α-halogenoacrylate anhydride and method for producing the same, and method for producing α-halogenoacrylate esters

Abstract

To provide an α-halogenoacrylate anhydride that enables the synthesis of α-halogenoacrylate esters in high yield. [Solution] The present invention relates to the following formula (1): TIFF2026144772000008.tif28155 [In formula (1), X represents a chlorine atom or a bromine atom.] It is an α-halogenoacrylic anhydride represented by [formula].

Description

[Technical Field]

[0001] The present invention relates to α-halogenoacrylate anhydride, a method for producing the same, and a method for producing α-halogenoacrylate esters. [Background technology]

[0002] Conventionally, in fields such as semiconductor manufacturing, polymers whose main chains are cleaved by irradiation with ionizing radiation such as electron beams or short-wavelength light such as ultraviolet light (hereinafter, ionizing radiation and short-wavelength light may be collectively referred to as "ionizing radiation, etc.") and whose solubility in developing solutions increases have been used as main-chain cleavage type positive resists, and various monomers constituting the polymers have been investigated in order to improve performance.

[0003] Against this backdrop, for example, Patent Documents 1 and 2 propose main-chain cleavage type resists that can be used with state-of-the-art lithography processing, and specifically, copolymers obtained using α-chloroacrylate esters have been found to have excellent performance.

[0004] Here, as a method for producing α-halogenoacrylic acid esters such as α-chloroacrylic acid esters used in the formation of the above copolymer, a method is known in which a halogen is added to a predetermined acrylic acid ester to synthesize an α,β-dihalogenopropionic acid ester, and the obtained α,β-dihalogenopropionic acid ester is brought into contact with a base such as an organic amine or an inorganic alkali to cause a dehalogenation hydrogenation reaction, thereby preparing an α-halogenoacrylic acid ester (Patent Documents 3, 4, etc.).

[0005] Furthermore, as another method for producing α-halogenoacrylate esters, for example, in Example 1 of Patent Document 5, it is described that α,β-dichloropropionic acid tetrafluoropropyl ester is synthesized by directly dehydrating and condensing tetrafluoropropanol and α,β-dichloropropionic acid in the presence of concentrated sulfuric acid, and then α,β-dichloropropionic acid tetrafluoropropyl ester is obtained by alkali treatment.

[0006] Furthermore, as a method for producing α-halogenoacrylate esters other than the above method, for example, Patent Document 6 describes a method for preparing α-halogenoacrylate esters by reacting a tertiary alcohol with α-chloroacrylate chloride in the presence of alkyllithium or alkylmagnesium halide. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2020 / 066806 [Patent Document 2] Japanese Patent Publication No. 2020-52144 [Patent Document 3] Japanese Patent Application Publication No. 57-118535 [Patent Document 4] International Publication No. 2006 / 54549 [Patent Document 5] Japanese Patent Publication No. 63-201145 [Patent Document 6] Japanese Patent Publication No. 2002-173467 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, the methods described in Patent Documents 3 and 4 have the problem that substituents bonded to the non-carbonyl oxygen atom of the acrylic acid ester, which is the starting material, greatly affect the halogen addition reaction. For example, if a hydrocarbon group with a strong electron-withdrawing property, such as a fluoro group, is bonded, it takes a considerable amount of time for the reaction to complete, resulting in a decrease in the yield of α-halogenoacrylate ester.

[0009] Furthermore, in the method described in Patent Document 5, the raw material, α,β-dichloropropionic acid, is highly hygroscopic, making it difficult to handle due to its tendency to absorb moisture and become sticky. In addition, the dehydration reaction between alcohols by concentrated sulfuric acid proceeds, inhibiting the esterification reaction. Moreover, since the chlorine atom at the β position of α,β-dichloropropionic acid is easily dehalogenated, the composition of the product may become complex. For these reasons, the method described in Patent Document 5 also has the problem of a reduced yield of α-halogenoacrylate ester.

[0010] Furthermore, in the method described in Patent Document 6, the alkyllithium or alkylmagnesium halide used in the reaction may cause the α-halogenoacrylate ester obtained during the reaction process to undergo polymerization. Therefore, the method described in Patent Document 6 also has the problem of a decrease in the yield of α-halogenoacrylate ester.

[0011] This invention was made under such circumstances, and aims to provide an α-halogenoacrylate anhydride and a method for producing the same that can synthesize α-halogenoacrylate esters in high yield. Furthermore, the present invention aims to provide a method for producing α-halogenoacrylate esters using the above-mentioned α-halogenoacrylate anhydride. [Means for solving the problem]

[0012] The inventors diligently conducted research to achieve the above objectives. They then discovered that the above problems could be solved by using an α-halogenoacrylate anhydride having a predetermined structure, and thus completed the present invention.

