WO2004007433A1 - アシルアセトニトリル化合物の製造方法 - Google Patents

アシルアセトニトリル化合物の製造方法 Download PDF

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WO2004007433A1
WO2004007433A1 PCT/JP2003/008700 JP0308700W WO2004007433A1 WO 2004007433 A1 WO2004007433 A1 WO 2004007433A1 JP 0308700 W JP0308700 W JP 0308700W WO 2004007433 A1 WO2004007433 A1 WO 2004007433A1
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general formula
group
compound represented
formula
reaction
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PCT/JP2003/008700
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French (fr)
Japanese (ja)
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Hirofumi Nakagawa
Masatoshi Hayashi
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Otsuka Chemical Co., Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the present invention relates to a method for producing an acylacetonitrile compound.
  • R 1 represents a C 2-4 alkenyl group, a C 2-4 alkynyl group, a (d-6 alkoxy) d-4 alkyl group, a '(d-4 alkylthio) d-4 alkyl group or a benzyl group.
  • X and Y each represent a halogen atom, a d-6 alkyl group or a C, -48-octaalkyl group.
  • m and n each represent an integer of 1 to 3. When m is 2 or 3, m Xs may be the same or different. When n is 2 or 3, n Ys may be the same or different.
  • an acylacetonitrile compound represented by the general formula (1) has been produced by, for example, a method shown in the following reaction formula-1.
  • R ′, X, Y, m and n are the same as above.
  • Z represents a halogen atom.
  • the acylacetonitrile compound represented by the general formula (1) is represented by a phenylacetonitrile compound represented by the general formula (7) and a compound represented by the general formula (8a).
  • the resulting carbonate compound is reacted in a solvent in the presence of a base to obtain a perfluorocyanoacetic acid ester compound represented by the general formula (4a) (step A).
  • step A It is produced by reacting an ⁇ -phenyl cyanoacetate compound represented by a) with a benzoyl halide compound represented by general formula (3) (step (2)).
  • the carbonate compound represented by the general formula (8a) used in the step A is a compound that is not commercially available and is difficult to obtain.
  • the ester carbonate compound represented by the general formula (8a) usually needs to be separately synthesized using a phosgene compound as a raw material compound.
  • phosgene compounds are toxic, there are environmental and safety issues.
  • An object of the present invention is to provide a method for industrially and advantageously producing an acylacetonitrile compound.
  • the present inventors have intensively studied to develop an industrially advantageous method for producing an acylacetonitrile compound.
  • the object of the present invention can be achieved by performing the reaction between the ⁇ -phenylcyanoacetic acid ester compound and the benzoyl octalide compound in a two-phase system of an organic solvent and water in the presence of a base and a phase transfer catalyst. I found out.
  • the present invention has been completed based on such knowledge.
  • the present invention provides the following method.
  • X represents a halogen atom, a d- 6 alkyl group or a d- 4 haloalkyl group.
  • m represents an integer of 1 to 3. When m is 2 or 3, each of the m Xs may be the same or different.
  • Y represents a halogen atom, a d-6 alkyl group or a d-4 amino group.
  • n shows the integer of 1-3. When n is 2 or 3, n Y's may be the same or different.
  • Z represents a halogen atom.
  • R 2 is C, - shows a 6 alkyl group.
  • X and m are the same as above. ]
  • R 1 is the same as above.
  • Alkali metal alkoxide has the general formula (9)
  • R 2 is the same as above.
  • M represents an alkali metal atom.
  • R 2 is the same as above.
  • X and m are the same as above.
  • R 1 is the same as above.
  • C 2 - Examples 4 alkenyl group for example, vinyl group, 1-loop port pair group, Ariru group, isopropenyl group, 1 Buarticulu group, 2-butenyl group, Examples thereof include linear or branched alkenyl groups having 2 to 4 carbon atoms, such as 3-butenyl group, 1-methyl-2-propenyl group, and 1,3-butenyl group.
  • the 4 alkynyl group for example, Echiniru group, 1 one-propynyl, 2-propynyl, 1 one methyl _ 2-propynyl group, 1 one Petit group, 2-heptynyl group, 3 - - C 2 heptynyl group And a linear or branched alkynyl group having 2 to 4 carbon atoms.
