WO1996016962A1 - Procede de production de derives de pyrazole - Google Patents

Procede de production de derives de pyrazole Download PDF

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Publication number
WO1996016962A1
WO1996016962A1 PCT/JP1995/002454 JP9502454W WO9616962A1 WO 1996016962 A1 WO1996016962 A1 WO 1996016962A1 JP 9502454 W JP9502454 W JP 9502454W WO 9616962 A1 WO9616962 A1 WO 9616962A1
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WIPO (PCT)
Prior art keywords
formula
compound
general formula
alkyl group
compound represented
Prior art date
Application number
PCT/JP1995/002454
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English (en)
Japanese (ja)
Inventor
Kazufumi Nakamura
Seiji Tomita
Ichiro Nasuno
Mitsuru Shibata
Original Assignee
Idemitsu Kosan Co., Ltd.
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
Priority claimed from JP6299230A external-priority patent/JPH08157472A/ja
Priority claimed from JP6322615A external-priority patent/JPH08176142A/ja
Application filed by Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Priority to AU39941/95A priority Critical patent/AU3994195A/en
Publication of WO1996016962A1 publication Critical patent/WO1996016962A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to a method for producing a virazole derivative useful as a herbicide, an intermediate useful for producing the virazole derivative, and a method for producing the intermediate.
  • Atrazine a triazine herbicide, and arachlor and metolachlor, which are acid anilide herbicides
  • Atrazine has a low activity against grass weeds.
  • Metrachlor on the other hand, has low activity against broadleaf weeds. Therefore, it is currently difficult to control grass and broadleaf weeds at once with a single agent.
  • the above herbicides require a high dose, which is not preferable in terms of environmental problems.
  • the present inventors have proposed a novel virazo having excellent selectivity that can control both grass and broadleaf weeds at a low dose without causing phytotoxicity to useful crops such as corn, wheat and barley.
  • a novel derivative was found (International Publication No. W095 / 0404).
  • R 1 represents a hydrogen atom or a ( ⁇ ⁇ 0 4 alkyl group;
  • R 2 is - ( ⁇ alkyl group;
  • X 1 is a hydrogen atom, a halogen atom or ( ⁇ ⁇ 4 alkyl group;
  • X 2 and X 3 Each It is independently C, -C 4 alkyl group;
  • X 4 is a hydrogen atom, the 7-position of Chiokuroman ring or 8-position by halogen atoms or substituted.
  • ⁇ C 4 alkyl group; and n is 0, 1 or represents the integer 2.
  • X 1 and X 4 are C, to C 4 alkyl groups, and the substitution position of X 4 is the 8-position of the chiochroman ring.
  • the following reaction steps are disclosed as a method for producing compound (a).
  • X 1 , X 3 and X 4 each independently represent a C! C alkyl group, and Ha 1 represents a halogen atom.
  • the above production method involves halogenating the thiochroman compound of the general formula (I), then subjecting the thiochroman compound to a Grignard reaction to carboxylize the halogen, and then oxidizing the halogen, and includes a Grignard reaction.
  • Grignard leather is expensive and not industrially advantageous.
  • Sun and moon are all 13 ⁇ 4
  • the object of the present invention is, in the broadest sense, to synthesize a pyrazole derivative useful as a herbicide and its intermediate with a carboxylic acid intermediate requiring a costly step such as the Grignard reaction as described above.
  • An object of the present invention is to provide an industrially advantageous production method without the need for steps or many complicated steps.
  • a first object of the present invention is to provide a novel method for producing a pyrazole derivative useful as a herbicide.
  • a second object of the present invention is to provide a method for producing a nuclear halogen compound which is a production intermediate for producing a novel virazole derivative and is a novel compound.
  • a third object of the present invention is to provide a process for producing the above-mentioned nuclear halogen compound, which is a production intermediate, and a novel compound, which is a novel compound.
  • Another object of the present invention is to provide a novel method for producing an aromatic carboxylic acid derivative which is useful as an intermediate for producing a birazol derivative which is useful as a herbicide.
  • a fifth object of the present invention is to provide a method for producing an acetylated sulfone compound, which is a production intermediate for producing an aromatic carboxylic acid derivative and is a novel compound.
