WO2017033955A1 - Procédé de production d'un dérivé d'ester acrylique halogéné - Google Patents

Procédé de production d'un dérivé d'ester acrylique halogéné Download PDF

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WO2017033955A1
WO2017033955A1 PCT/JP2016/074598 JP2016074598W WO2017033955A1 WO 2017033955 A1 WO2017033955 A1 WO 2017033955A1 JP 2016074598 W JP2016074598 W JP 2016074598W WO 2017033955 A1 WO2017033955 A1 WO 2017033955A1
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group
formula
production method
reaction
derivative
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貢 笠川
安田　新
祐 小野崎
聡史 河口
直輝 市野川
勇佑 冨依
卓志 秋谷
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旭硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/32—Compounds having groups or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/27—Preparation of carboxylic acid esters from ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/60—Preparation of compounds having groups or groups

Definitions

  • the present invention relates to a novel method for producing a halogenated acrylate derivative.
  • ⁇ -Fluoroacrylic acid esters which represent halogenated acrylic acid ester derivatives, are useful as synthetic intermediates for drugs, polymers, optical materials, paints, semiconductor resist materials, etc., or as monomers of functional polymers.
  • thionyl chloride is used to convert 3-hydroxy-2-fluoropropionic acid ester to 3-chloro-2-fluoropropionic acid ester, from which hydrogen chloride is eliminated and 2
  • Patent Document 1 using -fluoroacrylic acid ester is known.
  • Patent Document 2 discloses a method in which an ethylene derivative is led to a cyclopropane derivative using potassium t-butoxide and a large excess of chlorofluorocarbon, and this is decomposed to produce ⁇ -fluoroacrylic acid ethyl ester.
  • a method for synthesizing an ethylene derivative used in Patent Document 2 1,1-diethoxy-2-bromoethane is allowed to act on potassium t-butoxide to remove hydrobromic acid, and 1,1-diethoxyethene is obtained.
  • the method to obtain is known (nonpatent literature 1).
  • Patent No. 5628305 European Patent Publication No. 0127920
  • Patent Document 1 is industrially disadvantageous in that thionyl chloride needs to be used and highly corrosive hydrogen chloride is generated. Also, it is industrially disadvantageous in that F 2 (fluorine gas), which is difficult to handle, is used for preparing the raw material 3-hydroxy-2-fluoropropionic acid ester.
  • the method of Patent Document 2 is also industrially disadvantageous because it uses expensive potassium t-butoxide and a large excess of chlorofluorocarbon.
  • the method of Non-Patent Document 1 cannot be an industrially economical production of ethylene derivatives in that expensive potassium t-butoxide needs to be used and highly corrosive hydrogen bromide is generated.
  • the present inventors have found a novel method for producing a halogenated acrylic ester derivative that achieves high conversion, high selectivity, and high yield, and is excellent in terms of industrial economy, and a useful intermediate therefor. .
  • a compound represented by the following formula (1) and having a boiling point of 500 ° C. or lower is subjected to a de-R 3 OH reaction in the presence of a solid catalyst in a gas phase: A method for producing an ethene derivative represented by 2).
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent group essentially comprising a carbon atom, or R 1 and R 2 together form a ring with the carbon atom to which they are attached.
  • R 3 represents a monovalent group from which the group R 3 O can be removed by a de-R 3 OH reaction
  • R 4 and R 5 each independently represents a hydrogen atom or a monovalent group essentially comprising a carbon atom.
  • R 1 and R 2 are both hydrogen atoms
  • R 3 , R 4 and R 5 are each independently an alkyl group, a cycloalkyl group, an aryl group, an alkyl group having a substituent, or a substituent.
  • the solid catalyst is a catalyst containing at least one selected from the group consisting of zirconia, alumina, zeolite, and zinc oxide.
  • the solid catalyst is a catalyst containing zinc oxide.
  • the solid catalyst is at least one solid catalyst selected from natural minerals, molecular sieves, carbon black, metal chloride, metal fluoride, metal sulfate, metal sulfide, and metal phosphate [1] to [5]
  • the ethene derivative represented by the formula (2) is obtained by the production method according to any one of [1] to [10], and the ethene derivative is converted to the following formula in the presence of a basic compound and a phase transfer catalyst.
  • a cyclopropane derivative represented by the formula (4) and a propene derivative represented by the following formula (8) are obtained by the production method according to any one of [11] to [18].
  • a halogenated acrylate derivative can be produced from an inexpensive and readily available raw material through a novel and useful intermediate with high conversion, high selectivity and high yield.
  • alkyl group means a linear or branched monovalent saturated hydrocarbon group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert -Pentyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, neohexyl group and the like.
  • the “alkyl group” may be a monovalent saturated hydrocarbon group partially having a ring structure. For example, a cycloalkylalkyl group etc. are mentioned.
  • “Cycloalkyl group” means a cyclic monovalent saturated hydrocarbon group.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, still more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms.
  • the number of ring structures in the cycloalkyl group may be one or two or more. In the case of two or more, it has a condensed polycyclic structure, a bridged ring structure or a spiro ring structure.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
  • alkenyl group means a group in which any carbon-carbon single bond of the alkyl group (excluding a methyl group) is replaced with a carbon-carbon double bond.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
  • alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl Group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 1-hexenyl group and the like.
  • the “cycloalkenyl group” means a group in which any carbon-carbon single bond of the cycloalkyl group is replaced with a carbon-carbon double bond.
  • the number of ring structures in the cycloalkenyl group may be one or two or more. In the case of two or more, it has a condensed polycyclic structure, a bridged ring structure or a spiro ring structure.
  • the cycloalkenyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, still more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms.