  • Examples of the d- 6 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, Examples thereof include linear or branched alkoxy groups having 1 to 6 carbon atoms, such as isopentyloxy, neopentyloxy, n-hexyloxy, and isohexyloxy.
  • alkyl group examples include linear groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n_butyl group, isobutyl group, sec-butyl group and tert-butyl group. Or a branched alkyl group.
  • Ci-4 alkyl groups include, for example, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, sec-butoxymethyl group, tert —Butoxymethyl group, n —pentyloxymethyl group, n-hexyloxymethyl group, methoxyethyl group, ethoxyxetyl group, n-propoxyshethyl group, isopropoxyxyl group, n-butoxyxyl group, isobutoxyxyl group A straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms such as a butyl group, a sec-butoxyl group, a tert-butoxyl group, a 3-methoxypropyl group, a 3-ethoxypropyl group or a 3-ethoxybutyl group; Examples thereof include a linear or branched alkyl group having 1 to
  • alkylthio group include a methylthio group, Echiruchio group, n- propylthio group, isopropylthio group, n _ Puchiruchio group, Isopuchiruchio group, sec - Puchiruchio group, tert - Puchiruchio carbon atoms such as groups 1-4 And a straight-chain or branched-chain alkylthio group.
  • (C, -4alkylthio) d-4alkyl groups include, for example, methylthiomethyl group, methylthioethyl group, ethylthiomethyl group, ethylthioethyl group, ethylthiopropyl group, ethylthiobutyl group, n-propylthiomethyl group, isopropylthiomethyl group, A linear or branched alkyl group having 1 to 4 carbon atoms and having 1 or 2 alkylthio groups substituted with 1 to 4 carbon atoms such as an n-butylthioethyl group may be mentioned.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group
  • straight-chain or branched-chain alkyl groups having 1 to 6 carbon atoms, such as n-hexyl group and isohexyl group.
  • Examples of the d- 4 haloalkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, an 11-fluoroethyl group, a 2-fluoroethyl group, and a 2-chloroethyl group.
  • R 1 is preferably a (d- 6 alkoxy) d- 4 alkyl group.
  • the reaction between the ⁇ -phenyl cyanoacetate compound of the general formula (2) and the benzoyl halide compound of the general formula (3) is carried out by the reaction between an organic solvent and water in the presence of a base and a phase transfer catalyst. Performed in a two-phase system.
  • organic solvent an organic solvent having substantially no adverse effect on the above reaction, having low affinity and solubility with water, and forming a two-phase system with water is used.
  • organic solvents include, for example, aliphatic or alicyclic hydrocarbons such as ⁇ -hexane, cyclohexane, ⁇ -heptane and ⁇ -octane; and aromatic hydrocarbons such as toluene, xylene, and cyclobenzene. Hydrogen; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride; and esters such as methyl acetate and ethyl acetate.
  • aromatic hydrocarbons are preferred, and toluene, black benzene and the like are more preferred.
  • One of the above organic solvents can be used alone, or two or more can be used as a mixture.
  • the amount of the organic solvent used is usually about 0.5 to 20 parts by weight, preferably about 2 to 4 parts by weight, per 1 part by weight of the ⁇ -phenylcyanoacetate ester compound represented by the general formula (2). However, it is not limited to these.
  • water used in combination with the organic solvent examples include, but are not limited to, pure water, distilled water, deionized water, and tap water.
  • the amount of water used is about 1 to 15 parts by weight, preferably about 1.5 to 4 parts by weight, per 1 part by weight of the monophenyl cyanoacetate compound represented by the general formula (2).
  • the present invention is not limited to these. It is more preferable to use about 1 to 1.5 parts by weight of water with respect to 1 part by weight of the organic solvent.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as potassium carbonate, sodium carbonate and sodium hydrogen carbonate. No. Among these, alkali metal carbonates such as potassium carbonate, sodium carbonate and sodium hydrogen carbonate are preferred.
  • bases can be used alone or in combination of two or more.