[0013] That is, the present invention aims to advantageously solve the above problem. [1] The present invention provides an α-halogenoacrylic anhydride represented by the following formula (1):

Chemical Formula

[0014] The present invention also aims to advantageously solve the above problem. [2] The present invention provides a method for producing the α-halogenoacrylic anhydride of [1] above, comprising: contacting an alkali metal α-halogenoacrylate represented by the following formula (2):

Chemical Formula

[0015] [3] In the method for producing α-halogenoacrylic anhydride according to [2] above, it is preferable that the organic sulfonic anhydride is methanesulfonic anhydride, because methanesulfonic anhydride is easily available.

[0016] Furthermore, the present invention aims to advantageously solve the above-mentioned problems, [4] and the present invention is a method for producing α-halogenoacrylate esters by contacting the α-halogenoacrylate anhydride described in [1] above with a hydroxyl group-containing compound of at least one of alcohols and phenols. Using the above-described method for producing α-halogenoacrylate esters, it is possible to obtain α-halogenoacrylate esters in high yield.

[0017] [5] In the method for producing α-halogenoacrylate ester described in [4] above, the hydroxyl group-containing compound is preferably at least one of a secondary alcohol and a tertiary alcohol. If the hydroxyl group-containing compound is at least one of a secondary alcohol and a tertiary alcohol, the desired α-halogenoacrylate ester can be obtained. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide α-halogenoacrylate anhydride and a method for producing the same, which can be synthesized in high yield as α-halogenoacrylate esters. Furthermore, according to the present invention, a method for producing α-halogenoacrylate esters using the above-mentioned α-halogenoacrylate anhydride can be provided. [Modes for carrying out the invention]

[0019] Embodiments of the present invention will be described in detail below. Herein, the α-halogenoacrylic anhydride of the present invention is not particularly limited and can be advantageously used, for example, as a raw material for obtaining monomers used in the production of polymers. In particular, it can be advantageously used as a raw material for obtaining α-halogenoacrylic esters used in the production of polymers in which the main chain is cleaved by ionizing radiation or the like to reduce the molecular weight, which can be suitably used as a main chain cleavage type positive resist.

[0020] (α-halogenoacrylate anhydride) The α-halogenoacrylic anhydride of the present invention is of the following formula (1): [ka] This is a compound represented by (hereinafter sometimes referred to as "α-halogenoacrylic anhydride (1)"). Here, in equation (1), X represents a chlorine atom or a bromine atom. Using the α-halogenoacrylate anhydride (1) described above, α-halogenoacrylate esters can be synthesized in high yield.

[0021] (Method for producing α-halogenoacrylate anhydride) The method for producing α-halogenoacrylic anhydride (1) of the present invention (hereinafter sometimes referred to as "production method A") is as follows: [ka] Alkali metal α-halogenoacrylates represented by the following formula (hereinafter referred to as "Alkali metal α-halogenoacrylates (2)" and formula (3): (RSO2)2O (3) The organic sulfonic anhydride represented by (hereinafter sometimes referred to as "organic sulfonic anhydride (3)") is brought into contact with the product. With the above-described manufacturing method A, it is possible to obtain the α-halogenoacrylic anhydride (1) of the present invention, that is, an α-halogenoacrylic anhydride (1) that can synthesize α-halogenoacrylic acid esters in high yield.

[0022] Here, the contact between the alkali metal salt of α-halogenoacrylate (2) and the organic sulfonic anhydride (3) is usually carried out in an organic solvent. Furthermore, a polymerization inhibitor may be optionally added during the contact between the alkali metal salt of α-halogenoacrylate (2) and the organic sulfonic anhydride (3).

[0023] The product containing α-halogenoacrylate anhydride (1), obtained by contacting α-halogenoacrylate alkali metal salt (2) with organic sulfonic acid anhydride (3), may optionally be purified by methods such as vacuum distillation. However, since α-halogenoacrylate anhydride (1) is highly polymerizable, it is preferable to use it as is in esterification reactions, etc., to avoid problems such as the occurrence of unexpected polymerization reactions.

[0024] <Alkali metal salt of α-halogenoacrylate> The alkali metal salt of α-halogenoacrylate used in manufacturing method A of the present invention is a compound represented by the following formula (2). [ka]

[0025] In equation (2), X represents a chlorine atom or a bromine atom, and Y represents an alkali metal atom.