  • a sixth object of the present invention is to provide a method for producing an acetylated sulfide compound which is a production intermediate for producing the acetylated sulfone compound and is a novel compound. Disclosure of the invention
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, obtained from the following steps, an industrially advantageous biazole derivative which does not include a carboxylic acid synthesis step:
  • an industrially advantageous biazole derivative which does not include a carboxylic acid synthesis step:
  • a method for producing a novel intermediate used therefor and a simpler and industrially advantageous method for producing an aromatic carboxylic acid derivative containing no Grignard reaction, and a novel intermediate used therefor. It has been completed.
  • the first object of the present invention is to provide a compound represented by the general formula ( ⁇ )
  • X 1 , X 2 , X 3 and X 4 are represented by-(indicating a 4- alkyl group, X 5 being a halogen atom, and n being an integer of 0, 1 or 2).
  • a nuclear halogen compound and a compound represented by the general formula (II) are represented by-(indicating a 4- alkyl group, X 5 being a halogen atom, and n being an integer of 0, 1 or 2).
  • R 1 represents a hydrogen atom or a C, ⁇ . Alkyl group
  • R 2 represents a bisazole compound represented by ( ⁇ ⁇ ( ⁇ an alkyl group.)
  • a base and a metal catalyst Characterized by reacting with carbon monoxide in the presence of
  • a second object of the present invention is to provide a compound of the general formula (IV)
  • a second object of the present invention is to provide a compound of the general formula (IIIA-a)
  • X 1 , X 2 , X 3 , X 4 and X 5 are as defined above, and m represents 1 or 2.
  • a halogenated sulfoxide compound or a halogenated sulfone represented by the following formula: This can also be achieved by a method for producing a compound (corresponding to the compound of the general formula (IIIA) where n 1 or 2).
  • a second object of the present invention is to provide a compound of the general formula (IV)
  • halogenated thiochroman compound is first halogenated with a halogenating agent, and then oxidized.
  • X 1 , X 2 , X 3 and X 4 are as defined above, X 5 represents a halogen atom, and m represents an integer of 1 or 2.
  • a halogenated sulfoxide represented by the following formula: Compound or nuclear halogenated sulfone compound (in general formula (IIIA), n l or Is also achieved by the manufacturing method of
  • a third object of the present invention is to provide a compound of the general formula (V)
  • a third object of the present invention is to provide a compound represented by the general formula (VIII)
  • a fourth object of the present invention is to provide a compound of the general formula (X)
  • acetylated sulfone compound (X) wherein the compound is oxidized with an oxidizing agent, wherein the compound is represented by the general formula (IIIB):
  • aromatic carboxylic acid derivative (IIIB) ⁇ ) aromatic carboxylic acid derivative
  • a fifth object of the present invention is to provide a compound of the general formula (IX)
  • acetylated sulfide compound (IX) each independently represent a C, ⁇ ( ⁇ alkyl group.
  • Acetylated sulfide compound (IX) Oxidizing the compound represented by the general formula (X):
  • a sixth object of the present invention is to provide a compound of the general formula (IV)
  • thiochroman compound (IV) Is reacted with acetyl chloride or acetic anhydride in the presence of an acid catalyst to introduce an acetyl group at the 6-position of the thiochroman ring.
  • FIG. 1 is a view showing a production process of a birazol derivative (I) of the present invention without passing through an aromatic carboxylic acid derivative.
  • FIG. 2 is a view showing a production process of the aromatic carboxylic acid derivative (II IB) of the present invention without passing through the Grignard reaction.
  • the method for producing the nuclear halogen compound represented by -b) and the thiochroman compound represented by the general formula (IV) will be sequentially described.
  • the compound names in the reaction process diagram of FIG. 1 are abbreviated as follows.
  • the thiophenol compound of the general formula (V) is a “thiophenol compound (V)”
  • the thiochroman compound of the general formula (IV) is a “thiochroman compound (IV)”
  • the “nuclear halogenated sulfide compound (IIIA-b)” and the nuclear halogenated sulfoxide compound of the general formula (IIIA-b) and the nuclear halogenated sulfone compound are collectively referred to as “nuclear halogenated sulfoxide / sulfone compound (IIIA-b).
  • a nuclear halogen compound of the general formula (IIIA) is referred to as a "nuclear halogen compound (IIIA)", a virazole compound of the general formula (II) is referred to as a "virazole compound (II)", a general formula (VI) and a general formula (VII) Alcohol compounds (VI) and alcohol compounds (VII), and sulfide compounds of the general formula (VIII) as sulfide compounds VIII) ", and virazole derivatives of general formula (I) is referred to as” Birazo Ichiru derivative (I) ".
