyl, nitro; hydroxyl, sulfydryl, amino; fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl that has 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement, alkoxyl group, alkylthio; alkylamino, dialkyl amido or carbalkoxy and
R 6Represent hydrogen, carboxyl, cyano group; formamyl, thiocarbamoyl, nitro; hydroxyl, sulfydryl, amino; fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl that has 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement, alkoxyl group, alkylthio; alkylamino, dialkyl amido or carbalkoxy.
2. the Phenylpyridazinones of the replacement of claim 1 is characterized in that
R 1Represent hydrogen, fluorine or chlorine,
R 2Represent cyano group, formamyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl or trifluoromethyl,
R 3Represent group-A 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, methyl, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group, just-or different-propoxy-, methyl sulphonyl or ethylsulfonyl,
A 1Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases, propylene-1,3-two bases, acetylene-1,2-two bases, propine-1,2-two bases or propine-1,3-two bases
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, methyl, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group, just-or different-propoxy-, methyl sulphonyl, ethylsulfonyl, just-or different-sulfonyl propyl base or phenyl sulfonyl,
A 2Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases, propylene-1,3-two bases, acetylene-1,2-two bases, propine-1,2-two bases or propine-1,3-two bases
A 3Represent hydrogen, hydroxyl, amino; cyano group, nitro, formyl radical; carboxyl, formamyl, sulfo group; fluorine, chlorine, bromine; representative is optional separately by fluoro-, chloro-, and methoxyl group-or the methyl of oxyethyl group-replacement; ethyl, just-or different-propyl group, just-; different-, secondary-or tert-butyl, just-; different-, secondary-or uncle-amyl group, methoxyl group; oxyethyl group, just-or different-propoxy-, just-; different-, secondary-or uncle-butoxy, just-; different-, secondary-or uncle-pentyloxy, methylthio group; ethylmercapto group, just-or different-rosickyite base, just-; different-, secondary-or uncle-butylthio, methylsulfinyl; the ethyl sulfinyl, just-or different-propyl group sulfinyl, methyl sulphonyl; ethylsulfonyl, just-or different-sulfonyl propyl base, methylamino; ethylamino, just-or different-propyl group amino, just-; different-, secondary-or tert-butyl amino, dimethylamino; diethylamino, methoxycarbonyl, ethoxycarbonyl; just-or different-third oxygen carbonyl, dimethoxy phosphoryl, diethoxy phosphoryl or dipropoxy phosphoryl; diisopropoxy phosphoryl, representative are optional separately by the vinyl of fluoro-or chloro-replacement, propenyl; butenyl, propenyl oxygen base, butenyl oxygen base; propenyl amino, butenyl amino, propylidene amino; butylidene amino, propenyl oxygen base carbonyl, butenyl oxygen base carbonyl; ethynyl, proyl, butynyl; proyl oxygen base, butynyl oxygen base, proyl amino; butynyl amino, proyl oxygen base carbonyl or butynyl oxygen base carbonyl, representative is optional separately by fluoro-; chloro-, cyano group-, carboxyl-; methyl-, ethyl-, just-or different-propyl group-; methoxycarbonyl-or the cyclopropyl of ethoxycarbonyl-replacement; cyclobutyl, cyclopentyl, cyclohexyl; cyclopropyl oxygen base; cyclobutyl oxygen base, cyclopentyloxy, cyclohexyl oxygen base; the cyclopropyl methyl; cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl; cyclo propyl methoxy; cyclobutyl methoxy base, cyclopentyl methoxyl group, cyclohexyl methoxyl group; ring pentylidene amino; cyclohexylene amino, cyclopentyloxy carbonyl, cyclohexyl oxygen base carbonyl; cyclopentyl methoxycarbonyl or cyclohexyl methoxycarbonyl; perhaps representative optional separately by nitro-, cyano group-, carboxyl-; fluoro-; chloro-, bromo-, methyl-; ethyl-; just-or different-propyl group-, trifluoromethyl-, methoxyl group-; oxyethyl group-; just-or different-propoxy--, difluoro-methoxy-, trifluoromethoxy-; methoxycarbonyl-and/or the phenyl of ethoxycarbonyl-replacement; phenoxy group, benzyl, styroyl; benzyl oxygen base; carbobenzoxy, benzyl oxygen base carbonyl
A 3Also representative (optional separately quilt is hydrogenant wholly or in part) dioxolanyl ， alkyl dioxin, pyrryl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl ， oxazolyl ， isoxazolyl, thiazolyl, isothiazolyl ， oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl methyl, furyl methyl, thienyl methyl oxazolyl methyl ， isoxazolyl methyl, thiazolyl methyl, pyridylmethyl, Pyrimidylmethyl, pyrazolyl methoxyl group, furyl methoxyl group or pyridyl methoxyl group