  • Examples of the cycloalkenyl group include 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-methyl-2-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3- A cyclohexenyl group etc. are mentioned.
  • Alkynyl group refers to any carbon-carbon single bond of the alkyl group (excluding a methyl group) or any carbon-carbon single bond or carbon-carbon double bond of the alkenyl group. It means a group replaced with a carbon triple bond.
  • the alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
  • alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 1-pentynyl group, 1-pentynyl group, A hexynyl group etc. are mentioned.
  • Alkoxy group means a group in which the alkyl group is bonded to an etheric oxygen atom (—O—).
  • the structure of the alkoxy group is preferably linear or branched.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
  • Aryl group means a monocyclic or bicyclic or higher aromatic hydrocarbon group.
  • the aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms.
  • Examples of the aryl group include a phenyl group, o-, p- or m-tolyl group, naphthyl group, phenanthrenyl group, anthracenyl group, fluorenyl group and the like.
  • Heteroaryl group means an aromatic group having one or more heteroatoms. As a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable.
  • the heteroaryl group preferably has 3 to 21 carbon atoms, more preferably 3 to 17 carbon atoms, still more preferably 3 to 13 carbon atoms, and particularly preferably 3 to 9 carbon atoms.
  • heteroaryl group examples include pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, thienyl group, furyl group, pyrrolyl group, pyrazolyl group, triazolyl group, imidazolyl group, thiazolyl group, oxazolyl group, indolyl group, quinolyl group and the like. Can be mentioned.
  • Aryloxy group means a group in which the aryl group is bonded to an etheric oxygen atom (—O—).
  • the aryloxy group preferably has 7 to 23 carbon atoms, particularly preferably 7 to 19 carbon atoms, more preferably 7 to 15 carbon atoms, and still more preferably 7 to 11 carbon atoms. Examples of the aryloxy group include a phenoxy group.
  • Alkylthio group means a group in which the alkyl group is bonded to —S—.
  • the alkylthio group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • alkylthio group examples include a methanethio group, an ethanethio group, an n-propanethio group, an isopropanethio group, an n-butanethio group, an isobutanethio group, an s-butanethio group, a t-butanethio group, an n-pentanethio group, and an n-hexanethio group.
  • the “monoalkylamino group” means a group in which one hydrogen atom of an amino group (—NH 2 ) is replaced with the alkyl group.
  • the “dialkylamino group” means a group in which two hydrogen atoms of an amino group are replaced with the alkyl group.
  • the monoalkylamino group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the dialkylamino group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • Examples of the monoalkylamino group include a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, a t-butylamino group, an n-pentylamino group, and an n-hexylamino group.
  • Examples of the dialkylamino group include N, N-dimethylamino group and N, N-diethylamino group.
  • “Monoarylamino group” means a group in which one of the hydrogen atoms of the amino group is replaced with the aryl group.
  • the “diarylamino group” means a group in which two of the amino group hydrogen atoms are replaced with the aryl group.
  • the monoarylamino group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms.
  • the diarylamino group preferably has 12 to 24 carbon atoms, more preferably 12 to 20 carbon atoms, and still more preferably 12 to 16 carbon atoms. Examples of the monoarylamino group include a phenylamino group. Examples of the diarylamino group include a diphenylamino group.
  • Heterocyclyl group means a saturated or unsaturated monovalent heterocyclic group having one or more heteroatoms.
  • a hetero atom an oxygen atom, a sulfur atom, and a nitrogen atom are preferable.
  • the heterocyclyl group preferably has 3 to 21 carbon atoms, more preferably 3 to 17 carbon atoms, still more preferably 3 to 13 carbon atoms, and particularly preferably 3 to 9 carbon atoms.
  • Examples of the heterocyclyl group include azepanyl group, pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, tetrahydrofuryl group and the like.
  • Halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom.
  • alkyl group “cycloalkyl group”, “alkenyl group”, “cycloalkenyl group”, “alkynyl group”, “alkoxy group”, “aryl group”, “heteroaryl group”, “aryloxy group”,
  • alkylthio group “monoalkylamino group”, “dialkylamino group”, “monoarylamino group”, “diarylamino group” and “heterocyclyl group” may be substituted with a substituent.
  • a group substituted with the substituent is referred to as a group having a substituent.
  • substituents examples include alkyl groups, alkenyl groups, alkoxy groups, aryl groups, alkylthio groups, nitro groups, amino groups, carboxyl groups, cycloalkyl groups, hydroxyl groups, halogen atoms, cyano groups, phenyl groups, and heterocyclyl groups. It is done.
  • Step (i) is a compound represented by the formula (1) having a boiling point of 500 ° C. or lower (hereinafter, this compound is also referred to as “orthocarboxylic acid ester (1)”) in the gas phase.
  • this compound is also referred to as “orthocarboxylic acid ester (1)”
  • a de-R 3 OH reaction is carried out in the presence of a solid catalyst to produce an ethene derivative represented by the formula (2) (hereinafter also simply referred to as “ethene derivative (2)”).
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent group essentially comprising a carbon atom.
  • R 1 and R 2 are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, aryl group, heteroaryl group, aryloxy group, alkylthio group, monoalkylamino Group, dialkylamino group, monoarylamino group, diarylamino group, heterocyclyl group, substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted Cycloalkenyl group having a group, alkynyl group having a substituent, an alkoxy group having a substituent, an aryl group having a substituent, a heteroaryl group having a substituent , Aryloxy group having a substituent, alkylthio group having
  • R 1 and R 2 may together form a ring with the carbon atom to which they are attached.