  • the amount of the base to be used is generally about 0.5 to 5 mol, preferably 1 to 1.5 mol, per 1 mol of the ⁇ -phenyl cyanoacetate ester compound represented by the general formula (2). It is about.
  • the base is preferably used by dissolving in water used as the above-mentioned reaction solvent.
  • phase transfer catalysts can be widely used, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, and ether-based catalysts.
  • the quaternary ammonium salts for example, tetra (d - 4 alkyl) Anmoniumu halide, benzyltri (C, - 4 alkyl) halides, and the like. Tetra - Specific examples of (d 4 alkyl) ammonium Niu beam halides, tetra-n- butyl ammonium Niu skeleton chloride, Ru tetra n- Petit Ruan monitor ⁇ beam bromide and the like.
  • Benzyltri (C, - 4 alkyl) Specific examples of the halides, benzyltri-methyl ammonium Niu skeleton chloride, benzyltrimethylammonium E chill ammonium Niu skeleton chloride and the like can be mentioned up.
  • the quaternary Hosuhoniumu salts for example, Te us (C, - 4 alkyl) Hosuhoniu Muharaido the like. Tetra (C, - 4 alkyl) Specific examples of the phosphonyl ⁇ beam halides, tetra E chill phosphonyl ⁇ beam bromide, Te we n- Buchiruhosuho Niumuburomido the like.
  • examples of the ether catalyst include dibenzo-18-crown-6.
  • phase transfer catalysts quaternary ammonium salts are preferable, and tetra-n-butylammonium chloride, tetra-n-butylammonium bromide and the like are more preferable.
  • phase transfer catalysts can be used alone, or two or more can be used in combination.
  • the amount of the phase transfer catalyst to be used is generally about 0.01 to 0.2 mol, preferably about 0.0 mol, per 1 mol of the ⁇ -phenyl cyanoacetate ester compound represented by the general formula (2). It is about 0.3 to 0.05 mol.
  • the ⁇ -phenyl cyanoacetate ester compound represented by the general formula (2) is dissolved in the organic solvent, the base is dissolved in water, and then these solutions are mixed.
  • the above-mentioned phase transfer catalyst is added to the obtained two-phase solvent, and the benzoyl halide compound represented by the general formula (3) is added dropwise, whereby the process proceeds suitably.
  • the amount of the benzoyl halide compound represented by the general formula (3) is generally about 5 to 2 mol, preferably 1 to 2 mol per mol of the monophenyl cyanoacetate compound represented by the general formula (2). Is about 0.9 to 1.2 mol.
  • the reaction temperature of the above reaction is usually in the range of 0 to the boiling point of the organic solvent to be used or lower, preferably in the range of 20 to 30, but is not limited thereto.
  • This reaction is carried out usually for about 1 to 10 hours, preferably for about 3 to 6 hours, depending on the reaction temperature and the like.
  • the target compound obtained by the above reaction can be easily isolated from the reaction mixture by commonly used isolation means such as filtration, solvent extraction, distillation, recrystallization and the like. It is purified by known purification means.
  • the benzoyl halide compound of the general formula (3) used is a known compound or a compound which can be easily produced according to a known method.
  • the ⁇ -phenyl cyanoacetate compound of the general formula (2) is produced according to the method shown in the following reaction formula 13. Reaction formula 1 3
  • the ⁇ -phenylcyanoacetate ester compound represented by the general formula (4) is represented by the phenylacetonitrile compound represented by the general formula (7) and the compound represented by the general formula (8). It is produced by reacting with a carbonate compound to be prepared.
  • the ⁇ -phenyl cyanoacetate compound represented by the general formula (2) is composed of an ⁇ -phenyl cyanoacetate compound represented by the general formula (4) and an alcohol compound represented by the general formula (5). And is produced by reacting
  • the phenylacetonitrile compound represented by the general formula (7) and the ester carbonate compound represented by the general formula (8) are easily available known compounds or are easily produced according to known methods.
  • carbonate compound represented by the general formula (8) various compounds in which R 2 represents a Ci-6 alkyl group can be used.
  • Preferred carbonic ester compound, C, - 2 compound is Al kill group, i.e., a dimethyl carbonate and carbonate Jechiru. Dimethyl carbonate is more preferred.
