WO2004085374A1 - 含フッ素アクリル酸エステルの製法 - Google Patents
含フッ素アクリル酸エステルの製法 Download PDFInfo
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- WO2004085374A1 WO2004085374A1 PCT/JP2004/004017 JP2004004017W WO2004085374A1 WO 2004085374 A1 WO2004085374 A1 WO 2004085374A1 JP 2004004017 W JP2004004017 W JP 2004004017W WO 2004085374 A1 WO2004085374 A1 WO 2004085374A1
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- stirred
- palladium
- autoclave
- ester
- trifluoropropane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Definitions
- the present invention relates to a method for producing a fluorine-containing acrylate, which is a useful compound widely used as a raw material for pharmaceuticals and functional polymers, and the like.
- ⁇ -Trifluoromethylacrylic acid is reacted with thionyl chloride to form ⁇ -trifluoromethylacrylic acid chloride, and this compound is reacted with fluorinated alcohol in the presence of a base to give one trifluoromethyl chloride.
- Patent Document 1 A method for synthesizing romethyl acrylate (Patent Document 1).
- Patent Document 2 A method of reacting ⁇ -trifluoromethylacrylic acid with fluorinated alcohol or methanol in the presence of fuming sulfuric acid to synthesize ⁇ -trifluoromethylacrylic acid ester (Patent Document 2).
- Patent Document 3 (Patent Document 3).
- the method (1) has a drawback that the yield of the reaction for converting to trifluoromethylacrylic acid chloride is low and an acid anhydride is by-produced.
- the method (2) has a disadvantage that a large amount of fuming sulfuric acid, which is not easy to handle, must be used.
- the method (3) has a drawback that an alkoxy fluorinated propionate is given as a main product.
- "1 It can be converted directly to 2-halo-3,3,3-trifluoropropene in the system using 1,1-trifluoro-2,3-dihalopropane.
- Patent Document 1 Japanese Patent Publication No. 3-8332
- Patent Document 2 Japanese Patent Application Laid-Open No. Sho 60-42352
- Patent Document 3 Japanese Patent Application Laid-Open No. 58-154549
- An object of the present invention is to provide a simple and highly versatile method for producing a fluorinated acrylate ester which overcomes many of the drawbacks of the prior art as described above.
- the present inventors have conducted intensive studies to solve the above-mentioned drawbacks of the conventional method, and as a result, have found that 1-bromo-11-perfluoroalkylethene or 1,2-jib
- the present inventors have found a simple, versatile and highly selective method for producing a fluorine-containing acrylic acid ester from a fluoroalkylene as a raw material, and have completed the present invention.
- the present invention relates to a compound represented by the general formula (I) or (I) in the presence of a palladium catalyst, carbon monoxide and two or more bases.
- R f represents a perfluoroalkyl group.
- the alkyl group in the present invention means a linear, branched, or cyclic alkyl group having from 2 to 20 carbon atoms, preferably from 1 to 15 carbon atoms which may have a substituent that does not participate in the reaction.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a pentyl group, and a 1,1-dimethylpropyl group.
- the perfluoroalkyl group in the present invention means a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
- the fluorinated alkyl group include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group.
- the present invention is carried out in the presence of a palladium catalyst.
- palladium catalysts that can be used include metal palladium such as palladium black and palladium sponge, palladium Z carbon, palladium Z alumina, palladium asbestos, palladium Z barium sulfate, palladium / barium carbonate, and palladium Z calcium carbonate.
- Palladium, palladium Z supported palladium such as polyethyleneamine, palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, palladium sulfate, palladium cyanide, arylpalladium chloride dimer Palladium salts such as palladium acetyl acetate, sodium hexacloparadide, potassium hexachloroparadide, sodium tetracloparadet, potassium tetrac Bout paradate, power Lium tetrabromoparadate, borofluoride tetra (acetonitrile) palladium, ammonium tetrachloride parade, ammonium hexaclode parade, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, tris (dibenzylidene) Acetone
- an amine-based complex or a phosphine-based complex it can be prepared and used in a reaction system by adding a ligand to the precursor palladium compound.