R 4Represent hydrogen, carboxyl, cyano group, formamyl, thiocarbamoyl; nitro, hydroxyl, sulfydryl, amino, fluorine; chlorine, bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl, just-or different-propyl group; just-, different-, secondary-or tert-butyl, methoxyl group; oxyethyl group, methylthio group, ethylmercapto group, methylamino; ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl
R 5Represent hydrogen, carboxyl, cyano group, formamyl, thiocarbamoyl; nitro, hydroxyl, sulfydryl, amino, fluorine; chlorine, bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl, just-or different-propyl group; just-, different-, secondary-or tert-butyl, methoxyl group; oxyethyl group, methylthio group, ethylmercapto group, methylamino; ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl and
R 6Represent hydrogen, carboxyl, cyano group, formamyl, thiocarbamoyl; nitro, hydroxyl, sulfydryl, amino, fluorine; chlorine, bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl; just-or different-propyl group, just-, different-, secondary-or tert-butyl; methoxyl group, oxyethyl group, methylthio group, ethylmercapto group; methylamino, ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl.
3. the Phenylpyridazinones of the replacement of claim 1 is characterized in that
R 1Represent hydrogen, fluorine or chlorine,
R 2Represent cyano group or thiocarbamoyl,
R 3Represent group-A 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, methyl, ethyl, just-or different-propyl group, methyl sulphonyl or ethylsulfonyl,
A 1Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases or propylene-1,3-two bases,
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, methyl, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group, just-or different-propoxy-, methyl sulphonyl, ethylsulfonyl, just-or different-sulfonyl propyl base or phenyl sulfonyl,
A 2Also represent methylene radical, ethane-1,1-two bases, ethane-1,2-two bases, propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, ethene-1,2-two bases, propylene-1,2-two bases or propylene-1,3-two bases,
A 3Represent hydrogen, hydroxyl, amino; cyano group, nitro, carboxyl; formamyl, sulfo group, fluorine; chlorine, bromine, representative is optional separately by fluoro-; chloro-, methoxyl group-or the methyl of oxyethyl group-replacement, ethyl; just-or different-propyl group, just-, different-; secondary-or tert-butyl, just-, different-; secondary-or uncle-amyl group, methoxyl group, oxyethyl group; just-or different-propoxy-, just-, different-; secondary-or uncle-butoxy, just-, different-; secondary-or uncle-pentyloxy, methylthio group, ethylmercapto group; just-or different-rosickyite base, just-, different-; secondary-or uncle-butylthio, methylsulfinyl, ethyl sulfinyl; just-or different-propyl group sulfinyl, methyl sulphonyl, ethylsulfonyl; just-or different-sulfonyl propyl base, methylamino, ethylamino; just-or different-propyl group amino, just-, different-; secondary-or tert-butyl amino, dimethylamino, diethylamino; methoxycarbonyl, ethoxycarbonyl, just-or different-third oxygen carbonyl; representative is optional separately by the propenyl of fluoro-or chloro-replacement, butenyl, propenyl oxygen base; butenyl oxygen base, propenyl amino, butenyl amino; propylidene amino, butylidene amino, propenyl oxygen base carbonyl; butenyl oxygen base carbonyl, proyl, butynyl; proyl oxygen base, butynyl oxygen base, proyl amino; butynyl amino, proyl oxygen base carbonyl or butynyl oxygen base carbonyl, representative is optional separately by fluoro-; chloro-, cyano group-, carboxyl-; methyl-, ethyl-, just-or different-propyl group-; methoxycarbonyl-or the cyclopropyl of ethoxycarbonyl-replacement, cyclobutyl, cyclopentyl; cyclohexyl, cyclopropyl oxygen base, cyclobutyl oxygen base; cyclopentyloxy, cyclohexyl oxygen base, cyclopropyl methyl; cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl; cyclo propyl methoxy, cyclobutyl methoxy base, cyclopentyl methoxyl group; the cyclohexyl methoxyl group, ring pentylidene amino, cyclohexylene amino; the cyclopentyloxy carbonyl; cyclohexyl oxygen base carbonyl, cyclopentyl methoxycarbonyl or cyclohexyl methoxycarbonyl, perhaps representative optional separately by nitro-; cyano group-; carboxyl-, fluoro-, chloro-; bromo-; methyl-, ethyl-, just-or different-propyl group-; trifluoromethyl-; methoxyl group-, oxyethyl group-, just-or different-propoxy--; difluoro-methoxy-; trifluoromethoxy-, methoxycarbonyl-and/or the phenyl of ethoxycarbonyl-replacement, phenoxy group; benzyl; styroyl, benzyl oxygen base, carbobenzoxy; benzyl oxygen base carbonyl