  • the ring formed by R 1 and R 2 together with the carbon atom to which they are bonded include cycloalkanes such as cyclohexane or cycloalkanes having a substituent such as cyclohexane substituted with an alkyl group.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, a substituted alkyl group, or a substituted cycloalkyl group. Further, an alkoxy group having a substituent, an aryl group having a substituent, or an aryloxy group having a substituent is more preferable.
  • R 1 and R 2 are particularly preferably both hydrogen atoms.
  • R 3 is a monovalent group from which the group R 3 O can be removed by a de-R 3 OH reaction.
  • R 3 is an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclyl group, an alkyl group having a substituent, or a cycloalkyl having a substituent.
  • R 3 is more preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyl group having a substituent, a cycloalkyl group having a substituent, or an aryl group having a substituent.
  • R 3 is more preferably an alkyl group, and particularly preferably a methyl group.
  • R 4 and R 5 are each independently a hydrogen atom or a monovalent group essentially comprising a carbon atom, and specifically includes a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group.
  • R 4 and R 5 each independently have an alkyl group, a cycloalkyl group, an aryl group, an alkyl group having a substituent, a cycloalkyl group having a substituent, or a substituent.
  • An aryl group is more preferred.
  • R 4 and R 5 are each independently more preferably an alkyl group, and particularly preferably a methyl group.
  • Suitable orthocarboxylic acid esters (1) include R 1 and R 2 are both hydrogen atoms, and R 3 , R 4 and R 5 are each independently an alkyl group, a cycloalkyl group, an aryl group, an alkyl group having a substituent, or a substituent. It is a compound which is a cycloalkyl group or an aryl group having a substituent.
  • R 1 and R 2 are both hydrogen atoms, and R 3 , R 4 and R 5 are each independently an alkyl group.
  • R 1 and R 2 are both hydrogen atoms, and R 3 , R 4 and R 5 are both methyl groups.
  • the substituent in the orthocarboxylic acid ester (1) must be selected so that the boiling point of the orthocarboxylic acid ester (1) is 500 ° C. or less.
  • the orthocarboxylic acid ester (1) can be synthesized by a known method or a similar method according to a conventional method of organic chemistry.
  • the typical trimethyl orthoacetate is commercially available and can be obtained very easily.
  • the boiling point of the orthocarboxylic acid ester (1) is preferably the temperature at which the orthocarboxylic acid ester (1) is vaporized at the reaction temperature and reaction pressure.
  • the boiling point in the following refers to the boiling point at 1 atmosphere (absolute pressure).
  • the orthocarboxylic acid ester (1) has a boiling point of 500 ° C. or lower, preferably 450 ° C. or lower, more preferably 400 ° C. or lower. Further, from the viewpoint of easy handling, the boiling point of the orthocarboxylic acid ester (1) is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 50 ° C. or higher.
  • the solid catalyst used in the reaction of step (i) is selected from catalysts that promote the de-R 3 OH reaction of the orthocarboxylic acid ester (1), and is a solid catalyst having a solid acid amount that promotes the de-R 3 OH reaction. It is preferred that it be selected.
  • solid catalysts include metal catalysts, metal oxide catalysts, natural minerals, molecular sieves, and carbon black.
  • the natural mineral is preferably acidic clay, kaolinite, bentonite, montmorillonite, talc, zirconium silicate, or zeolite.
  • the carbon black is preferably amorphous carbon, charcoal, activated carbon, graphite or fullerenes.
  • the solid catalyst is preferably at least one selected from metal catalysts and metal oxide catalysts, and more preferably metal oxide catalysts.
  • a catalyst composed of Group IVB and Group VIII metals of the periodic table is preferable, and molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridium, osmium, rhodium, rhenium, or ruthenium is preferable. .
  • a metal oxide catalyst is a catalyst containing a metal oxide, such as silica, alumina, zirconia, titania, tungsten oxide, magnesium oxide (magnesia), vanadium oxide, chromium oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, Copper oxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, boron oxide (boria), zeolite, or mixtures thereof are preferred.
  • a metal oxide such as silica, alumina, zirconia, titania, tungsten oxide, magnesium oxide (magnesia), vanadium oxide, chromium oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, Copper oxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, boron oxide (boria), zeolite, or mixtures thereof are preferred.
  • Metal oxide catalysts can be used as complex metal oxides such as silica-alumina, silica-magnesia, silica-boria, alumina-boria, silica-titania, silica-zirconia, zinc oxide-zirconia, molecular sieves, etc. in any molar ratio. May be.
  • the metal oxide catalyst from the viewpoint of activity, a catalyst containing at least one selected from the group consisting of zirconia (zirconium oxide), alumina, zeolite and zinc oxide is more preferable, and a catalyst containing zinc oxide is particularly preferable.
  • the content of at least one metal oxide selected from the group consisting of zirconia, alumina, zeolite and zinc oxide in the metal oxide catalyst is preferably 50% by mass or more based on the metal oxide catalyst. More preferably, it is more preferably 70% by mass or more.
  • zeolites include A-type zeolite, L-type zeolite, X-type zeolite, Y-type zeolite, MFI zeolite represented by ZSM-5 type, MWW-type zeolite, ⁇ -type zeolite, mordenite, ferrierite, Or erionite is preferable.
  • Examples of the solid catalyst used in the reaction in the step (i) other than the above include metal chlorides such as aluminum chloride, metal fluorides such as aluminum fluoride and calcium fluoride, metal sulfates such as iron sulfate, and zinc sulfide. Examples thereof include metal sulfides, metal phosphates such as zinc phosphate, solid catalysts such as metallosilicate catalysts, and solid catalysts in which a phosphorus compound, boron compound or the like is supported on an inert carrier.
