+

WO1996037463A1 - Procede de fabrication des derives de n-methyle-methoxyimino-acetamide et intermediaires dans ce procede - Google Patents

Procede de fabrication des derives de n-methyle-methoxyimino-acetamide et intermediaires dans ce procede Download PDF

Info

Publication number
WO1996037463A1
WO1996037463A1 PCT/JP1996/001349 JP9601349W WO9637463A1 WO 1996037463 A1 WO1996037463 A1 WO 1996037463A1 JP 9601349 W JP9601349 W JP 9601349W WO 9637463 A1 WO9637463 A1 WO 9637463A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
general formula
formula
oxo
derivative
Prior art date
Application number
PCT/JP1996/001349
Other languages
English (en)
Japanese (ja)
Inventor
Masatsugu Oda
Manabu Katsurada
Original Assignee
Mitsubishi Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Publication of WO1996037463A1 publication Critical patent/WO1996037463A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups

Definitions

  • the present invention relates to a method for producing a methoxyiminoacetic acid amide derivative useful as an agricultural and horticultural fungicide, an intermediate for producing the same, and a method for producing an intermediate.
  • Japanese Patent Application Laid-Open No. 07-076464 discloses an N-methyl-methoxyiminoacetic acid amide derivative having excellent bactericidal activity.
  • the publication describes a method for amidating a methoxyiminoacetic acid ester derivative, but this method may involve a side reaction in some cases, and thus the target compound is not necessarily stably obtained. You don't get it.
  • W094Z221812 contains 1-hydroxy-14-methoxymino-2-methyl-3-methyl-1, 2,3,4—tetrahydroisoquinoline as a raw material.
  • a method for producing a methyl-methoxyiminoacetic acid amide derivative is described, but according to the examples in the publication, the yield is as low as 38%, which is not industrially satisfactory.
  • JP-A-63-323852, JP-A-Heisei 3-4 6268, JP-A-1986-964, JP-A-1981-64, and JP-A-5-435 3, 3, 5-7, 976, 6-, 5-3, 1124, 6-251, 32, etc. also describe biologically active methoxyiminoacetic acid derivatives and their production methods.
  • problems such as that the yield is low or that they cannot be applied to the production of N-methyl-methoxyiminoacetic acid amide derivative described in the above-mentioned JP-A-7-076564.
  • R 1 represents an alkyl group of d—C 4.
  • R 1 represents an alkyl group of d—C 4.
  • R 2 represents a hydrogen atom or a group represented by the general formula —C (R 3 ) (R 4 ) —Ar, wherein R 3 and R 4 are each independently a hydrogen atom or C! - represents a ⁇ alkyl group of C 4, A r represents a Teroariru group to which may be optionally substituted Ariru group or substituted.
  • R 3 and R 4 are each independently a hydrogen atom or C! - represents a ⁇ alkyl group of C 4
  • a r represents a Teroariru group to which may be optionally substituted Ariru group or substituted.
  • the compound of the general formula (I) is a novel compound, and the present invention also relates to such a novel compound and a method for producing the same.
  • R 1 represents a C 1 -C 4 straight or branched alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, .sec-butyl and the like. Of these, it is rather preferably R 1 is methyl or Echiru, is properly favored by al is methyl.
  • R 2 represents a hydrogen atom or a group represented by the general formula C (R 3 ) (R 4 ) —Ar.
  • R 3 and R 4 each independently represent a hydrogen atom; a C i -C 4 linear or branched alkyl group such as methyl, ethyl, n-propyl, is 0-propyl, n-butyl, sec-butyl and the like. Of these, it is preferred that R 3 and R 4 are each independently hydrogen or methyl. C More preferably, R 3 is hydrogen and R 4 is methyl.
  • Ar is an aryl group such as phenyl or naphthyl which may be substituted by the following group; or a heteroaryl group such as pyridyl, phenyl or thiazolyl which may be substituted by the following group.