- ligands of the amine complex which can be prepared and used in the system include, for example, ammonia, getylamine, triethylamine, 1,2-bis (dimethylamino) ethane, 1,2-bis (diphenylamino) ethane , 1,2-bis (dimethylamino) propane, 1,3-bis (dimethylamino) propane, pyridine, aminopyridin, dimethylaminopyridine, 2,2'-biviridyl, 4,4'-dimethyl-2, Examples include 2'-bipyridyl, 2,2, -piquinoline, phenanthroline, and tetramethylphenanthroline.
- phosphine complex ligands examples include, for example, triphenylphosphine, tricyclohexylphosphine, tributylphosphine, 1,2-bis (diphenylphosphino) 1,2-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1, —bis (diphenylphosphino) phene, diphenylphosphinobenzene—3— Sodium sulfonic acid salt, tricyclohexylphosphine, tri (2-furyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-methylphenyl) ) Phosphine, Tris (3-methylphenyl) phosphine, Tris (2-methylphenyl) phosphine, etc.
- the amount of these palladium catalysts used may be a so-called catalytic amount, and is 0.001 to 0.1 with respect to the 1,2-dibutorone 1-perfluoroalkylethane represented by the general formula (I).
- a range of about 1 equivalent is selected, but usually about 0.001 to 0.05 equivalent may be used.
- the alcohol represented by the general formula (III) means a linear, branched, or cyclic aliphatic alcohol having 1 to 20 carbon atoms which may have a substituent that does not participate in the reaction.
- Examples of alcohols include, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, cyclohexylethanol, 2-propanol, 2-methyl-2-propanol, 2-butanol.
- 2-hexanol amyl alcohol, 2-methyl-11-propanol, cyclopentanol, cyclohexanol, cyclooctanol, 3-methylcyclohexanol, 4-methylcyclohexanol, benzyl alcohol, 2, 2, 2-trifluoroethanol, ethylene glycol monomethyl ether, 2 Examples thereof include 2-methyl-2-adamanol, 2-ethyl-2-adamantanol, 2-butyl-2-adamantanol, 1,3-adamantanediol, and 2-norpolanol.
- the alcohol is used in an amount of 1 equivalent to a large excess with respect to 1,2-dibutanol per 1-perfluoroalkylethane represented by the general formula (I), and may also serve as a solvent. Yes, but usually 1 to 5 equivalents should be used.
- the reaction is carried out under carbon monoxide pressure.
- the reaction method is not particularly limited, and may be, for example, a batch method or a semi-batch method.
- the carbon monoxide pressure is usually selected from the range of 0.1 to 10 MPaG, but from the viewpoint of safety, economy and the like, about 0.5 to 5 MPaG is preferable from the viewpoint of reaction efficiency.
- the present invention is carried out in the presence of two or more bases, and preferably at least one of the two or more bases is an inorganic base, an inorganic salt or an organic metal, or preferably at least one base One of them is amines.
- inorganic bases examples include, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium methoxide, potassium tert-butoxide, and magnesium methoxide.
- alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium methoxide, potassium tert-butoxide, and magnesium methoxide.
- alkaline earth metal alkoxides such as oxide and magnesium dimethoxide, and anion exchange resins.
- Examples of the inorganic salts that can be used include, for example, alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride, and alkaline earth metal hydrides such as beryllium hydride, magnesium hydride, and calcium hydride.
- Metal hydroxide such as lithium hydroxide, sodium hydroxide, hydroxide hydroxide, alkaline earth metal hydroxide such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbonate, carbonate
- Alkali metal carbonates such as sodium and potassium carbonate
- alkaline earth metal carbonates such as beryllium carbonate, magnesium carbonate and calcium carbonate Examples can be given.