  • the solid catalyst used for the reaction in step (i) may be used alone or in combination of two or more.
  • the solid acid amount of the solid catalyst is preferably more than 0 to 5.0 mmol / g, more preferably more than 0 to 3.0 mmol / g, still more preferably more than 0 to 1.0 mmol / g. If the amount of solid acid of a solid catalyst is more than a lower limit, the conversion rate of orthocarboxylic acid ester (1) will improve. If the amount of the solid acid of the solid catalyst is not more than the upper limit value, it is easy to suppress the formation of by-products.
  • the specific surface area of the solid catalyst is preferably 0.1 ⁇ 1000m 2 / g, more preferably 0.5 ⁇ 500m 2 / g, 1 ⁇ 350m 2 / g is more preferred.
  • the specific surface area of a solid catalyst is more than a lower limit, the conversion rate of orthocarboxylic acid ester (1) will improve. If the specific surface area of the solid catalyst is less than or equal to the upper limit, it is easy to suppress the formation of by-products.
  • the reaction of step (i) is performed in the gas phase.
  • the reaction in the gas phase can be performed by a conventional gas phase circulation method.
  • the gas phase circulation method is a method in which a solid catalyst is filled in a reactor, and the vaporized orthocarboxylic acid ester (1) is caused to flow through the solid catalyst layer to be reacted.
  • Specific examples include reaction systems such as a fixed bed circulation system, a fixed bed circulation system, and a fluidized bed circulation system, and any of these reaction systems can be applied in the present invention.
  • the vaporized orthocarboxylic acid ester (1) is circulated through the solid catalyst layer, but the orthocarboxylic acid ester (1) may be circulated alone or with a carrier gas.
  • a carrier gas Good.
  • Inert gas such as nitrogen gas, helium gas, argon gas, or these mixed gas is preferable.
  • the amount of carrier gas used is preferably more than 0 to 20 moles, more preferably more than 0 to 10 moles per mole of orthocarboxylic acid ester (1).
  • the conversion rate of orthocarboxylic acid ester (1) decreases
  • the amount of carrier gas is small, by-products are generated, impurities such as carbides adhere to the surface of the solid catalyst, and the catalytic activity decreases.
  • the optimum amount used also depends on the reaction temperature and contact time.
  • the reaction pressure is not particularly limited, and may be increased pressure, normal pressure, or reduced pressure. Since the operation is easy, the reaction pressure is preferably from normal pressure to slight pressure. If desired, a filler such as a static mixer or Raschig ring can be added.
  • the method of heating the reactor is not particularly limited, but a method of heating using a heat medium oil, a molten salt, an electric heater or sand is preferable.
  • the reaction temperature in step (i) is preferably from 100 to 500 ° C, more preferably from 120 to 450 ° C, still more preferably from 150 to 400 ° C.
  • the conversion rate of the orthocarboxylic acid ester (1) decreases, when the temperature is high, by-products are generated, impurities such as carbides adhere to the surface of the solid catalyst, and the catalytic activity decreases. there is a possibility.
  • the optimum reaction temperature also depends on the contact time.
  • the reaction time in step (i) corresponds to the time for which the orthocarboxylic acid ester (1) is in contact with the solid catalyst (hereinafter referred to as “contact time”).
  • the contact time is preferably from 0.1 to 60 seconds, more preferably from 1 to 30 seconds.
  • the contact time is short, the conversion rate of the orthocarboxylic acid ester (1) is lowered, when it is long, a by-product is formed, impurities such as carbides adhere to the surface of the solid catalyst, and the catalytic activity is lowered. There is sex.
  • the optimum contact time depends on the reaction temperature. For example, if the contact time is extremely short at 100 ° C., the reaction may not proceed substantially. If the contact time is extremely long at 500 ° C., by-products are generated or tar or oil is generated. The reactor may become clogged.
  • Step (i) is a step in which the production of the ethene derivative (2), which has been difficult in the past by using a solid catalyst, is performed by a gas phase reaction that is extremely advantageous in terms of handling, productivity, and the like.
  • the reaction in the step (i) is a gas phase reaction
  • the ethene derivative (2) can be continuously produced by, for example, a reaction mode in which the orthocarboxylic acid ester (1) is circulated through a tubular reactor. It is extremely superior in productivity than the conventional manufacturing method. Further, since the reaction is carried out in the gas phase, it is very easy to separate the products. Furthermore, step (i) is highly industrially very advantageous because it does not produce highly corrosive hydrogen chloride or the like, has high safety, and has few restrictions on the reaction apparatus.
  • the ethene derivative (2) (1,1-dimethoxyethene) in which R 4 and R 5 are methyl which was difficult to produce industrially and economically by the conventional method, is easy and Obtained in high yield.
  • the ethene derivative (2) obtained in step (i) is useful as a synthetic intermediate for various chemicals.
  • Step (ii) In the step (ii), the ethene derivative (2) obtained in the step (i) is converted into a halogenated methane represented by the formula (3) in the presence of a basic compound and a phase transfer catalyst (hereinafter simply referred to as “halogenation”).
  • halogenation a phase transfer catalyst
  • This is a step for producing a cyclopropane derivative represented by the formula (4) (hereinafter also simply referred to as “cyclopropane derivative (4)”) by reacting with methane (3) ”.
  • the ethene derivative (2) obtained in the step (i) may be used in the reaction of the step (ii) as it is without being purified. May be.
  • the purification method include known methods such as extraction using a solvent, distillation, and crystallization. In the purification, the orthocarboxylic acid ester (1) contained unreacted in the product of the step (i) can be separated and reused in the step (i). Can be improved.
  • step (ii) the halogenated methane (3) used is considered to generate a carbene by the action of the basic compound and be inserted into the double bond of the ethene derivative (2).