  • aryl group such as phenyl or naphthyl which may be substituted by the following group
  • heteroaryl group such as pyridyl, phenyl or thiazolyl which may be substituted by the following group.
  • it represents phenyl which may be substituted by the following groups.
  • Examples of the group substituted by the aryl group represented by Ar include cyano; a halogen atom such as fluorine, chlorine, and bromine; methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, and the like.
  • the groups may together form a methylenedioxy group, an ethylenedioxy group or the like to form a condensed ring with the aryl group.
  • the number of substituents is 1-5, preferably 1-2.
  • the aryl group has a plurality of substitution groups, they may be the same or different.
  • Examples of the group which may be substituted with the heteroaryl group represented by Ar include cyano; halogen atoms such as fluorine, chlorine and bromine; methyl, ethyl, n-propyl, iso-propyl, n A C 1 -Cs alkyl group such as —butyl, sec-butyl, etc .; a C 1 -C 4 haloalkyl group such as trifluoromethyl, difluoromethyl, trichloromethyl or dichlorodifluoroethyl; or a halogen atom or C
  • Ci-Cs alkoxy groups such as 0-propoxy and n-butoxy are exemplified.
  • the alkyl chains of these groups may be straight or branched.
  • preferred substituents for the heteroaryl group include C! -An alkyl group of C 4 ; a halogen atom; or trifluoromethyl.
  • the number of substituents is the same or different and is 1 or 2.
  • the N-methyl-methoxyiminoacetic acid amide derivative represented by the general formula (III) is a compound represented by the general formula (I).
  • the compound represented by the formula It can be produced via the compound of (VI).
  • R 1 and R 2 are as previously defined.
  • Scheme 1 The oxamine derivative of the formula (II) may be used as it is or, in some cases, in the form of a salt such as a hydrochloride.
  • the amount to be used is 1 to 3 equivalents, preferably 1 to 3 times, relative to the 1-alkoxy-14-methoxyminnow 2-methyl-3-oxo-1,1,2,3,4-tetrahydridoisoquinoline derivative of the formula (I). 1.5 equivalents.
  • Examples of the acid used include organic acids such as acetic acid and trifluoroacetic acid; hydrohalic acids such as hydrochloric acid; hydrogen halides such as hydrogen chloride and hydrogen bromide; methanesulfonic acid, ⁇ -toluenesulfonic acid or sulfuric acid Sulfonic acids such as pyridine; acid addition salts of organic bases such as pyridin hydrochloride and pyridine sulfate; and Lewis acids such as zinc chloride, iron chloride and aluminum chloride. Of these, sulfonic acids and hydrogen halides are preferred.
  • the above acid is used in an amount of from a catalytic amount to 5 times equivalent, preferably 1 equivalent, of the 1-alkoxy-14-methoxyimimino 2-methyl-3-oxo-1,2,3,4-tetrahydroisoquinoline derivative of the general formula (I). It is used up to twice the equivalent of the catalyst.
  • the reaction is usually performed in a solvent.
  • solvent used examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloromethane, and the like; getyl ether, tetrahydrofuran, dioxane Ethers; esters such as ethyl acetate; alcohols such as methanol, ethanol, and propanol Coals; polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, diacid, and water, and the like, whether a single solvent or a mixed solvent. good. Of these, ethers such as tetrahydrofuran and dioxane; polar solvents such as N, N-dimethylformamide, dimethylsulfoxide and acetic acid are preferred.
  • the reaction is carried out at a temperature of from 0 ° to the boiling point of the solvent used, preferably from 20 to 120 °.
  • the reaction time is usually about 30 minutes to 24 hours, preferably about 1 to 8 hours.
  • N-methyl-methoxyiminoacetic acid amide derivative represented by the general formula (III) can be converted by adding an acid and continuing the reaction in the same manner as described above.