- organic metal examples include, for example, organic alkali metal compounds such as butyllithium, t-butyllithium, phenyllithium, sodium trifluoromethyl, ethyl sodium, methylmagnesium bromide, dimethylmagnesium, phenyl Examples thereof include organic alkaline earth metal compounds such as magnesium chloride, phenyl calcium bromide, and bis (dicyclopentadiene) calcium.
- organic alkali metal compounds such as butyllithium, t-butyllithium, phenyllithium, sodium trifluoromethyl, ethyl sodium, methylmagnesium bromide, dimethylmagnesium, phenyl
- organic alkaline earth metal compounds such as magnesium chloride, phenyl calcium bromide, and bis (dicyclopentadiene) calcium.
- amines examples include, for example, trimethylamine, triethylamine, triptylamine, N, N-dimethylaniline, dimethylpenzylamine, N, N, ⁇ ', ⁇ , -tetramethyl_1,8-naphthalenediamine
- tertiary amines such as amines
- heteroaromatic amines such as pyridine, pyrrol, peracyl, collidine, and lutidine.
- an inorganic base, an inorganic salt, or a base obtained by combining an organic metal with an amine is preferable in terms of yield, reaction efficiency, and selectivity.
- the amount of the inorganic base, the inorganic salt or the organic metal to be used is preferably at least one kind in a molar ratio of 0.001 to 1 with respect to the compound of the general formula (I) or (II). It is preferable in terms of efficiency, reaction efficiency and selectivity.
- the amount of the amine to be used is selected in a range of 1 to a large excess in molar ratio with respect to the compound of the general formula (I) or ( ⁇ ), but usually about 1 to 8 equivalents may be used.
- the alcohol of the above general formula (III) can also serve as a solvent, but it is preferable to use a solvent which does not participate in the reaction.
- Solvents that can be used include aromatic solvents such as benzene, toluene, and xylene, hydrocarbon solvents such as hexane and oxane, acetone, acetonitrile, sulfolane, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, and dimethyl.
- examples thereof include polar solvents such as methylpyrrolidone, 1,3-dimethyl_2-imidazolidinone, and hexamethyltriamide phosphate.
- the amount of the solvent used is not particularly limited as long as a part or all of the raw materials are dissolved at the reaction temperature.
- the reaction temperature can be appropriately selected from the range of room temperature to 300 ° C., but the range of 50 ° C. to 160 ° C. is preferable in view of the reaction efficiency.
- Example 1 In an autoclave, 2,3-dibromo-1,1,1-trifluoropropane (0.2559 g, 1. Ommo 1), ethanol (0.057 g, 1.24 mmo 1), triethylamine (0.202 g, 2. Ommo 1), 60% —sodium hydride (0.0080 g, 0.2 mmol), dichlorobis (triphenylphosphine) palladium (() (0.0070 g, 0.0 lmmo 1), tetrahydrofuran (2 . OmL), carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 100 ⁇ for 15 hours.
- 2,3-dibromo-1,1,1-trifluoropropane (0.2559 g, 1. Ommo 1), ethanol (0.057 g, 1.24 mmo 1), triethylamine (0.202 g, 2. Ommo 1), 60% —sodium hydride (0.0080 g,
- 2,3-Jib mouth 1,1,1-trifluoropropane (0.2559 g, 1. Ommo 1), cyclohexylmethanol (0.137 g, 1.2 mmo 1), triethylamine (0.202 g, 2.0 mm o 1), sodium carbonate (0.0106 g, 0.1 lmmo 1), dichlorobis (triphenylphosphine) palladium ( ⁇ ) (0.0070 g, 0. 01 mmol), tetrahydrofuran (2. OmL), and carbon monoxide (1. OMP aG).
- 2,3_Jib mouth mo 1,1,1_Trifluoropropane (0.2559 g, 1. Ommo 1), cyclohexylmethanol (0.137 g, 1.2 mmo 1), triethylamine (0 223 g, 2.2 mmo 1), dichloropis (triphenylphosphine) palladium (II) (0.0070 g, 0.0 lmmol), tetrahydrofuran (2. OmL), and carbon monoxide (1. OMP a G) was introduced, and the mixture was stirred at 120 ° C for 5 hours.