  • halogenated methane (3) for example, chloroform, dichlorofluoromethane, chlorodifluoromethane, or trifluoromethane is preferable.
  • Halogenated methane (3) in which X is a fluorine atom and Y is a chlorine atom or a fluorine atom is more preferred, and dichlorofluoromethane, chlorodifluoromethane, and trifluoromethane are more preferred.
  • Halogenated methane (3) in which X is a fluorine atom and Y is a chlorine atom is more preferable, and specifically, dichlorofluoromethane and chlorodifluoromethane are more preferable.
  • the halogenated methane (3) may be gasified and reacted, or may be reacted as a liquid. Further, the reaction solution may be extracted continuously and continuously, or may be performed batchwise without simultaneously extracting the reaction solution. From the viewpoint of productivity, it is advantageous to carry out continuously.
  • the amount of halogenated methane (3) to be used is preferably 1 mol or more, more preferably 1 to 5 mol, and further preferably 1 to 2 mol, relative to 1 mol of the ethene derivative (2).
  • the basic compound used in the reaction of step (ii) is a compound that accelerates the reaction for generating carbene from the halogenated methane (3).
  • Examples of basic compounds include alkaline earth or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and t-butoxy potassium; alkalis such as sodium hydride Metal hydride; alkyl lithium such as butyl lithium; alkali metal carbonate such as sodium carbonate and potassium carbonate; alkali metal hydrogen phosphate such as sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate or alkali Metal phosphates are preferred.
  • More preferred basic compounds are alkali metal hydroxides, alkali metal alkoxides, alkali metal hydrides or alkyllithiums.
  • a more preferred basic compound is an alkali metal hydroxide.
  • the most preferred basic compound is sodium hydroxide or potassium hydroxide.
  • a basic compound may be used individually by 1 type, and may use 2 or more types together. These basic compounds may be used as an aqueous solution, or may be used by mixing with an organic solvent.
  • the concentration of the basic compound in the solvent is preferably 5 to 60% by weight, and more preferably 10 to 60% by weight. If the concentration of the basic compound in the solution is low, the conversion rate of the ethene derivative (2) decreases, and if it is high, the conversion rate of the ethene derivative (2) increases.
  • the amount of the basic compound used in the reaction of step (ii) is an amount that can generate sufficient carbene for the reaction with the ethene compound from the halogenated methane (3).
  • 1 to 10 mol is preferable with respect to 1 mol, more preferably 1 to 8 mol, and still more preferably 1 to 6 mol.
  • step (ii) is performed in the presence of a phase transfer catalyst together with the basic compound.
  • a phase transfer catalyst As the phase transfer catalyst, general formula (R a ) 4 M + A ⁇ (wherein R a is independently a hydrogen atom or a C 1-25 hydrocarbon group, M is N or P, and A is OH, F, Br, Cl, I, HSO 4 , CN, CH 3 SO 3 or PhCH 2 CO 2 , where Ph represents a phenyl group) and crown ethers are preferred.
  • Specific examples include quaternary ammonium salts such as tetrabutylammonium salt, trioctylmethylammonium salt, and benzyldimethyloctadecylammonium salt.
  • phase transfer catalysts are preferably quaternary ammonium salts such as tetrabutylammonium bromide and tetrabutylammonium chloride. These phase transfer catalysts may be used as an aqueous solution, or may be used by mixing with an organic solvent.
  • the amount of the phase transfer catalyst used is preferably from 0.001 to 5 mass%, more preferably from 0.01 to 3 mass%, still more preferably from 0.05 to 2 mass%, based on the mass of the ethene derivative (2).
  • the reaction can be promoted by using a phase transfer catalyst.
  • Use of a general-purpose phase transfer catalyst (quaternary ammonium salt or the like) is advantageous in terms of cost.
  • the phase transfer catalyst may be used as a catalyst between an aqueous phase and an organic phase, or as a catalyst between two organic phases to be phase separated, such as a chlorinated fluorinated hydrocarbon solvent and a hydrocarbon solvent. Also good.
  • the use of a phase transfer catalyst can accelerate the reaction using two kinds of solvents that undergo phase separation.
  • the reaction in step (ii) is preferably carried out in the liquid phase and in the presence of a solvent.
  • the solvent is preferably water, an aliphatic hydrocarbon, a halogenated aliphatic hydrocarbon, an aromatic hydrocarbon, or a halogenated aromatic hydrocarbon.
  • the solvent examples include benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, petroleum ethers, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, dichloromethane, Examples include chloroform and carbon tetrachloride.
  • a solvent may be used individually by 1 type and may use 2 or more types together. When water is used as a solvent, a synergistic effect is obtained in combination with an organic solvent.
  • the contact efficiency with water decreases, so The reaction can be suppressed.
  • a water-soluble basic compound since it becomes a uniform state in an aqueous phase, a local side reaction can be suppressed.
  • the amount of the solvent used is preferably 10 to 1000% by volume, more preferably 50 to 800% by volume with respect to 100% by volume of the ethene derivative (2).
  • the order of introducing the ethene derivative (2), the halogenated methane (3), the basic compound, and the phase transfer catalyst into the reaction vessel is not particularly limited, and may be simultaneously introduced into the reactor and mixed. Good. Alternatively, the ethene derivative (2) and the halogenated methane (3) may be added sequentially or simultaneously after mixing the basic compound and the phase transfer catalyst in the reactor. Alternatively, the halogenated methane (3) may be added last. In general, when a reaction is performed, a solvent, a catalyst, and the like are mixed in advance, and then raw materials and the like are added sequentially or simultaneously. When the reaction exotherm is large, it is preferable to add all or part of the raw materials sequentially.