A 3Also represent pyrazolyl, imidazolyl, triazolyl, furyl, thienyl oxazolyl ， isoxazolyl, thiazolyl, isothiazolyl oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl methyl, furyl methyl, thienyl methyl oxazolyl methyl ， isoxazolyl methyl, thiazolyl methyl, pyridylmethyl, Pyrimidylmethyl, pyrazolyl methoxyl group, furyl methoxyl group or pyridyl methoxyl group
R 4Represent hydrogen, cyano group, thiocarbamoyl, nitro, fluorine, chlorine, bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group, methylthio group, ethylmercapto group, methylamino, ethylamino or dimethylamino,
R 5The methyl that representative is replaced by fluoro-and/or chloro-separately, ethyl, just-or different-propyl group and
R 6Represent hydrogen, cyano group, thiocarbamoyl, nitro, fluorine, chlorine; bromine, perhaps representative is optional separately by the methyl of fluoro-and/or chloro-replacement, ethyl, just-or different-propyl group, methoxyl group, oxyethyl group; methylthio group, ethylmercapto group, methylamino, ethylamino, dimethylamino, methoxycarbonyl or ethoxycarbonyl.
4. according to each the Phenylpyridazinones of replacement of claim 1-3, it is characterized in that R 1Represent fluorine.
5. according to each the Phenylpyridazinones of replacement of claim 1-4, it is characterized in that R 2Represent cyano group.
6. according to each the Phenylpyridazinones of replacement of claim 1-5, it is characterized in that R 4And R 6Represent hydrogen or methyl.
7. according to each the Phenylpyridazinones of replacement of claim 1-6, it is characterized in that R 5Represent trifluoromethyl.
8. according to each the Phenylpyridazinones of replacement of claim 1-7, it is characterized in that R 3Represent A 3
9. according to each the Phenylpyridazinones of replacement of claim 1-8, it is characterized in that A 1Representative-NH-and A 2Represent SO 2
10. according to each the Phenylpyridazinones of replacement of claim 1-9, it is characterized in that A 1Represent methylidene alkylsulfonyl or ethylsulfonyl and A 2Representative-CO-.
11. each the method for Phenylpyridazinones of replacement of preparation claim 1-10 is characterized in that:
(a) if if suitably in the presence of reaction promoter and suitably in the presence of thinner, the halogenated aryl hydrocarbon of logical formula II reacts with the pyridazinone of logical formula III or reacts with the sour affixture or an alkali metal salt of logical formula III compound:
Figure A9980714300081
Wherein
R 1, R 2And R 3Such as claim 1-3 in each definition and
X 1Represent halogen,
Figure A9980714300082
Wherein
R 4, R 5And R 6Such as claim 1-3 in each definition,
Perhaps
(b) if if suitably in the presence of reaction promoter and suitably in the presence of thinner, the aryl hydrazine of logical formula IV and the β-trihalogenmethyl of general formula (V)-ketenes react:
Figure A9980714300083
Wherein
R 1, R 2And R 3Such as claim 1-3 in each definition and
Figure A9980714300091
Wherein
R 4, R 5And R 6Such as claim 1-3 in each definition,
X 2Represent halogen,
Perhaps
(c) the hydrazone carboxylic acid of logical formula VI carries out the closed loop condensation, promptly reacts with dewatering agent:
Figure A9980714300092
Wherein
R 1, R 2, R 3, R 4, R 5And R 6Such as claim 1-3 in each definition,
Perhaps
(d) nitrated general formula (I a) 2, the dibasic Phenylpyridazinones of 4-, promptly react with nitrating agent:
Figure A9980714300093
Wherein
R 1, R 2, R 4, R 5And R 6Such as claim 1-3 in each definition,
Perhaps
(e) separately randomly in the presence of reaction promoter and randomly in the presence of thinner, the positive phosphine reaction of carbalkoxy methylene radical of the hydrazone carbonyl compound of general formula (VII) and general formula (VIII) or with the phosphono-carboxylic acids trialkyl ester reaction of general formula (IX):
Figure A9980714300101
Wherein
R 1, R 2, R 3, R 5And R 6Such as claim 1-3 in each definition,
Figure A9980714300102
Wherein
R 4Such as claim 1-3 in each definition and
The R representative has the alkyl of 1-6 carbon atom,
Figure A9980714300103
Wherein
R 4Such as claim 1-3 in each definition and
The R representative has the alkyl of 1-6 carbon atom.