  • the amount of the carbonate compound represented by the general formula (8) is usually about 1 to 20 mol, preferably about 3 to 6 mol, per 1 mol of the phenylacetonitrile compound represented by the general formula (7). It is.
  • Phenylacetonitrile compound of the general formula (7) and carbonate ester of the general formula (8) In reacting the compound with the compound, it is preferable that an alkali metal alkoxide is present in the reaction system.
  • alkali metal alkoxide examples include d-4 saturated aliphatic alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl alcohol, and alkali metals. And the like. Among them, alkali metal alkoxides obtained from methanol or ethanol and alkali metals are preferable, and sodium methoxide and sodium ethoxide are particularly preferable.
  • an alkali metal alkoxide obtained from an alcohol composed of the same alkyl as the ester portion (R 2 ) of the carbonate compound represented by the general formula (8) and an alkali metal It is preferable to use an alkali metal alkoxide represented by 2 OM (wherein, R 2 is the same as above, and M represents an alkali metal atom).
  • the amount of the alkali metal alkoxide to be used is generally about 1 to 5 mol, preferably about 1.2 to 2 mol, per 1 mol of the phenylacetonitrile compound represented by the general formula (7).
  • the alcohol used as the alcohol solution of the alkali metal alkoxide is usually an alcohol composed of the same alkyl group as the alkali metal alkoxide portion used (that is, R 2 OH, wherein R 2 is The same is true for).
  • the concentration of the alkali metal alkoxide in the alcohol solution is usually about 5 to 35% by weight, preferably about 25 to 30% by weight.
  • the lowering speed of the alcohol solution of the alkali metal alkoxide can be appropriately selected depending on the concentration of the solution, the reaction scale, the temperature, the progress of the reaction, and the like.
  • solvent used in this reaction examples include hydrocarbons such as toluene, xylene, benzene, heptane, and octane; ethers such as tetrahydrofuran, dioxane, and diisopropyl ether.
  • the amount of these solvents to be used is generally about 1 to 10 parts by weight, preferably about 2 to 5 parts by weight, per 1 part by weight of the phenylacetonitrile compound represented by the general formula (7). It is not limited to these.
  • an alcohol ie, an alcohol represented by the general formula R 2 OH
  • an alcohol in an alcohol solution of the alkyl metal alkoxide ie, the general formula R 2 (Alcohol represented by OH) is preferably removed from the reaction system.
  • a solvent having a boiling point higher than the boiling point of the alcohol is preferably used.
  • This reaction may be performed under reduced pressure in consideration of the boiling point of the alcohol to be removed out of the system, the boiling point of the solvent used, the reaction temperature, and the like.
  • the pressure in the reaction system is usually about 6666 Pa to 6666 Pa, preferably about 33330 Pa to 53333 Pa. Is good.
  • the reaction temperature of this reaction can be appropriately set in the range of usually 50 to around the boiling point of the solvent, preferably about 70 to 100 ° C., in consideration of the boiling point and the degree of reduced pressure of the solvent used. .
  • This reaction is carried out usually for about 1 to 10 hours, preferably for about 2 to 5 hours, depending on the reaction temperature.
  • This reaction is preferably carried out in the presence of at least one catalyst selected from the group consisting of aluminum alkoxides and titanium alkoxides, while removing the alcohol formed as the reaction proceeds outside the reaction system.
  • This reaction can be carried out in an appropriate solvent.
  • the alcohol compound represented by the general formula (5) used as a reaction reagent is used in a large excess, and the alcohol compound is also used as a reaction solvent. Is preferred.
  • solvent used examples include aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane, n-heptane and n-octane; and aromatic hydrocarbons such as toluene, xylene, and benzene.
  • aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane, n-heptane and n-octane
  • aromatic hydrocarbons such as toluene, xylene, and benzene.
  • Halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride
  • esters such as methyl acetate and ethyl acetate.