- 2,3-dibromo-1-1,1,1-trifluoropropane (0.2559 g, 1. Ommo 1), benzyl alcohol (0.130 g, 1.2 mmol), triethylamine (0.202 g) g, 2. Ommo 1), lithium carbonate (0.0148 g, 0.2 mmo 1), dichlorobis (triphenylphosphine) palladium (II) (0.0070 g, 0.0 lmmo 1), tetrahydrofuran (2.0 mL), carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 120 ° C for 5 hours.
- 2,3_ jib mouth 1,1,1_ trifluoropropane (0.2559 g, 1. Ommo 1), benzyl alcohol (0.119 g, 1. lmmol), triethylamine ( 0.223 g, 2.2 mmo 1), dichlorobis (triphenylphosphine) palladium (II) (0.0070 g, 0.0 lmmo 1), tetrahydrofuran (2.OmL) were charged, and carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 120 ° C for 15 hours.
- 2,3-Jib mouth mo 1,1,1_ trifluoropropane (0.2559 g, 1. Ommo 1), cyclohexanol (0.120 g, 1.2 mmo 1), triethylamine (0 202 g, 2. Ommo 1), sodium carbonate (0.0106 g, 0.1 lmmo 1), diclomouth bis (triphenylphosphine) palladium (II) (0.00070 g, 0.01 mmol), Toluene (2. OmL) was charged, carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 100 ° C for 15 hours.
- 2,3-Jib mouth mo 1,1,1 _ trifluoropropane (0.2559 g, 1. Ommo 1), cyclohexanol (0.120 g, 1.2 mmol), triethylamine ( 0.223 g, 2.2 mmo 1), dichloromethane (bis (triphenylphosphine) palladium (II) (0.00070 g, 0.0 lmmo 1), and toluene (2. OmL) were charged, and carbon monoxide ( 1. OMP aG) was introduced, and the mixture was stirred at 120 ° C for 5 hours.
- 2,3-dibromo-1,1,1-trifluoropropane (0.2559 g, 1. Ommo 1), cyclooctanol (0.154 g, 1.2 mmol), triethylamine (0. 223 g, 2.2 mmo 1), dichloromethane (bis (triphenylphosphine) palladium (II) (0.0070 g, 0.0 lmmo 1), toluene (2.OmL), and carbon monoxide (1. OMP aG) was introduced and the mixture was stirred at 120 for 5 hours.
- 2,3-dibromo-1,1,1-trifluoropropane (0.2559 g, 1. Ommo 1), cyclooctanol (0.154 g, 1.2 mmol), triethylamine (0. 223 g, 2.2 mmo 1), dichloromethane (bis (triphenylphosphine) palladium (II) (0.0070
- 2,3-dibromo-1,1,1-trifluoropropane (0.2559 g, 1. Ommo 1), 1-cyclohexylethanol (0.154 g, 1.2 mmo 1), triethylamine in an autoclave (0.202 g, 2.0 mmo 1), sodium t-butoxide (0.0192 g, 0.2 mmo 1), dichlorobis (triphenylphosphine) palladium (II) (0.0070 g, 0. 01mmo l), Luen (2. OmL) was charged, carbon monoxide (1.0MPaG) was introduced, and the mixture was stirred at 120 ° C for 5 hours.
- 2,3 _ jib-mouth 1,1, 1 _ trifluoropropane (0.2559 g, 1. Ommol), 1-cyclohexylethanol (0.154 g, 1.2 mmol) ), Triethylamine (0.223 g, 2.2 mmol), dichlorobis (triphenylphosphine) palladium ( ⁇ ) (0.0070 g, 0.01 mmol), and toluene (2.0 mL)
- carbon monoxide 1.0MPaG
- 2,3-Dibromo-1,1,1-trifluoropropane (0.2559 g, 1.0 mmol), 1-adamantanol (0.283 g, 1.2 mmol), Triethylamine (0.202 g, 2. Ommo 1), lithium carbonate (0.0074 g, 0.1 lmmo 1), dichlorobis (triphenylphosphine) palladium (II) (0.0070 g, 0.01 mmo) l) and tetrahydrofuran (2.0 mL) were charged, carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 100 for 5 hours.