[0026] Here, the alkali metal salt (2) of α-halogenoacrylate is not particularly limited and can be synthesized by conventionally known methods. For example, it can be synthesized by the method described in "Journal of Chemical Society, 779 (1968)" or the method described in "Synthetic Communications, Vol. 33, 1109 (2003)". Specifically, "Journal of Chemical Society, 779 (1968)" describes a method for synthesizing sodium α-chloroacrylate by neutralizing α-chloroacrylic acid with sodium hydroxide in an aqueous ethanol solvent, and "Synthetic Communications, Vol. 33, 1109 (2003)" describes a method for synthesizing sodium α-chloroacrylate by contacting 2,3-dichloropropionic acid with 2 equivalents of sodium hydroxide in an aqueous solvent. Furthermore, as a method for synthesizing alkali metal salts of α-halogenoacrylate (2) other than those mentioned above, the "Supporting Information in Organic Letters, Vol. 9, 4607 (2007)" describes a method in which α-bromoacrylic acid is synthesized by dehydrochlorinating 2,3-dibromopropionic acid in a dimethyl sulfoxide-water mixed system under heating conditions, and then sodium α-bromoacrylate is synthesized by neutralizing the obtained α-bromoacrylic acid with an aqueous sodium hydroxide solution.

[0027] Specific examples of alkali metal salts of α-halogenoacrylate (2) include alkali metal salts of α-chloroacrylate such as lithium α-chloroacrylate, sodium α-chloroacrylate, potassium α-chloroacrylate, and cesium α-chloroacrylate; and alkali metal salts of α-bromoacrylate such as lithium α-bromoacrylate, sodium α-bromoacrylate, potassium α-bromoacrylate, and cesium α-bromoacrylate. Among these, sodium α-chloroacrylate, potassium α-chloroacrylate, sodium α-bromoacrylate, and potassium α-bromoacrylate are preferred because they can be synthesized inexpensively. The alkali metal salts of α-halogenoacrylate listed above (2) may be used individually or in combination of two or more.

[0028] The amount of alkali metal salt α-halogenoacrylate (2) used is preferably 2 molar equivalents or more, more preferably 2.2 molar equivalents or more, preferably 4 molar equivalents or less, and more preferably 2.6 molar equivalents, relative to the organic sulfonic acid anhydride (3). If the amount of alkali metal salt α-halogenoacrylate (2) used is above the lower limit mentioned above, the yield of the resulting α-halogenoacrylate anhydride (1) can be effectively improved. On the other hand, if the amount of alkali metal salt α-halogenoacrylate (2) used is below the above upper limit, the risk of excessive solvent usage can be effectively reduced. Furthermore, the risk of polymerization reactions, etc., proceeding with the raw material alkali metal salt α-halogenoacrylate (2) and / or the α-halogenoacrylate anhydride (1) produced in the reaction can be effectively reduced.

[0029] <Organic sulfonic anhydride> The organic sulfonic acid anhydride used in production method A of the present invention is a compound represented by the following formula (3). (RSO2)2O (3)

[0030] In formula (3), R represents a hydrocarbon group which may have substituents.

[0031] Examples of hydrocarbon groups for R include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Examples of aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups; and alkenyl groups. Examples of aromatic hydrocarbon groups include phenyl groups and tolyl groups.

[0032] Examples of substituents that a hydrocarbon group may have include fluoro groups and chloro groups. Among these, fluoro groups are preferred.

[0033] Examples of organic sulfonic acid anhydrides (3) include aliphatic sulfonic acid anhydrides such as methanesulfonic acid anhydride, ethanesulfonic acid anhydride, trifluoromethanesulfonic acid anhydride, and nonafluorobutanesulfonic acid anhydride, and aromatic sulfonic acid anhydrides such as benzenesulfonic acid anhydride and p-toluenesulfonic acid anhydride. Among these, methanesulfonic acid anhydride, trifluoromethanesulfonic acid anhydride, and p-toluenesulfonic acid anhydride are preferred because they are readily available. The organic sulfonic anhydrides (3) listed above may be used individually or in combination of two or more.