  • the method for producing the virazole derivative (I) that achieves the first object of the present invention comprises a reaction scheme
  • Examples of the metal catalyst used in this reaction include transition metals such as palladium, rhodium, ruthenium, and platinum, but palladium is preferable.
  • the amount of the metal catalyst to be added is 0.1 to 1.0 times, preferably 0 to 0.5 times the weight of the nuclear halogen compound (0).
  • the ligand used for the metal of the metal catalyst is not particularly limited, but an organophosphine compound such as triphenylphosphine or tri-n-butylphosphine is preferred.
  • the addition amount of the ligand is 2.0 to: L 0.0 equivalent, preferably 2.0 to 4.0 equivalent, based on the metal of the metal catalyst.
  • an organic base such as pyridine, triethylamine, N, N-dimethylaniline, or an inorganic base such as sodium carbonate, potassium carbonate, or sodium hydroxide can be used, and preferably triethylamine.
  • the amount of the base to be added is 1.0 to 20.0 equivalents, preferably 1.0 to 10.0 equivalents to the nuclear halogen compound (IIIA).
  • a phase transfer catalyst such as tetra-n-butylamine bromide together with these bases is effective from the viewpoint of improving the reactivity.
  • This reaction is performed in a carbon monoxide atmosphere.
  • the pressure of carbon monoxide is in the range of normal pressure to 200 kg / cm 2 , and is usually preferably about 50 to 150 kg / cm 2 .
  • the reaction temperature is from room temperature to 200 ° (preferably from 50 to 180 ° C.
  • the reaction time is from 30 minutes to 200 hours, usually completed in 1 to 100 hours.
  • the reaction solvent interferes with the reaction.
  • the amount of the virazole compound ( ⁇ ⁇ ⁇ ) used in the reaction is 1.0 to the amount of the nuclear halogen compound ( ⁇ ). To 10.0 equivalents, preferably 1.0 to 5.0 equivalents.
  • the reaction solvent is distilled off according to a conventional method, and an organic solvent (insoluble in water, for example, ethyl acetate, toluene, methylene chloride, etc.) is added to the obtained residue, and an aqueous solution of alcohol (for example, Extract the target with an aqueous solution of sodium bicarbonate, aqueous solution of sodium carbonate). Adjust the pH to 1 by adding an acid (eg, hydrochloric acid) to the resulting aqueous layer Then, the precipitated solid is collected by filtration and dried to isolate the target crystal.
  • halogenating agent used in this reaction examples include bromine, sulfuryl chloride, and chlorine, and bromine is preferable.
  • the amount of the halogenating agent is 1 to 2 equivalents, preferably 1 to 1.1 equivalents, relative to the thiochroman compound (IV).
  • the solvent used is not particularly limited as long as it does not hinder the reaction, and includes acetic acid, methylene chloride, chloroform, carbon tetrachloride and the like, and preferably methylene chloride.
  • the reaction temperature is usually from 0 to 80 ° C, preferably from 20 to 30 ° C.
  • the reaction time is usually 1 to 80 hours, preferably 1 to 3 hours.
  • a reducing agent for example, an aqueous solution of sodium hydrogen sulfite
  • a reaction solution for washing to remove the remaining excess halogenating agent according to a conventional method.
  • the reaction solution is washed with an aqueous alkaline solution (eg, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium carbonate, etc.) to remove the generated hydrogen halide.
  • an aqueous alkaline solution eg, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium carbonate, etc.
  • the target substance can be isolated by purifying the obtained oily substance by means such as silica gel column chromatography and distillation.
  • the oxidizing agent used in this reaction includes hydrogen peroxide, peracetic acid, sodium metaperiodate, and the like, and hydrogen peroxide is preferred.
  • the solvent used is not particularly limited as long as it does not interfere with the reaction, and includes acetic acid, water, methanol and the like, with acetic acid being preferred.
  • the reaction temperature is not particularly limited from room temperature to the reflux temperature of the solvent, but is preferably about 80 ° C.
  • the reaction time is about 30 minutes to 24 hours, preferably about 1 to 3 hours.
  • a reducing agent for example, an aqueous solution of sodium hydrogen sulfite
  • a reducing agent for example, an aqueous solution of sodium hydrogen sulfite
  • Steps B and C in Fig. 1 can be performed in succession in one pot instead of as separate steps, and the halogenated sulfoxide / sulfone compound (IIIA-b) can be directly obtained from the thiochroman compound (IV). It is.