- 2,3-dibromo-1,1,1,1-trifluoropropane (0.2559 g, 1.Ommo 1), 2-methyl-2-adamantanol (0.332 g, 2.Ommol), Triethylamine (0.223 g, 2.2 mmol), dichloromethane bis (triphenylphosphine) palladium (II) (0.0070 g, 0.
- 2,3-dibutone 1,1,1-trifluoropropane (0.2559 g, 1.0 mmol), 2-methyl-2-adamantanol (0.249 g, 1.5 mmol) ), Triethylamine (0.202 g, 2.Ommol), lithium carbonate (0.0369 g, 0.5 mmo1), dichloride bis (triphenylphosphine) palladium (II) (0.0070 g, 0.070 g 0 lmmo 1) and tetrahydrofuran (2. OmL) were charged, carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 100 ° C for 15 hours.
- 2,3-dibromo-1,1,1-trifluorotrifluoropropane (0.2559 g, 1. Ommo 1), 1,3-adamantanediol (0.202 g, 1.2 mmol), Triethylamine (0.202 g, 2. Ommo 1)> 60% sodium monohydride (0.0080 g, 0.2 mmo 1), diclomouth bis (triphenylphosphine) palladium (II) (0.0070 g) , 0. Olmmol) and tetrahydrofuran (2. OmL) were introduced, carbon monoxide (1. OMPaG) was introduced, and the mixture was stirred at 100 ° C for 15 hours.
- 2,3-Jib mouth mode 1, 1-Trifluoropropane (0, 2559 g, 1. Ommo 1), 1,3-Adamantanediol (0.2202 g, 1.2 mmo l), Triethylamine (0.202 g, 2. Ommo 1), sodium carbonate (0.0106 g) , 0.1 lmmo 1), dichlorobis (triphenylphosphine) palladium (II) (0.0070 g, 0.01 mm o 1), tetrahydrofuran (2. OmL), and carbon monoxide (1. OMP aG) and stirred at 100 ° C for 15 hours.
- Ommo 1 t-butyl alcohol (0.089 g, 1.2 mmo 1), triethylamine (0.101 g) in autoclave , 1. Ommo 1), lithium carbonate (0.014 8 g, 0.2 mmo 1), dichlorobis (triphenylphosphine) palladium (II) (0.0070 g, 0.01 mmo 1), tetrahydrofuran (2. OmL), and carbon monoxide (1. OMP aG) and stirred at 100 ° C for 5 hours. After the reaction was completed, the autoclave was cooled, opened, benzotrifluoride was added as an internal standard substance, stirred, and allowed to stand for a while to precipitate salts.
- 2-Bromo-1,3,3,3-trifluoropropene (0.175 g, 1. Ommo 1), 2-methyl-12-adamanmannol (0.200 g, 1.2 mmol) ), Triethylamine (0.101 g, 1. Ommo 1), lithium carbonate (0.0369 g, 0.5 mmo 1), dichlorobis (triphenylphosphine) palladium ( ⁇ ) (0.0070 g, 0.0 lmmo) 1), tetrahydrofuran (2. OmL) was charged, carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 100 ° C for 15 hours.
- 2-Bromo-1,3,3,3-trifluoropropene (0.175 g, 1. Ommo 1), 2-butyl-2-adamantanol (0.250 g, 1.2 mmol) ), Triethylamine (0.101 g, 1. Ommo 1), Lithium carbonate (0.0148 g, 0.2 mmo 1), Dichroic bis (triphenylphosphine) palladium (II) (0.0070 g, 0.10 g) 0 lmmo 1) and cyclopentyl methyl ether (2. OmL) were charged, carbon monoxide (1. OMP aG) was introduced, and the mixture was stirred at 10 O for 15 hours.