  • Examples of the alcohol compound ( ⁇ ⁇ ) represented by the general formula (5) used in this reaction include, for example, 1-propenyl alcohol, aryl alcohol, isopropenyl alcohol, 1-butenyl alcohol, 2-butenyl alcohol. Thenyl alcohol, 3-butenyl alcohol, 1-methyl-2-propenyl alcohol, 1,3-butenyl genyl alcohol, ethynyl alcohol, 1-propynyl alcohol, 2-propynyl alcohol, 1-methyl — 2-propynyl alcohol, 1-butynyl alcohol, 2-butynyl alcohol, 3-butynyl alcohol, methoxymethyl alcohol, ethoxymethyl alcohol, n-propoxymethyl alcohol, isopropoxymethyl alcohol, n-butoxymethyl Alcohol, sec—butoxymethyl alcohol, tert—but Cimethyl alcohol, n-pentyloxymethyl alcohol, n-hexyloxymethyl alcohol, methoxyethyl alcohol, ethoxyethyl alcohol, n-prop
  • the amount of the alcohol compound represented by the general formula (5) is usually about 1 to 10 mol, preferably 2 to 1 mol per 1 mol of the ⁇ -phenylcyanoacetate compound represented by the general formula (4).
  • the amount may be about 4 to about 4 mol, but when it is also used as a reaction solvent, it is usually about 2 to 20 mol and preferably about 7 to 15 mol.
  • the catalyst used in this reaction is at least one selected from the group consisting of aluminum alkoxides and titanium alkoxides.
  • R 4 represents a 4- alkyl group.
  • aluminum alkoxides such as aluminum alkoxide, and more specifically, aluminum ethoxide, aluminum isopropoxide, aluminum trisec-butoxide and the like.
  • titanium alkoxide for example, the general formula (11)
  • titanium alkoxides such as titanium alkoxides represented by the following formulas, and more specifically, tetraisopropyl titanate, tetra n-butyl titanate and the like.
  • One of these catalysts can be used alone, or two or more of them can be used in combination.
  • the amount of the catalyst used is usually about 0.01 to 1 mol, preferably 0.1 to 0.2 mol, per 1 mol of the ⁇ -phenylcyanoacetate ester compound represented by the general formula (4). It is about.
  • the pressure should be reduced in consideration of the boiling point of the excluded alcohol, the boiling point of the alcohol compound represented by the general formula (5), and the reaction temperature.
  • the reaction may be performed below.
  • the general formula (1) the general formula (1)
  • the reaction is preferably performed under reduced pressure.
  • the degree of reduced pressure is usually about 6666 Pa to 6666 OPa, preferably about 33330 Pa to 53328 Pa.
  • the reaction temperature of this reaction is usually from 50 ° C. in consideration of the boiling point and the degree of vacuum of the alcohol compound represented by the general formula (5) to be used, or the alcohol compound represented by the general formula (5). Below, preferably within the range of about 80 to 130 ° C.
  • This reaction is carried out usually for about 1 to 15 hours, preferably for about 4 to 8 hours, depending on the reaction temperature.
  • Each product obtained in each of the above reactions is easily isolated from the reaction mixture by commonly used isolation means such as, for example, filtration, solvent extraction, distillation, and recrystallization, and further, for example, column chromatography. It is purified by commonly used purification means such as chromatography.
  • the ⁇ -phenyl cyanoacetate compound of general formula (4) and the ⁇ -phenyl cyanoacetate compound of general formula (2) obtained as shown in Reaction Scheme 13 are It can be used for the subsequent reaction without isolating and purifying it from the reaction mixture or by performing a simple purification operation, for example, a solvent extraction operation.
  • the acylacetonitrile compound represented by the general formula (1) can be industrially advantageously produced.
  • each reaction product is obtained in high yield. Therefore, the target compound ( 1) can be produced in extremely high yield.
  • the method of the present invention is also excellent in environmental and safety aspects because the compound is easily available and has low toxicity.
  • thermometer a dropping funnel and a distillation column were attached to a 500 ml three-necked flask, and a condenser and a receiver were attached to the distillation column.
  • the temperature of the mixed solution was maintained at 75 to 80 ° C, and an azeotropic mixture of methanol, toluene and dimethyl carbonate vaporized from the start of the dropwise addition was collected in a receiver of a distillation apparatus, and methanol was removed to the outside of the reaction system.