  • the reaction temperature in step (ii) is preferably ⁇ 20 ° C. to + 50 ° C., more preferably ⁇ 10 ° C. to + 40 ° C., and further preferably 0 ° C. to + 30 ° C.
  • the reaction pressure is not particularly limited, and the reaction can be carried out under pressure, normal pressure, or reduced pressure.
  • step (ii) can be carried out continuously, and is extremely superior in productivity over conventional production methods that are batch-type. Furthermore, highly corrosive hydrogen chloride or the like is not generated, and the safety is high and there are few restrictions on the reaction apparatus, which is extremely advantageous industrially.
  • the propene derivative (8) can be converted into a halogenated acrylate derivative (5) which is a product of the step (iii) described later by decomposing under acidic conditions in the presence of a solvent. Therefore, the yield and productivity can be improved by recovering the propene derivative (8) and producing a halogenated acrylic ester.
  • the decomposition reaction of the propene derivative (8) is preferably carried out under acidic conditions, preferably at pH 0-7, more preferably at pH 0-5. In order to make it acidic conditions, it is preferable to make acids, such as hydrochloric acid and a sulfuric acid, exist in a reaction system.
  • the solvent used for the decomposition reaction is preferably an alcohol such as methanol or ethanol.
  • the amount of the solvent used is preferably 10 to 1000% by volume, more preferably 20 to 800% by volume with respect to 100% by volume of the propene derivative (8).
  • the reaction temperature is preferably ⁇ 20 to + 100 ° C., more preferably ⁇ 10 to + 80 ° C.
  • Preferred examples of the propene derivative (8) include a compound represented by the following formula (7).
  • the cyclopropane derivative (4) obtained in step (ii) is useful as an intermediate for drugs, polymers and the like.
  • the cyclopropane derivative (4) in which X is a fluorine atom and Y is a chlorine atom or a fluorine atom in the formula (4) is useful.
  • Me represents a methyl group
  • Y 1 represents a chlorine atom or a fluorine atom.
  • Specific examples of the compound represented by the formula (6) include the following compounds.
  • the compound represented by the formula (6) of the present invention has a low boiling point, it can be purified by distillation at 20 ° C. or less using the same vacuum distillation apparatus, and its decomposition is less than 1%. Therefore, it is very useful industrially and economically.
  • Step (iii) In the step (iii), the cyclopropane derivative (4) obtained in the step (ii) is heated in a liquid phase or a gas phase to cause a de-R 4 Y reaction, and the halogenation represented by the formula (5).
  • This is a process for producing an acrylate derivative (hereinafter also simply referred to as “halogenated acrylate derivative (5)”).
  • the product obtained in step (ii) may be used in the reaction of step (iii) without purification or may be used after purification.
  • a purification method of the cyclopropane derivative (4) for example, a known method such as extraction using a solvent, distillation, or crystallization can be used.
  • the ethene derivative (2) and halogenated methane (3) contained unreacted in the cyclopropane derivative (4) obtained in step (ii) are separated into step (ii). It is also possible to return.
  • step (iii) the cyclopropane derivative (4) obtained in step (ii) is heated in a reactor.
  • the reaction in step (iii) is an elimination reaction, and the compound represented by the formula R 4 Y is eliminated.
  • the reaction in step (iii) may be performed in the gas phase or in the liquid phase.
  • the reaction temperature in step (iii) is preferably 80 ° C. to 400 ° C., more preferably 100 ° C. to 350 ° C., and further preferably 120 ° C. to 300 ° C.
  • the reaction pressure is not particularly limited, and the reaction can be performed under pressure, normal pressure, or reduced pressure. In general, when the temperature is low, the conversion rate of the cyclopropane derivative (4) decreases, and when the temperature is high, a by-product is formed, polymerization is accelerated, and the like. The optimum reaction temperature depends on the contact time.
  • the raw material may be introduced into a preheated reactor, may be introduced before heating, or preferably preheated.
  • the reaction liquid and reaction gas containing the halogenated acrylic ester derivative (5) may be continuously extracted and may be performed continuously, or may be performed batchwise without being simultaneously extracted. From the viewpoint of productivity, it is advantageous to carry out continuously.
  • the residence time in the reactor may be a time during which the cyclopropane derivative (4) is sufficiently converted, and is preferably 1 second or longer, more preferably 10 seconds or longer. Preferably, 30 seconds or more is more preferable. Further, from the viewpoint of suppressing side reactions such as polymerization, it is preferably within 5 hours, more preferably within 2 hours, and even more preferably within 1 hour. In general, if the contact time is short, the conversion rate of the cyclopropane derivative (4) may decrease, and if the contact time is long, a by-product may be generated, polymerization may be promoted, and the like.
  • step (iii) When step (iii) is carried out in the liquid phase, it can be carried out in the presence or absence of a solvent, preferably in the presence of a solvent.
  • a solvent When a solvent is used in step (iii), the solvent is stable to heating, and an inert solvent in the reaction of step (iii) is preferable.
  • the solvent examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene; halogenated aromatic hydrocarbon solvents such as monochlorobenzene, dichlorobenzene and trichlorobenzene; cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, Hydrocarbon solvents such as tridecane and tetradecane; alcohol solvents such as methanol, ethanol and propanol; halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride are preferred.
  • the amount of the solvent used is preferably 0 to 1000% by volume, more preferably 0 to 800% by volume with respect to 100% by volume of the cyclopropane derivative (4).