  • the 1-alkoxy-1-methoxyiminor 2-methyl-3-oxo-1,2,3,4-tetrahydroisoquinoline derivative of the general formula (I) is a novel compound, and has the formula (IV) according to the following scheme 2.
  • X represents a chlorine atom or a bromine atom, and R 1 is as defined above.
  • the alcohol of the formula (V) is used in an amount of 1 equivalent to a large excess, preferably 2 equivalents to an amount of a solvent, based on the benzol halide derivative of the formula (IV).
  • the base used may be either an inorganic base or an organic base.
  • the inorganic base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate.
  • Alkali metal hydrides such as sodium bicarbonate and potassium hydrogen carbonate; alkali metal hydrides such as sodium hydride
  • alkali metal such as metallic sodium
  • organic base examples include tertiary amines such as triethylamine; aromatic bases such as pyridine and picoline; alkali metal alcoholates such as sodium methethylate and potassium t-butoxy.
  • alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides and alkali metal alcoholates Preferable examples include alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides and alkali metal alcoholates.
  • the above base is used in an amount of 1 equivalent to 10 equivalents, preferably 2 equivalents to 5 equivalents, based on the benzol halide derivative of the general formula (IV).
  • the reaction is usually performed in a solvent.
  • solvent used examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, dioxane, and the like.
  • Ethers esters such as ethyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol, propanol and butanol; -triles such as acetonitrile; N-dimethylformamide, N-methylpyrrolide And a polar solvent such as dimethyl sulfoxide, acetic acid, and water.
  • the solvent may be a single solvent or a mixed solvent.
  • Preferable examples include ethers, alcohols, and polar solvents such as N, N-dimethylformamide and dimethylsulfoxide.
  • the reaction is carried out at a temperature from room temperature to the boiling point of the solvent used, preferably at 20 to 150 ° C.
  • the reaction time is usually about 30 minutes to 48 hours, preferably about 1 to 10 hours.
  • the benzal halide derivative of the formula (used as a starting material can be produced, for example, by the method shown in the following scheme 3 or a method analogous thereto. (In the following scheme, X is as defined above. )
  • the glyoxylic acid ethyl ester of the formula (VI I) is oxidized by a method known per se (for example, described in JP-A-5-977768) or a method analogous thereto, thereby obtaining the compound of the formula (VI II) Or a methoxyiminoacetic acid derivative of the formula (IX).
  • the hydroxyiminoacetic acid derivative of the formula (VIII) can be easily converted to a methoxyiminoacetic acid derivative of the formula (IX) by treating with a methylating agent such as dimethyl sulfate or methyl iodide.
  • an inert solvent eg, halogenated hydrocarbons such as carbon tetrachloride
  • a catalyst such as perbenzoic acid, 2,2'-azobis (isobutyrate), or light in the presence of methoxyimino diacid of the above formula (IX).
  • the derivative is treated with a halogenating agent such as chlorine, bromine, N-bromosuccinic acid imide, N-chlorosuccinic acid imide or sulfuryl chloride to give the benzal halide acetate derivative of formula (X).
  • a halogenating agent is required at least twice equivalent to the methoxyiminoacetic acid derivative of the formula (IX).
  • acetate derivative of benzal halide of the formula (X) can be reacted with methylamine in an inert solvent to lead to the desired benzal halide derivative of the formula (IV).