  • the method for obtaining the nuclear halogenated sulfoxide / sulfone compound (IIIA-b) in this one pot is represented by the reaction formula
  • X 1 , XX 3 , X 4 , X 5 and m are as defined above.
  • An oxidizing agent is added to the reaction system without isolation of the reaction product, the nuclear halogenated sulfide compound (IIIA-a), and the same oxidation reaction is performed continuously as in the above step. , and the indicated by step C 2 in FIG. 1.
  • the solvent used in this reaction is not particularly limited as long as it does not hinder the reaction, but includes acetic acid, water and the like, and acetic acid is preferred.
  • Examples of the halogenating agent and the oxidizing agent to be used include those exemplified in the above Steps B and.
  • the reaction conditions are the same as in Steps B and B above for the nuclear halogenation and oxidation.
  • a reducing agent for example, an aqueous solution of sodium bisulfite
  • a reaction solution for example, an organic solvent
  • an organic solvent insoluble in water, for example, ethyl acetate, toluene, methylene chloride, etc.
  • an aqueous alkaline solution for example, aqueous sodium bicarbonate, sodium carbonate, etc.
  • the desired product can be isolated by distilling off the organic solvent and purifying the obtained oily substance by means such as silica gel column chromatography.
  • a method for producing a thiochroman compound (IV), which achieves the third object of the present invention, comprises a reaction formula
  • Examples of the solvent used in this step include acetic anhydride, acetic acid, and formic acid, and formic acid is preferred.
  • the amount of the alcohol compound (VI) or (VI I) is 1 to 5 equivalents, preferably 1 to 1.5 equivalents, relative to the thiophenol compound (V).
  • the reaction temperature is not particularly limited from room temperature to the reflux temperature of the solvent, but is preferably the reflux temperature of the solvent.
  • the reaction time is usually 30 minutes to 24 hours, but preferably about 7 hours.
  • an organic solvent insoluble in water, for example, ethyl acetate, toluene, methylene chloride, etc.
  • an organic solvent is added to the reaction solution to extract the desired product according to a conventional method. Wash the organic layer with an aqueous alkali solution (eg, aqueous sodium bicarbonate, aqueous sodium carbonate, etc.). After distilling off the organic solvent, the target substance can be isolated by purifying the obtained oily substance by means such as distillation and silica gel column chromatography.
  • a method for producing a thiochroman compound (IV), which achieves the third object of the present invention, comprises a reaction formula
  • step 1 this is indicated by step A-3.
  • the sulfide compound (VIII) can be synthesized by the method described in International Publication WO95 / 04054.
  • Examples of the acid used in this reaction include Lewis acids such as aluminum chloride, zinc chloride, and iron chloride; protonic acids such as methyl sulfonic acid; and acidic ion exchange resins. Acid ion exchange resins are preferred.
  • the amount of the acid used is 0.1 to 3 equivalents, preferably 0.1 to 1.2 equivalents, relative to the sulfide compound (VIII).
  • the solvent used is not particularly limited as long as it does not hinder the reaction, and includes toluene, benzene, nitrobenzene, dichloromethane, n-hexane and the like, and is preferably toluene.
  • the reaction temperature is from 0 ° C to the reflux temperature of the solvent, preferably the reflux temperature of the solvent.
  • the reaction time is usually 1 to 80 hours, preferably 3 to 12 hours.
  • the target product can be isolated by filtering off the resin after completion of the reaction and distilling off the filtrate.
  • an aqueous alkali solution for example, aqueous sodium bicarbonate, aqueous sodium carbonate, etc.
  • aqueous sodium bicarbonate for example, aqueous sodium bicarbonate, aqueous sodium carbonate, etc.
  • the desired product can be isolated by purification by means such as silica gel column chromatography.
  • the first novel intermediate is a compound obtained as a result of the reaction in step A in FIG.
  • X ′, X 2 , X 3 and X 4 in the formula each represent a c! C ⁇ alkyl group, preferably each a methyl group.
  • X 1 , X 2 , X 3 and X 4 in the formula each represent a C! C ⁇ alkyl group, preferably each a methyl group.
  • X 5 represents a halogen atom, and is preferably a bromine atom.
  • n represents an integer of 0, 1 or 2, and is preferably 2.
  • an aromatic carboxylic acid derivative ( ⁇ ), an acetylated sulfone compound (X), an acetylated sulfide compound ( IX) will be described sequentially.