  • the halogenated acrylic ester derivative (5) obtained in the step (iii) can be purified by a known method such as extraction using a solvent, distillation, or crystallization. Further, the halogenated acrylic ester derivative (5) obtained in the step (iii) may be easily polymerized to produce a polymer depending on the structure during the step (iii) or after isolation and purification. In that case, it is preferable to prevent polymerization during the step (iii) or after isolation and purification by adding a polymerization inhibitor.
  • a polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polymerization inhibitor used is preferably 10 ppm or more, particularly preferably 20 to 50,000 ppm, based on the halogenated acrylic ester derivative (5) obtained in step (iii). If the amount of the polymerization inhibitor used is small, the polymerization inhibitory effect is low, and if it is large, the amount of waste increases and the cost may be inferior.
  • the addition method of the polymerization inhibitor is not particularly limited, and the polymerization inhibitor is preferably present in the system in which the halogenated acrylic ester derivative (5) is present. Specifically, it is preferable that a polymerization inhibitor be present in the reaction system, in the kettle during distillation purification, and in the halogenated acrylic ester derivative (5) after distillation purification. Moreover, the self-polymerization in the gaseous-phase state of a halogenated acrylate derivative (5) can also be effectively suppressed by combining a polymerization inhibitor and aeration in the distillation purification.
  • the amount of oxygen introduced in the aeration during distillation is not particularly limited, but may be an amount that does not induce an explosion including the entire distillation system.
  • step (iii) can be carried out continuously, and is extremely excellent in productivity as compared with conventional production methods that are batch-type. Further, when the reaction is carried out in the gas phase, the separation of the product is extremely easy. Furthermore, there is no production of highly corrosive hydrogen chloride, etc., which is highly safe and less restrictive of the reaction apparatus, which is extremely advantageous industrially.
  • the halogenated acrylate derivative (5) is useful as a raw material for pharmaceuticals, polymers, optical materials, paints, semiconductor resist materials and the like.
  • ⁇ -fluoroacrylic acid ester derivatives are extremely useful as pharmaceuticals and as basic raw materials for polymers and optical materials. That is, by polymerizing the halogenated acrylate derivative represented by the formula (5) obtained by the production method of the present invention, a method for producing a polymer containing a polymer unit based on the halogenated acrylate derivative is provided. Realized industrially and economically.
  • halogenated acrylic ester derivative (5) examples include a compound represented by the following formula (9).
  • step (i) to (iii) can be carried out independently, but it is industrially advantageous to carry out the steps continuously. For example, after step (i) is carried out in the gas phase, the product is cooled, step (ii) is carried out in the liquid phase without purification, and the product of step (ii) is heated unpurified.
  • the process (iii) can be carried out as a continuous process. A more productive process can be constructed by adding a path for separating the unreacted raw material and returning it to the previous step as described above.
  • steps (i) to (iii) of the present invention are preferably performed on the following reaction substrates.
  • Intermediates and final product compounds obtained in each step are useful compounds as intermediates for pharmaceuticals, polymers and the like.
  • Step (i)> The reaction was carried out by heating with an electric heater so that the temperature of the catalyst layer became the temperature shown in Table 1, and circulating trimethyl orthoacetate as a raw material under the conditions shown in Table 1.
  • the crude liquid at the outlet of the reactor was collected with a cold trap at 0 ° C. and analyzed by gas chromatography to analyze the composition of the reaction product. Moreover, it reacted by the same operation as Example 1 without using a solid catalyst as a comparative example. The results are shown in Table 1.
  • 1,1-dimethoxyethene is obtained as a colorless liquid by fractional distillation by atmospheric distillation using a packed column.
  • the 1 H-NMR of 1,1-dimethoxyethene is shown below. 1 H-NMR (400 MHz, CDCl 3 ), ⁇ ppm; 2.91 (s, 2H), 3.41 (s, 6H).
  • Examples 4 to 6 The reaction was carried out in the same manner as in Example 2 except that the catalyst was changed. The results are shown in Table 2.
  • Catalyst 1 Spherical ⁇ -alumina (specific surface area 3 m 2 / g, solid acid amount 0.9 mmol / g (NH 3 conversion), “HD ball” manufactured by Nikkato) * Catalyst 2: Cylindrical ⁇ -alumina (specific surface area 280 m 2 / g, solid acid amount 0.2 mmol / g (NH 3 conversion), “Sexsorb COS” manufactured by NE Chemcat) * Catalyst 3: 5% zinc oxide-zirconium oxide (specific surface area 60 m 2 / g, solid acid amount 0.06 mmol / g (NH 3 conversion), manufactured by NE Chemcat)
  • Examples 7 to 15 The reaction was carried out in the same manner as in Example 2 except that the catalyst was changed. The results are shown in Table 3.
  • Example 16 [Example 16 (step (ii))] In a 300 ml flask, 20 g of 1,1-dimethoxyethene, 0.1 g of tetrabutylammonium bromide, 80 g of 48% potassium hydroxide aqueous solution and 40 g of hexane were mixed, cooled to 5 ° C. and stirred, and 32 g of dichlorofluoromethane was added. Was continuously fed so that the reaction temperature did not exceed 10 ° C. After completion of the feed of dichlorofluoromethane, 40 g of distilled water was added after confirming the disappearance of 1,1-dimethoxyethene by gas chromatography, and the organic layer was separated into two layers.
  • the content of 2-fluoro-3,3,3-trimethoxy-1-propene was 1.7 g from 1 H-NMR (determined by the internal standard method). The yield was 5.0%.
  • the 1 H-NMR and 19 F-NMR of 2-fluoro-3,3,3-trimethoxy-1-propene are shown below.
  • 19 F-NMR 400 MHz, CDCl 3 ), ⁇ ppm; ⁇ 126.09 (dd, 1F).