  • Methylamine can be used in an amount ranging from 1 equivalent to a large excess with respect to the acetic acid ester derivative of benzylhalide of the formula (X), but is preferably used in an amount equivalent to 13 equivalents.
  • Solvents used include: aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloromethane, and the like; getyl ether, tetrahydrofuran Ethers, such as dioxane; dioxane; ketones, such as acetone and methylethyl ketone; alcohols, such as methanol, ethanol, and propanol; N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, Examples thereof include polar solvents such as acetonitrile and water, which may be a single solvent or a mixed solvent. Preferred solvents include toluene, tetrahydrofuran, ethanol or water.
  • the reaction is carried out at a temperature of from 178 C to the boiling point of the solvent, preferably from 0 to 60.
  • the glyoxylic acid ester derivative of the formula (VII) used as a starting material in Scheme 3 can be prepared by a known method ⁇ for example, a method described in Synthetic Communication, 11, 943 (1981) ⁇ , Alternatively, it is manufactured by a method according to it.
  • Examples of the acid used for the isomerization reaction include organic acids such as acetic acid and trifluoroacetic acid; hydrohalic acids such as hydrochloric acid; hydrogen halides such as hydrogen chloride; methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid and the like. Sulfonic acids; acid addition salts of organic bases such as pyridine hydrochloride and pyridine sulfate; and Lewis acids such as zinc chloride, iron chloride and aluminum chloride. Preferred are organic acids, hydrogen halides and sulfonic acids.
  • the acid used is used in an amount of from the catalytic amount to the solvent amount, preferably from the catalytic amount to 1 equivalent.
  • solvent used examples include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; and hydrocarbons such as getyl ether, tetrahydrofuran and dioxane.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane
  • hydrocarbons such as getyl ether, tetrahydrofuran and dioxane.
  • Ethers examples include polar solvents such as amide, N-methylpyrrolidone, dimethyl sulfoxide, acetic acid, and water, which may be a single solvent or a mixed solvent.
  • polar solvents such as amide, N-methylpyrrolidone, dimethyl sulfoxide, acetic acid, and water, which may be a single solvent or a mixed solvent.
  • Preferred are ethers such as tetrahydrofuran and dioxane, alcohols, polar solvents such as N, N-dimethylformamide and acetic acid.
  • the reaction is carried out at a temperature ranging from room temperature to the boiling point of the solvent used, preferably at a temperature of 20 to 120.
  • the 1-alkoxy-1-methoxyoximino 2-methyl-3-oxo-1,1,2,3,4-tetrahydroisoquinoline derivative of the formula (I) is converted to the 4-methyoxyisoquinoline of the formula (XII)
  • Toximinino 2-methyl-3-oxo-1,2,3,4-tetrahydroquinoline is converted to HO—R 1 of the above formula (V) in the presence of a base, wherein R 1 is already defined.
  • the compound can be produced by reacting with an alcohol represented by the formula and a halogenating agent.
  • the alcohol of the formula (V) is a one-fold equivalent to a large excess of the 4-methoxymino 2-methyl-3-oxo-1,1,2,3,4-tetrahydroisoquinoline of the formula (XII) Preferably, it is used in an amount from 2 equivalents to the amount of solvent.
  • Examples of the base to be used include sodium hydroxide, alkali metal hydroxides such as sodium hydroxide, sodium carbonate, sodium carbonate, calcium carbonate and the like.
  • Alkali metal or alkaline earth metal carbonates Alkali metal bicarbonates such as sodium bicarbonate and hydrogen bicarbonate realms; Alkali metal bicarbonates such as sodium acetate Metal acetates; Tertiary amines such as triethylamine; Aromatic bases such as pyridine and picolin; Polyvinylpyrrolidone (cr0ss-1 inked), polyvinylpyridine, etc.