  • the method for producing the aromatic carboxylic acid derivative ( ⁇ ), which is the fourth object of the present invention comprises a reaction scheme
  • X 1 , X 2 , X 3 and X 4 are as defined above.
  • the acetyl group at the 6-position of the acetylated sulfone compound (X) is formed by using an oxidizing agent. It is converted to a carboxyl group to obtain an aromatic carboxylic acid derivative (II IB), which is shown by step G in FIG.
  • oxidizing agent examples include permanganate, chromate, halogen, oxygen, sulfuric acid, and the like, and halogen is preferable.
  • halogen chlorine and bromine are preferable as the halogen.
  • a halogen is used as an oxidizing agent, it is used as a hypohalite together with a sodium hydroxide such as sodium hydroxide or potassium hydroxide or a carbonate such as sodium carbonate or potassium carbonate to form a hypohalogen. It is preferable to use 3 or more equivalents of the acid salt with respect to the acetylated sulfone compound (X).
  • the amount of halogen used for this purpose is preferably 3 equivalents or more based on the acetylated sulfone compound (X), and the amount of the hydroxyl hydroxide or carbonate is preferably 9 equivalents or more based on the acetylated sulfone compound (X).
  • hypohalite instead of generating hypohalite from halogen and alkali hydroxide or carbonate, hypohalite can be directly used as an oxidizing agent.
  • sodium hypochlorite is preferred as the hypohalite.
  • the amount of hypohalite used in this case is the same as described above.
  • the solvent used is not particularly limited as long as it does not interfere with the reaction, but water, dioxane and the like are preferable.
  • the reaction temperature is generally preferably from room temperature to the reflux temperature of the solvent.
  • the reaction time is generally preferably about 3 to 24 hours.
  • the target substance can be isolated by dehydrating the obtained organic layer with a dehydrating agent such as anhydrous sodium sulfate and distilling off the solvent.
  • the isolated aromatic carboxylic acid derivative ( ⁇ ) is used for producing the virazole derivative (I).
  • the method for producing the acetylated sulfone compound (X), which is the fifth object of the present invention, comprises a reaction scheme
  • Examples of the oxidizing agent that can be used in this reaction include hydrogen peroxide, peracetic acid, sodium periodate and the like, and hydrogen peroxide is preferable.
  • the amount of the oxidizing agent used is 2 equivalents or more based on the acetylated sulfide compound (IX).
  • the solvent to be used is not particularly limited as long as it does not hinder the reaction, but includes acetic acid, water, methanol and the like, and is preferably acetic acid.
  • the reaction temperature is generally not particularly limited from the room temperature to the reflux temperature of the solvent, but is preferably about 80 to 100 ° C.
  • the reaction time is preferably about 30 minutes to 2 hours.
  • the reaction mixture is cooled according to a conventional method, and sodium bisulfite or the like is added thereto to remove excess oxidizing agent, and the target substance (acetylated sulfone compound (X)) is dissolved in an organic solvent such as ethyl acetate. Extract.
  • the desired product can be isolated by dehydrating the obtained organic layer with a dehydrating agent such as anhydrous sodium sulfate and then distilling off the solvent.
  • the acetylated sulfone compound (X) thus obtained is a novel compound, It is useful as an intermediate for producing the aromatic carboxylic acid derivative (IIIB).
  • the method for producing the acetylated sulfide compound (IX), which is the sixth object of the present invention, comprises:
  • Lewis acids such as zinc chloride and iron chloride, or protonic acids such as hydrogen fluoride, sulfuric acid and phosphoric acid, preferably aluminum chloride.
  • the amount of the acid catalyst used is based on the amount of the chiochroman compound (IV). Usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents
  • acetyl halide used in this reaction for example, acetyl chloride, acetyl chloride, acetyl chloride or acetyl chloride is used. And the like, chlorides Asechiru are preferred.
  • the amount of acetyl halide or acetic anhydride used in this reaction is generally 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, relative to the thiochroman compound (IV).
  • This reaction is carried out in a solvent.
  • solvents include methylene chloride, nitromethane, acetonitrile, benzene and the like, and preferably, methylene chloride.
  • the reaction temperature is usually 0-80. C, but 0. C to around room temperature is preferred.
  • the reaction time is generally about 30 minutes to 8 hours, preferably about 30 minutes to 3 hours.