[0034] <organic solvents> In manufacturing method A, polar solvents can be suitably used as organic solvents. Among polar solvents, aprotic polar solvents are preferred. Examples of aprotic polar solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclopentanone; ether solvents such as t-butyl methyl ether, tetrahydrofuran, diisopropyl ether, and 1,2-dimethoxyethane; and nitrile solvents such as acetonitrile and propionite nitrile. Among these, ketone solvents and ether solvents are preferred because they are readily available and can be easily removed by distillation after the reaction is complete, with acetone, methyl ethyl ketone, tetrahydrofuran, and 1,2-dimethoxyethane being more preferred, and acetone and tetrahydrofuran being even more preferred. The organic solvents listed above may be used individually or in combination of two or more. Furthermore, from the viewpoint of reactivity, the organic solvent is preferably an anhydrous form from which water has been removed.

[0035] The amount of organic solvent used in manufacturing method A is preferably 0.5 times or more, more preferably 1 time or more, preferably 3 times or less, and more preferably 2 times or less, relative to the total mass of alkali metal salt of α-halogenoacrylate (2) and organic sulfonic acid anhydride (3). If the amount of organic solvent used is above the lower limit mentioned above, the risk of polymerization reactions of the raw material α-halogenoacrylate alkali metal salt (2) and / or the α-halogenoacrylate anhydride (1) produced in the reaction can be effectively reduced. In addition, insufficient stirring can be effectively suppressed, and contact between the α-halogenoacrylate alkali metal salt (2) and the organic sulfonic acid anhydride (3) can be carried out efficiently. On the other hand, if the amount of organic solvent used is below the above upper limit, the alkali metal salt of α-halogenoacrylate (2) and the organic sulfonic anhydride (3) will not be excessively diluted, effectively suppressing the excessive slowing of the production rate of α-halogenoacrylate anhydride (1), and as a result, the reaction time can be effectively shortened.

[0036] <Polymerization inhibitors> The polymerization inhibitor that can be used in manufacturing method A is capable of preventing unexpected side reactions (e.g., polymerization reactions) during the reaction. Since both the α-halogenoacrylate alkali metal salt (2), which is the raw material, and the α-halogenoacrylate anhydride (1), which is produced in the reaction, are polymerizable, polymerization reactions and the like can be effectively suppressed by using a polymerization inhibitor.

[0037] Examples of polymerization inhibitors include phenolic compounds such as hydroquinone, p-methoxyphenol (hydroquinone monomethyl ether), 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, tert-butyl-catechol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol, tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), and 2-sec-butyl-4,6-dinitrophenol; N,N'-diisopropylparaphenylenediamine, N,N'-di-2-naphthylpara. Examples include amine compounds such as phenylenediamine, N-phenylene-N'-(1,3-dimethylbutyl)paraphenylenediamine, N,N'-bis(1,4-dimethylphenyl)-paraphenylenediamine, N-(1,4-dimethylphenyl)-N'-phenyl-paraphenylenediamine, and phenothiazine; and N-oxyl compounds such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate.

[0038] Here, the polymerization inhibitors listed above may be used individually or in combination of two or more, but it is preferable to use them in combination of two or more. When using two or more polymerization inhibitors, it is preferable to use a phenolic compound and an amine compound, and more preferably to use p-methoxyphenol and phenothiazine.

[0039] The amount of polymerization inhibitor used (total amount if two or more polymerization inhibitors are used) is preferably 1.00 mmol or more, preferably 3.00 mmol or more, preferably 30.00 mmol or less, and more preferably 20.00 mmol or less, based on 100 mol of alkali metal salt α-halogenoacrylate (2).

[0040] <Contact conditions> The temperature at which the alkali metal salt of α-halogenoacrylate (2) and the organic sulfonic anhydride (3) are brought into contact (hereinafter sometimes referred to as "reaction temperature A") is preferably 0°C or higher, more preferably 20°C or higher, preferably 50°C or lower, and more preferably 35°C or lower. If the reaction temperature A is above the lower limit mentioned above, the reaction time can be effectively shortened. On the other hand, if the reaction temperature A is below the above upper limit, the risk of polymerization reactions of the raw material α-halogenoacrylate alkali metal salt (2) and / or the α-halogenoacrylate anhydride (1) produced in the reaction proceeding can be effectively reduced.

[0041] The time for contacting the alkali metal salt of α-halogenoacrylate (2) and the organic sulfonic anhydride (3) (hereinafter sometimes referred to as "reaction time A") may depend on the reaction temperature A, but is preferably 1 hour or more, more preferably 3 hours or more, preferably 48 hours or less, and more preferably 30 hours or less. If the reaction time A is above the lower limit mentioned above, the reaction will not be completed, and the large amount of the starting material, alkali metal salt α-halogenoacrylate (2), that remains can be effectively suppressed. On the other hand, if the reaction time A is below the above upper limit, the risk of polymerization reactions, etc., of the raw material α-halogenoacrylate alkali metal salt (2) and / or the α-halogenoacrylate anhydride (1) produced in the reaction can be effectively reduced.