12. general formula (VII hydrazone carbonyl compound a)
Wherein
R 1Represent fluorine, chlorine or bromine,
R 2-1Represent cyano group, formamyl, thiocarbamoyl, perhaps representative is optional separately by the alkyl that has 1 or 2 carbon atom separately of fluoro-and/or chloro-replacement, alkoxyl group or alkylthio,
R 3Represent group-A 1-A 2-A 3,
Wherein
A 1Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 3-C 4-alkenyl, C 3-C 4-alkynes base, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 1Also representative is optional separately by fluoro-, the C that chloro-or bromo-replace 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 2Represent singly-bound, represent oxygen, sulphur ,-SO-,-SO 2-,-CO-or group-N-A 4-, A wherein 4Represent hydrogen, hydroxyl, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, phenyl, C 1-C 4-alkyl sulphonyl or phenyl sulfonyl,
A 2Also representative is optional separately by fluoro-, the C that chloro-or bromo-replace 1-C 6-alkane 2 basis, C 2-C 6-olefin 2 base, C 2-C 6-azepine olefin 2 base, C 2-C 6-alkynes two bases, C 3-C 6-naphthenic hydrocarbon two bases, C 3-C 6-cyclenes two bases or phenylene,
A 3Represent hydrogen, hydroxyl, amino, cyano group, isocyano-, thiocyano, nitro, carboxyl, formamyl, thiocarbamoyl, sulfo group, chlorosulfonyl, fluorine, chlorine, bromine, representative is optional separately by fluoro-, chloro-or C 1-C 4The alkyl that has 1-6 carbon atom in the comfortable alkyl of each of-alkoxyl group-replacement, alkoxyl group, alkylthio; alkyl sulphinyl, alkyl sulphonyl, alkylamino; dialkyl amido; carbalkoxy or dialkoxy (sulfo-) phosphoryl, representative optional separately by fluoro-or chloro-replace at alkenyl, have the alkenyl of 2-6 carbon atom in alkylidene group or the alkynes base separately; alkenyl oxy; alkenyl amino, alkylidene amino, alkenyl oxy carbonyl; the alkynes base; alkynes base oxygen base, alkynes base amino or alkynes base oxygen base carbonyl, representative is optional separately by fluoro-; chloro-; cyano group-, carboxyl-, C 1-C 4-alkyl-and/or C 1-C 4Have 3-6 carbon atom in each comfortable cycloalkyl of-alkoxyl group-carbonyl-replacement and randomly in alkyl, have the cycloalkyl of 1-4 carbon atom, cycloalkyl oxy, cycloalkylalkyl, cycloalkyl alkoxy, the ring alkylidene amino, cycloalkyl oxy carbonyl or cycloalkyl alkoxy carbonyl, perhaps representative optional separately by nitro-, cyano group-, carboxyl-, fluoro-, chloro-, bromo-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-and/or C 1-C 4The phenyl of-carbalkoxy-replacement, phenoxy group, phenyl-C 1-C 4-alkyl, phenyl-C 1-C 4-alkoxyl group, carbobenzoxy or phenyl-C 1-C 4-carbalkoxy,
A 3Also quilt hydrogenant pyrryl wholly or in part, pyrazolyl, imidazolyl, triazolyl are chosen in representative separately wantonly, furyl, Oxyranyle, oxetanyl, dioxolanyl, thienyl ， oxazolyl isoxazolyl, thiazolyl, isothiazolyl oxadiazole base, thiadiazolyl group, pyridyl, pyrimidyl, triazinyl, pyrazolyl-C 1-C 4-alkyl, furyl-C 1-C 4-alkyl, thienyl-C 1-C 4-alkyl ， oxazolyl-C 1-C 4-alkyl ， isoxazolyl-C 1-C 4-alkyl, thiazolyl-C 1-C 4-alkyl, pyridyl-C 1-C 4-alkyl, pyrimidyl-C 1-C 4-alkyl, the pyrazolyl methoxyl group, the furyl methoxyl group is represented perhydro pyranyl methoxyl group or pyridyl methoxyl group,
R 5Represent hydrogen, cyano group, thiocarbamoyl, nitro, hydroxyl; sulfydryl, amino, fluorine, chlorine, bromine; the perhaps optional separately alkyl that in alkyl, has 1-4 carbon atom separately that is replaced by fluoro-and/or chloro-of representative, alkoxyl group, alkylthio, alkylamino or dialkyl amido and
R 6Represent hydrogen, cyano group, thiocarbamoyl, nitro, hydroxyl; sulfydryl, amino, fluorine, chlorine, bromine; perhaps representative is optional separately by the alkyl, alkoxyl group, alkylthio, alkylamino or the dialkyl amido that have 1-4 carbon atom in alkyl separately of fluoro-and/or chloro-replacement.