  • Bases alkali metal alcoholates such as sodium ethylate and t-butoxy potassium. Of these, alkali metal carbonates, alkali metal bicarbonates, or alkali metal acetates are preferred. New
  • the above base is used in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to compound (XII).
  • halogenating agents used include chlorine, bromine, sulfuryl chloride, sulfuryl bromide, N-chlorosuccinic acid imid, N-bromosuccinic acid imid, and 1,3-dibromobutane. , 5-dimethylhydantoin and the like.
  • N-bromosuccinic acid imide or bromine is used.
  • the halogenating agent used is used in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, relative to compound (XII).
  • the reaction is usually performed in a solvent.
  • solvent used examples include: aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, propanol and butanol; and nitriles such as acetate-tolyl.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like
  • getyl ether, tetrahydrofuran Ethers
  • Ethers such as dioxane
  • esters such as eth
  • a polar solvent such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetic acid, and water may be used, and a single solvent or a mixed solvent thereof may be used. Of these, aromatic hydrocarbons and alcohols are preferred.
  • the reaction is carried out at a temperature from room temperature to the boiling point of the solvent used, preferably from 20 to 150.
  • the reaction time is usually 30 minutes to 24 hours, preferably 1 to 8 hours.
  • the 4-methoxyminnow 2-methyl-3-oxo- 1,2,3,4-tetrahydroquinoline of the formula (XII) is a novel compound, and it comprises a benzyl halide derivative of the formula (XI) and methylamine.
  • a base eg, triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc.
  • an inert solvent eg, ethanol, toluene, tetrahydrofuran, etc.
  • the 4-methoxymino-2-methyl-3-oxo-1,1,2,3,4-tetrahydroisoquinoline of the formula (XII) is a compound of N-benzylmethylamine (XIII) and oxalic acid derivative.
  • free 2-Methyl-3,4-dioxo-1,2,3,4-tetrahydroisoquinoline (XIV) obtained by a Delkraft reaction or the like can be produced by a method known per se (for example, described in JP-A-5-977768). It can also be manufactured by oxidation.
  • the compound obtained in any of the above reactions can be easily separated and purified from the reaction mixture by a method known per se, for example, extraction, recrystallization, or column chromatography.
  • a novel intermediate, a 1-alkoxy-14-methoxyimimino 2-methyl-3-oxo-1 1,2,3,4-tetrahydroisoquinoline derivative By passing through, the methoxyiminoacetic acid amide derivative of the general formula (II) can be efficiently produced. According to the method of the present invention, it is possible to obtain a methoxyiminoacetic acid amide derivative in a high yield of about 80%.
  • the methoxyiminoacetic acid amide derivative obtained according to the present invention has a high control effect on, for example, wheat powder rust, leaf rust and the like of barley as described in JP-A-7-076464. It is an excellent agricultural and horticultural fungicide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention se rapporte à un procédé de fabrication d'un dérivé de N-méthyle-méthoxyimino-acétamide de formule générale (III). Dans ladite formule, R2 représente hydrogène, etc. Le procédé consiste à faire réagir un nouveau dérivé de 1-alcoxy-4-méthoxyimino-2-méthyle-3-oxo-1,2,3,4-tétrahydro-iso-quinoline de formule générale (I), où R1 représente alkyle C¿1-4?, avec un dérivé d'oxyamine de la formule générale suivante (II): H2NO-R?2¿, dans ladite formule, R2 a la définition indiquée ci-dessus.
PCT/JP1996/001349 1995-05-23 1996-05-22 Procede de fabrication des derives de n-methyle-methoxyimino-acetamide et intermediaires dans ce procede WO1996037463A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP12411395A JPH08319265A (ja) 1995-05-23 1995-05-23 Ｎ−メチル−メトキシイミノ酢酸アミド誘導体の製造法およびその中間体
JP7/124113 1995-05-23