  • the reaction mixture is poured into an aqueous acid solution such as hydrochloric acid to which ice has been added according to a conventional method. Separate the organic layer. The obtained organic layer is washed successively with a saturated aqueous sodium hydrogen carbonate solution, a saturated saline solution and the like, dehydrated with a dehydrating agent such as anhydrous sodium sulfate, and then the solvent is distilled off to isolate the desired product.
  • aqueous acid solution such as hydrochloric acid to which ice has been added according to a conventional method.
  • the acetylated sulfide compound (IX) thus obtained is a novel compound and is useful as an intermediate for producing the acetylated sulfone compound (X).
  • Step A-1 except that 3-methyl-1,3-butanediol (alcohol compound (VII)) was used in place of 3-methyl-2-buten-1-ol used in (Step A-1) above.
  • the same procedure as described above was carried out to obtain 0.91 g (yield 44%) of the title compound (Tiochroman compound (IV)).
  • 6-Acetyl-4,4,5,8-tetramethylthiochroman-1,1-dioxide obtained in Example 8 above (Compound No. 6) 2.10 g (7.5 To 10 ml of a dioxane solution (mmol) was added 31 ml (22.5 mmol, 3.0 equivalents) of a 5% aqueous solution of sodium hypochlorite (oxidizing agent) at room temperature, followed by stirring for 3 hours. To the reaction mixture, 10 ml of a 10% aqueous sodium hydroxide solution was added, and the mixture was washed with methylene chloride.
  • a novel virazole derivative capable of selectively controlling both grasses and broadleaf weeds at a low dose without causing phytotoxicity to useful crops such as corn, wheat, barley, etc.
  • a method that can be industrially advantageously produced without requiring many steps is provided.
  • an aromatic carboxylic acid derivative which is a useful intermediate for producing a birazol derivative useful as a herbicide, does not involve a costly Grignard reaction, and is simpler and more industrial.
  • the present invention provides a method for producing an aromatic carboxylic acid derivative which is more advantageous.
  • a virazole derivative can be produced at lower cost.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Cette invention se rapporte à un procédé permettant de produire des dérivés de pyrazole selon la formule de réaction (A), où R1 représente H ou alkyle C¿1?-C4; R?2, X1, X2, X3 et X4¿ représentent chacun alkyle C¿1?-C4; X?5¿ représente halogène; et n est égal à 0, 1 ou 2; ainsi qu'à un procédé pour produire un dérivé carboxylique aromatique selon la formule de réaction (B) où X?1, X2, X3 et X4¿ représentent chacun séparément alkyle C¿1?-C4.
PCT/JP1995/002454 1994-12-02 1995-12-01 Procede de production de derives de pyrazole WO1996016962A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39941/95A AU3994195A (en) 1994-12-02 1995-12-01 Process for producing pyrazole derivative

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP6/299230 1994-12-02
JP6299230A JPH08157472A (ja) 1994-12-02 1994-12-02 ピラゾール誘導体の製造方法
JP6/322615 1994-12-26
JP6322615A JPH08176142A (ja) 1994-12-26 1994-12-26 芳香族カルボン酸誘導体の製造法

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Publication Number Publication Date
WO1996016962A1 true WO1996016962A1 (fr) 1996-06-06

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018031A1 (fr) * 1992-03-03 1993-09-16 Idemitsu Kosan Co., Ltd. Derive de pyrazole
JPH06340654A (ja) * 1991-01-25 1994-12-13 Nippon Kayaku Co Ltd 新規ヒドラジン誘導体およびそれを有効成分とする殺虫組成物
WO1995004054A1 (fr) * 1993-08-02 1995-02-09 Idemitsu Kosan Co., Ltd. Derive de pyrazole
JPH0826914A (ja) * 1994-07-15 1996-01-30 Idemitsu Kosan Co Ltd トリケトン誘導体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06340654A (ja) * 1991-01-25 1994-12-13 Nippon Kayaku Co Ltd 新規ヒドラジン誘導体およびそれを有効成分とする殺虫組成物
WO1993018031A1 (fr) * 1992-03-03 1993-09-16 Idemitsu Kosan Co., Ltd. Derive de pyrazole
WO1995004054A1 (fr) * 1993-08-02 1995-02-09 Idemitsu Kosan Co., Ltd. Derive de pyrazole
JPH0826914A (ja) * 1994-07-15 1996-01-30 Idemitsu Kosan Co Ltd トリケトン誘導体

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AR001772A1 (es) 1997-12-10

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