[0042] <Specific example of manufacturing method A of the present invention> The following describes a specific example of manufacturing method A of the present invention, but manufacturing method A of the present invention is not limited to this example.

[0043] As a specific example of manufacturing method A, first, predetermined amounts of the raw material α-halogenoacrylate alkali metal salt (2), organic solvent, and polymerization inhibitor as needed are charged into a reactor, and stirring is started under an inert atmosphere. Next, the reactor is brought to a predetermined temperature, and then organic sulfonic acid anhydride (3) is added to the reactor, and stirring is continued for a predetermined time. After the reaction is complete, the by-product alkali metal salt of sulfonic acid is removed by filtration, and the organic solvent is removed from the filtrate, thereby obtaining the desired α-halogenoacrylate anhydride (1).

[0044] (Method for producing α-halogenoacrylate esters) The method for producing α-halogenoacrylate esters of the present invention (hereinafter sometimes referred to as "production method B") involves contacting the α-halogenoacrylate anhydride (1) of the present invention described above with a hydroxyl group-containing compound containing at least one of alcohols and phenols (hereinafter sometimes simply referred to as "hydroxyl group-containing compound"). Since production method B of the present invention uses the α-halogenoacrylate anhydride (1) of the present invention, which is capable of synthesizing α-halogenoacrylate esters in high yield, α-halogenoacrylate esters can be obtained in high yield.

[0045] Here, the contact (esterification reaction) between α-halogenoacrylic anhydride (1) and the hydroxyl group-containing compound is usually carried out in an organic solvent. Furthermore, during the contact between α-halogenoacrylic anhydride (1) and the hydroxyl group-containing compound, polymerization inhibitors and basic compounds may be optionally added.

[0046] After contacting α-halogenoacrylate anhydride (1) with the hydroxyl group-containing compound, the reaction solution may optionally be filtered to remove by-products such as α-halogenoacrylate salts, or the reaction solution may be washed with water to remove by-products such as α-halogenoacrylate salts. Alternatively, the filtrate after filtration or the solution after washing may be contacted with a diluted acid (e.g., dilute hydrochloric acid, dilute sulfuric acid, etc.) to remove excess basic compounds. Furthermore, the filtrate after filtration, the solution after washing, or the solution after removal of basic compounds may be washed with water or an aqueous solution of diluted alkaline carbonate or alkaline bicarbonate (an aqueous solution with a concentration of 5-20% by mass), and then washed with saturated saline solution. The resulting solution may then be dried with a drying agent such as sodium sulfate or magnesium sulfate, and the solvent may be removed from the dried solution by distillation.

[0047] Furthermore, after contacting α-halogenoacrylate anhydride (1) with a hydroxyl group-containing compound, and optionally removing α-halogenoacrylate salts, basic compounds, etc., the obtained α-halogenoacrylate ester may be purified to increase its purity by methods such as distillation, column chromatography, or recrystallization in the case of a solid. However, a polymerization inhibitor may be added to prevent deterioration such as the occurrence of unexpected polymerization reactions.

[0048] <α-halogenoacrylic anhydride> The α-halogenoacrylic anhydride (1) used in the manufacturing method B of the present invention is the α-halogenoacrylic anhydride (1) of the present invention described above. Furthermore, as the α-halogenoacrylic anhydride (1), the α-halogenoacrylic anhydride (1) obtained by the production method A of the present invention described above may be used.

[0049] The amount of α-halogenoacrylic anhydride (1) used is preferably 1 molar equivalent or more, more preferably 1.2 molar equivalents or more, preferably 3 molar equivalents or less, and more preferably 1.5 molar equivalents or less, relative to the hydroxyl group-containing compound. If the amount of α-halogenoacrylate anhydride (1) used is above the lower limit mentioned above, the reaction time can be effectively shortened and the yield of the resulting α-halogenoacrylate ester can be effectively improved. On the other hand, if the amount of α-halogenoacrylate anhydride (1) used is below the above upper limit, the risk of polymerization reactions and other processes occurring in the resulting α-halogenoacrylate ester can be effectively reduced.

[0050] <Hydroxy group-containing compounds> The hydroxyl group-containing compound is at least one of alcohols and phenols.