Publications (1)

Publication Number Publication Date
WO1996037463A1 true WO1996037463A1 (fr) 1996-11-28

Family

ID=14877251

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1996/001349 WO1996037463A1 (fr) 1995-05-23 1996-05-22 Procede de fabrication des derives de n-methyle-methoxyimino-acetamide et intermediaires dans ce procede

Country Status (2)

Country Link
JP (1) JPH08319265A (fr)
WO (1) WO1996037463A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998023582A1 (fr) * 1996-11-26 1998-06-04 Mitsubishi Chemical Corporation Derives de methoxyiminoacetamide optiquement actifs, procedes de preparation de ces derives, intermediaires associes et pesticides contenant ces derives en tant qu'ingredient actif
JP2001240583A (ja) * 1999-12-17 2001-09-04 Mitsubishi Chemicals Corp ジハロプロペニルオキシベンゼン誘導体及びこれを有効成分とする有害生物防除剤
EP0765304B2 (fr) † 1994-06-10 2007-08-22 Bayer CropScience AG Procede de preparation de methylamides d'acide alpha-methoxyiminocarboxylique et intermediaires utilises a cet effet

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994022812A1 (fr) * 1993-03-29 1994-10-13 Basf Aktiengesellschaft Amides d'acide phenylacetique imino-substitues, leur preparation et fongicides les contenant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994022812A1 (fr) * 1993-03-29 1994-10-13 Basf Aktiengesellschaft Amides d'acide phenylacetique imino-substitues, leur preparation et fongicides les contenant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ACTA CHIM. HUNG., 114(1), (1983), TIKK I. et al., p. 69-77. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0765304B2 (fr) † 1994-06-10 2007-08-22 Bayer CropScience AG Procede de preparation de methylamides d'acide alpha-methoxyiminocarboxylique et intermediaires utilises a cet effet
WO1998023582A1 (fr) * 1996-11-26 1998-06-04 Mitsubishi Chemical Corporation Derives de methoxyiminoacetamide optiquement actifs, procedes de preparation de ces derives, intermediaires associes et pesticides contenant ces derives en tant qu'ingredient actif
JP2001240583A (ja) * 1999-12-17 2001-09-04 Mitsubishi Chemicals Corp ジハロプロペニルオキシベンゼン誘導体及びこれを有効成分とする有害生物防除剤

Also Published As

Publication number Publication date
JPH08319265A (ja) 1996-12-03

Similar Documents

Publication Publication Date Title
JP2783130B2 (ja) メトキシイミノ酢酸誘導体およびこれを有効成分とする農園芸用殺菌剤
JP4725977B2 (ja) ２−ジハロアシル−３−アミノ−アクリル酸エステルおよび３−ジハロメチル−ピラゾール−４−カルボン酸エステルの製造方法
US7335780B2 (en) Method for preparing 3-halo-4,5-dihydro-1H-pyrazoles
US6124466A (en) Nitroisourea derivative
CZ282922B6 (cs) Způsob syntézy (4R-cis)-1,1-dimethylethyl-6-kyanomethyl-2,2-dimethyl-1,3-dioxan-4-acetátu a meziprodukty pro tento způsob
HU198909B (en) Process for producing pyridine-dicarbocylic acid esters
US4923994A (en) 2-carboxy-3-cyano-4-aryl-pyrroles
US5624942A (en) 2-phenoxy-6-thienylmethyloxypyridine derivative and herbicidal composition containing same
WO1996037463A1 (fr) Procede de fabrication des derives de n-methyle-methoxyimino-acetamide et intermediaires dans ce procede
US5691277A (en) 2-(unsubstituted or substituted) (benzyloxy or phenoxy)-4-substituted-6-(meta-substituted phenoxy)pyridine, process for producing the same, and herbicidal composition
JP3915063B2 (ja) Ｎ−メチル−メトキシイミノ酢酸アミド誘導体の製造方法およびその中間体
RU2157363C2 (ru) Производные валинамида, способ их получения и способы получения промежуточных продуктов
KR100641908B1 (ko) 피리딘 유도체, 그의 제조방법, 및 제초제 중간체로서의용도
JP2002524546A (ja) 立体選択性ニトロ化合物の製造方法
EP0891972A1 (fr) Derives d'acide benzoique a substitution 3-(isoxazol-5-yl) et leur procede de production
JPH08283223A (ja) Ｎ−メチル−メトキシイミノ酢酸アミド誘導体の製造法およびその中間体
JPH04270248A (ja) ベンジルフェニルケトン誘導体
JP4075357B2 (ja) ４，５−ジ置換−１，２，３−トリアゾール及びその製造法
Al-Omran et al. Synthesis of 2, 6-dimethyl-4-substituted pyridine-3, 5-dicarbonitriles from β-aminoacrylonitriles
JP4828740B2 (ja) １，２，５−チアジアゾイルメタノン誘導体の製造方法及びジオキシム誘導体
JP3013414B2 (ja) ピラゾール―５―カルボン酸エステル類の製造法
US7189855B2 (en) Process for production of phenoxy-substituted 2-pyridone compounds
KR810000815B1 (ko) 4-벤조일피라졸 유도체 및 그의 알루미늄염의 제조법
JPWO2002076962A1 (ja) ３−オキソ−２−（２−チアゾリル）プロパンニトリルの製造方法および中間体
JPH07258219A (ja) Ｎ−ピラゾリルカーバメート誘導体およびこれを有効成分とする農園芸用殺菌剤

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CN JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载