- the present invention provides a simple, versatile and highly selective method for producing a fluorine-containing acrylate ester, which is a useful compound widely used as a raw material for pharmaceuticals and functional polymers.
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Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04722998.4A EP1637514B1 (en) | 2003-03-26 | 2004-03-24 | Method for producing fluorine-containing acrylate |
US10/550,387 US7470808B2 (en) | 2003-03-26 | 2004-03-24 | Method for producing fluorine-containing acrylate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2003-085164 | 2003-03-26 | ||
JP2003085164 | 2003-03-26 |
Publications (1)
Publication Number | Publication Date |
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WO2004085374A1 true WO2004085374A1 (ja) | 2004-10-07 |
Family
ID=33095017
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PCT/JP2004/004017 WO2004085374A1 (ja) | 2003-03-26 | 2004-03-24 | 含フッ素アクリル酸エステルの製法 |
Country Status (3)
Country | Link |
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US (1) | US7470808B2 (ja) |
EP (1) | EP1637514B1 (ja) |
WO (1) | WO2004085374A1 (ja) |
Families Citing this family (3)
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JP5231973B2 (ja) | 2007-12-26 | 2013-07-10 | 東レ・ダウコーニング株式会社 | 有機ケイ素化合物およびその製造方法 |
CN103058851B (zh) * | 2012-11-06 | 2015-02-11 | 西安近代化学研究所 | 一种2-三氟甲基丙烯酸的制备方法 |
GB2577315A (en) | 2018-09-21 | 2020-03-25 | Mexichem Fluor Sa De Cv | Methods |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58154529A (ja) * | 1982-03-09 | 1983-09-14 | Sagami Chem Res Center | α‐トリフルオロメチルアクリル酸およびその誘導体の製造方法 |
JPS63152342A (ja) * | 1986-07-11 | 1988-06-24 | Sagami Chem Res Center | 含フツ素カルボン酸エステルの製法 |
JPH08104661A (ja) * | 1994-10-05 | 1996-04-23 | Sumitomo Chem Co Ltd | 芳香族カルボン酸類の製造方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3771598D1 (de) | 1986-07-11 | 1991-08-29 | Sagami Chem Res | Verfahren zur herstellung eines esters einer fluorhaltigen carbonsaeure. |
-
2004
- 2004-03-24 EP EP04722998.4A patent/EP1637514B1/en not_active Expired - Fee Related
- 2004-03-24 US US10/550,387 patent/US7470808B2/en not_active Expired - Fee Related
- 2004-03-24 WO PCT/JP2004/004017 patent/WO2004085374A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58154529A (ja) * | 1982-03-09 | 1983-09-14 | Sagami Chem Res Center | α‐トリフルオロメチルアクリル酸およびその誘導体の製造方法 |
JPS63152342A (ja) * | 1986-07-11 | 1988-06-24 | Sagami Chem Res Center | 含フツ素カルボン酸エステルの製法 |
JPH08104661A (ja) * | 1994-10-05 | 1996-04-23 | Sumitomo Chem Co Ltd | 芳香族カルボン酸類の製造方法 |
Non-Patent Citations (2)
Title |
---|
MATTEOLI U. ET AL: "Esters and N,N-dialkylamides of 2-(trifluoromethyl)acrylic acid (TFMAA) through Pd-catalysed carbonylation of fluorinated unsaturated substrates", J. OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 143, no. 1-3, 1999, pages 287 - 295, XP002980361 * |
See also references of EP1637514A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP1637514B1 (en) | 2014-05-07 |
US7470808B2 (en) | 2008-12-30 |
EP1637514A4 (en) | 2006-09-20 |
US20060122423A1 (en) | 2006-06-08 |
EP1637514A1 (en) | 2006-03-22 |
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