  • thermometer and a distillation column were attached to a 500 ml three-necked flask, and a cooler, a receiver, and a pressure reducer were attached to the distillation column.
  • thermometer and a dropping funnel were attached to a 1000 ml three-necked flask.
  • the entire toluene solution of 2-methoxyethyl 2- (4-tert-butylphenyl) cyanoacetate prepared in (1-b) above was added the entire toluene solution of 2-methoxyethyl 2- (4-tert-butylphenyl) cyanoacetate prepared in (1-b) above, and potassium carbonate 38 g (0.275 mol) and 0.8 g (0.0025 mol) of tetra-n-butylammonium bromide in 120 ml of water were added to obtain a two-phase reaction solution.
  • thermometer a thermometer, a dropping funnel, and a distillation column were attached to a three-necked flask of 50 Om1, and a condenser and a receiver were attached to the distillation column.
  • the temperature of the mixed solution was maintained at 75 to 80 ° C, and an azeotropic mixture of toluene / methanol / dimethyl carbonate vaporized from the start of the dropwise addition was collected in a receiver of a distillation apparatus, and methanol was removed to the outside of the reaction system.
  • thermometer and a dropping funnel were attached to a 1 000 m 1 three-necked flask, and the 2- (4-chlorophenyl) cyanoacetic acid 2-methoxyshethyl prepared in (2-b) above was placed in a flask. 59. O g (Purity 96%, 0.223 mol) and toluene 125 ml were added, and potassium carbonate 38 g (0.275 mol) and tetra-n-butylammonium bromide 0.8 g (0.20025 mol) were added to water 12 Om 1. An aqueous solution dissolved in was added to obtain a two-phase reaction solution.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/JP2003/008700 2002-07-11 2003-07-09 アシルアセトニトリル化合物の製造方法 WO2004007433A1 (ja)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN102140071A (zh) * 2011-03-10 2011-08-03 天津市施普乐农药技术发展有限公司 2-(4-叔丁基苯基)-氰基乙酸(2-甲氧基)乙基酯的合成方法

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4031243A (en) * 1975-07-03 1977-06-21 Juste, S.A. Quimico-Farmaceutica 2-(4-Isobutyl phenyl)butyric acid, salts thereof, and pharmaceutical compositions containing the same
JPS62175438A (ja) * 1986-01-25 1987-08-01 Nippon Synthetic Chem Ind Co Ltd:The マロン酸誘導体の製造方法
WO2001036380A2 (en) * 1999-11-19 2001-05-25 Closure Medical Corporation Transesterification method for making cyanoacrylates
WO2002014263A1 (fr) * 2000-08-11 2002-02-21 Otsuka Chemical Co., Ltd. Acylacetonitriles, leur procede de preparation et acaricides renfermant ces acylacetonitriles

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US4031243A (en) * 1975-07-03 1977-06-21 Juste, S.A. Quimico-Farmaceutica 2-(4-Isobutyl phenyl)butyric acid, salts thereof, and pharmaceutical compositions containing the same
JPS62175438A (ja) * 1986-01-25 1987-08-01 Nippon Synthetic Chem Ind Co Ltd:The マロン酸誘導体の製造方法
WO2001036380A2 (en) * 1999-11-19 2001-05-25 Closure Medical Corporation Transesterification method for making cyanoacrylates
WO2002014263A1 (fr) * 2000-08-11 2002-02-21 Otsuka Chemical Co., Ltd. Acylacetonitriles, leur procede de preparation et acaricides renfermant ces acylacetonitriles

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HALL H.K. JR. ET AL.: "Condensation polymerization of alpha-alpha'-dimethoxycarbonyl-p-xylylenedicyanide (1) and oxidation to a quinodimethane polymer", POLYMER BULLETIN, vol. 7, no. 4, 1982, pages 173 - 176, XP002974105 *
SAIGO K. ET AL.: "Enantioselective alkylation using optically active phase transfer catalyst", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 52, no. 10, 1979, pages 3119 - 3120, XP002974104 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102140071A (zh) * 2011-03-10 2011-08-03 天津市施普乐农药技术发展有限公司 2-(4-叔丁基苯基)-氰基乙酸(2-甲氧基)乙基酯的合成方法

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