  • 1-chloro-1-fluoro-2 which was obtained in the same manner except that 1,1-dimethoxyethene in Example 16 was changed to 1,1-diethoxyethene using the same vacuum distillation apparatus,
  • the organic layer crude liquid containing 2-diethoxycyclopropane was distilled, it could be distilled under conditions of a bath temperature of 50 ° C. and a pressure of 10 hPa.
  • the decomposition rate of 1-chloro-1-fluoro-2,2-diethoxycyclopropane in distillation was 24%.
  • Example 17 to 22 The reaction was performed in the same manner as in Example 16 except that the amounts of tetrabutylammonium bromide, 48% aqueous potassium hydroxide solution and dichlorofluoromethane were changed.
  • Table 4 The results are shown in Table 4.
  • TBAB represents tetrabutylammonium bromide
  • KOH solution represents a 48% aqueous potassium hydroxide solution
  • CHCl 2 F represents dichlorofluoromethane.
  • Example 23 The reaction was performed in the same manner as in Example 16, except that 32 g of dichlorofluoromethane was changed to 27 g of chlorodifluoromethane.
  • the content of 1,1-difluoro-2,2-dimethoxycyclopropane contained in the obtained organic layer crude liquid was 26 g from 1 H-NMR (determined by the internal standard method). The yield was 81.5%.
  • 1 H-NMR and 19 F-NMR of 1,1-difluoro-2,2-dimethoxycyclopropane are shown below.
  • 1 H-NMR 400 MHz, CDCl 3 ), ⁇ ppm; 1.55 (m, 2H), 3.30 (s, 6H).
  • Example 24 (step (iii))] To a 100 ml three-necked flask connected to a reactor for reactive distillation (cooled to 0 ° C., initially added 0.5 g of 2,6-di-tert-butyl-4-methylphenol (BHT) as a polymerization inhibitor) 0.5 g of 6-di-tert-butyl-4-methylphenol (BHT) and 100 ml of 1,2,4-trichlorobenzene were added and the degree of vacuum was 360 torr. The dropping of 45 g of the organic layer crude liquid produced in Example 16 was started at a temperature heated to 145 ° C., and the dropping was continued at such a rate that the internal temperature was maintained at 145 ° C.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • the produced methyl ⁇ -fluoroacrylate collected in the distillation receiver was 10 g from 1 H-NMR (determined by the internal standard method). The yield was 94.6%.
  • Example 25 The reaction was carried out in the same manner as in Example 24 except that the organic layer crude liquid produced in Example 16 was changed to the organic layer crude liquid produced in Example 23.
  • the yield of methyl ⁇ -fluoroacrylate contained in the crude liquid collected in the distillation receiver was 91.7% according to 1 H-NMR (determined by the internal standard method).
  • the method for producing a halogenated acrylate derivative according to the present invention is based on a readily available ortho carboxylic acid derivative as a raw material, and the final product is a halogenated acrylate derivative with high conversion, high selectivity and high yield. This method is very useful industrially.
  • the intermediates and final product compounds produced by the method for producing a halogenated acrylic ester derivative according to the present invention are useful compounds as intermediates for pharmaceuticals, polymers and the like.

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Abstract

La présente invention concerne un nouveau procédé de production d'un dérivé d'ester acrylique halogéné. Le procédé selon la présente invention consiste à : soumettre, en phase gazeuse, un composé représenté par la formule (1) (dans la formule, R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe monovalent contenant essentiellement un atome de carbone, ou R1 et R2 peuvent former conjointement un cycle ensemble avec un atome de carbone auquel R1 et R2 sont liés, R3 représente un groupe monovalent duquel peut être éliminé un groupe R3O par une réaction d'élimination de R3OH, et R4 et R5 représentent chacun indépendamment un atome d'hydrogène ou un groupe monovalent contenant essentiellement un atome de carbone) et possédant un point d'ébullition inférieur ou égal à 500 °C, pour la réaction d'élimination de R3OH en présence d'un catalyseur solide afin d'obtenir un dérivé d'éthylène représenté par la formule (2) ; faire réagir le dérivé d'éthylène représenté par la formule (2) avec un méthane halogéné représenté par la formule (3) (dans la formule, X, Y, et Z représentent chacun indépendamment un atome d'halogène) en présence d'un composé basique et d'un catalyseur de transfert de phase afin d'obtenir un dérivé de cyclopropane représenté par la formule (4) ; et chauffer le dérivé de cyclopropane représenté par la formule (4) en phase liquide ou en phase gazeuse de sorte que le dérivé de cyclopropane subisse une réaction d'élimination de R4Y afin d'obtenir un dérivé d'ester acrylique halogéné représenté par la formule (5).
PCT/JP2016/074598 2015-08-27 2016-08-24 Procédé de production d'un dérivé d'ester acrylique halogéné WO2017033955A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2017163756A1 (fr) * 2016-03-23 2017-09-28 旭硝子株式会社 Procédé de production d'ester d'acide α-fluoro acrylique, et composition contenant un dérivé de fluorocyclopropane très pur, et composition contenant l'ester d'acide α-fluoro acrylique très pur
JPWO2017163756A1 (ja) * 2016-03-23 2019-01-31 Ａｇｃ株式会社 α−フルオロアクリル酸エステルの製造方法、高純度なフルオロシクロプロパン誘導体を含む組成物、および、高純度なα−フルオロアクリル酸エステルを含む組成物
US10981857B2 (en) 2016-03-23 2021-04-20 AGC Inc. Method for producing α-fluoro acrylic acid ester, and composition containing highly-pure fluorocyclopropane derivative, and composition containing highly-pure α-fluoro acrylic acid ester

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