13. the crop protection composition is characterized in that containing each the Phenylpyridazinones and the conventional expansion agent and/or the tensio-active agent of replacement of at least a claim 1-10.
14. the plant do not expected of control or the method for animal pest is characterized in that making each the Phenylpyridazinones of at least a replacement of claim 1-10 to act on plant or the animal pest and/or their dried rhizome of rehmannia of not expecting of dwelling.
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* Cited by examiner, † Cited by third party
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6121201A (en) 1998-09-11 2000-09-19 Ishihara Sangyo Kaisha, Ltd. Diaryl ethers and processes for their preparation and herbicidal and desiccant compositions containing them
JP3890816B2 (en) 1998-12-09 2007-03-07 住友化学株式会社 Method for producing pyridazin-3-one derivative
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US20030130123A1 (en) * 2000-04-14 2003-07-10 Michael Puhl 2-Phenyl-2h-pyridazine-3-ones
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AR092742A1 (en) 2012-10-02 2015-04-29 Intermune Inc ANTIFIBROTIC PYRIDINONES
MX2016012808A (en) 2014-04-02 2017-01-05 Intermune Inc Anti-fibrotic pyridinones.
MX2018012303A (en) * 2016-04-15 2019-01-14 Syngenta Participations Ag Herbicidal pyridazinone compounds.
GB201717080D0 (en) 2017-10-18 2017-11-29 Syngenta Participations Ag Chemical process

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH373919A (en) * 1959-02-02 1963-12-15 Ciba Geigy Method of controlling weeds
DE2808193A1 (en) * 1978-02-25 1979-09-06 Basf Ag PYRIDAZONE CONNECTIONS
DE19520613A1 (en) * 1995-06-06 1996-12-12 Bayer Ag Phenylpyridazinones
IL123162A (en) * 1995-08-21 2003-01-12 Sumitomo Chemical Co Pyridazin-3-one derivatives and herbicidal compositions comprising them
AR009380A1 (en) * 1996-10-21 2000-04-12 Sumitomo Chemical Co PROCESS OF PREPARATION OF A DERIVATIVE OF PIRIDAZIN-3-ONA, USEFUL AS A HERBICIDE, CARBOXYLIC ACID FOR USE THEREOF, SALE OF THIS LAST AND PROCESS TO PREPARE SUCH CARBOXYLIC ACID
ZA978995B (en) * 1996-10-21 1998-08-25 Sumitomo Chemical Co Production of pyridazine herbicide
DE19754348A1 (en) * 1996-12-11 1998-06-18 Ciba Geigy Ag New 2-(hetero)aryl-2(3H)-pyridazinone derivatives
IL123339A0 (en) * 1997-02-19 1998-09-24 Sumitomo Chemical Co Pyridazin-3-one derivatives and their use
IL123340A0 (en) * 1997-02-20 1998-09-24 Sumitomo Chemical Co Pyridazin-3-one derivatives and their use

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103974939A (en) * 2011-12-09 2014-08-06 先正达有限公司 Herbicidal compounds
WO2014036952A1 (en) * 2012-09-06 2014-03-13 华东理工大学 Pyridazinone compound and its use
CN103664795A (en) * 2012-09-06 2014-03-26 华东理工大学 Pyridazine ketone compound and use thereof
CN103664795B (en) * 2012-09-06 2017-10-03 华东理工大学 Pyridazinone compound and application thereof

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