[0051] There are no particular limitations on the type of alcohol used; primary, secondary, or tertiary alcohols can all be used. Here, secondary and tertiary alcohols are generally prone to dehydration reactions between alcohols, and in conventional methods, these dehydration reactions can proceed and inhibit the esterification reaction. However, the production method B of the present invention can effectively suppress the dehydration reactions between alcohols, and is therefore particularly useful when at least one of a secondary alcohol and a tertiary alcohol is used as the alcohol. That is, in the production method B of the present invention, the hydroxyl group-containing compound is preferably at least one of a secondary alcohol and a tertiary alcohol. And if the hydroxyl group-containing compound is at least one of a secondary alcohol and a tertiary alcohol, the desired α-halogenoacrylate ester can be obtained.

[0052] Examples of secondary alcohols include aliphatic alcohols such as 2-propanol, 2-butanol, 3-pentanol, cyclopentanol, cyclohexanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 1-methylcyclohexanol, hexafluoro-2-propanol, norbornan-2-ol, and 2-adamantanol; and aromatic ring-containing alcohols such as 1-phenylethanol and 2,2,2-trifluoro-1-phenylethanol. Among the above, 2,2,2-trifluoro-1-phenylethanol, norbornan-2-ol, and 2-adamantanol are preferred, and 2,2,2-trifluoro-1-phenylethanol is more preferred. The secondary alcohols listed above may be used individually or in combination of two or more.

[0053] Examples of tertiary alcohols include aliphatic alcohols such as t-butyl alcohol, t-amyl alcohol, 2-methyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-phenyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 1-adamantanol, 2-ethyl-2-adamantanol, hydroxycitronellal, linalool, terpineol, 2-methylisoborneol, and 2-methyl-2-norbornanol; and alcohols having aromatic rings such as 1,1-diphenylethanol. Among these, 2-phenyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, 1-methylcyclopentanol, 2-ethyl-2-adamantanol, 2-methyl-2-norbornanol, and 1,1-diphenylethanol are preferred, and 2-phenyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, and 1-methylcyclopentanol are more preferred. The tertiary alcohols listed above may be used individually or in combination of two or more.

[0054] Examples of phenols include phenol, 4-methoxyphenol, 4-fluorophenol, 4-bromophenol, 4-trifluoromethylphenol, 3,5-bis(trifluoromethyl)phenol, 1-naphthol, 2-naphthol, hydroquinone, and resorcinol. The phenols listed above may be used individually or in combination of two or more.

[0055] <organic solvents> Examples of organic solvents that can be used in manufacturing method B include halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane; ether-based solvents such as t-butyl methyl ether, tetrahydrofuran, diisopropyl ether, and cyclopentyl methyl ether; and aromatic hydrocarbons such as toluene, xylene, and chlorobenzene. Among these, halogenated hydrocarbons and ether-based solvents are preferred, and methylene chloride, chloroform, t-butyl methyl ether, tetrahydrofuran, and diisopropyl ether are more preferred, as the organic solvent can be easily removed from the reaction solution by distillation. The above organic solvents may be used individually or in combination of two or more. Furthermore, from the viewpoint of reactivity, the organic solvent is preferably an anhydrous form from which water has been removed.

[0056] <Polymerization inhibitors> The polymerization inhibitor that can be used in manufacturing method B is the same as the polymerization inhibitor that can be used in manufacturing method A.

[0057] <Basic compounds> The basic compounds that can be used in manufacturing method B are those that can promote the esterification reaction. Examples of basic compounds include organic amines and inorganic bases. Examples of organic amines include tertiary amines such as triethylamine, diisopropylethylamine, and tributylamine; pyridines such as pyridine, 2-methylpyridine, 2,6-dimethylpyridine, and 2,4,6-trimethylpyridine; dialkylanilines such as dimethylaniline and diethylaniline; and heterocyclic aromatic compounds such as quinoline and isoquinoline. Examples of inorganic bases include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, and sodium amide. Among these, organic amines are preferred, tertiary amines and pyridines are more preferred, and triethylamines and pyridines are even more preferred. The basic compounds described above may be used individually or in combination of two or more.

[0058] The amount of basic compound used is preferably 1 molar equivalent or more, more preferably 1.2 molar equivalents or more, preferably 3 molar equivalents or less, and more preferably 2 molar equivalents or less, relative to the number of hydroxyl groups (OH groups) in the hydroxyl group-containing compound used as a raw material. If the amount of basic compound used is above the lower limit mentioned above, the reaction time can be effectively shortened and the yield of the resulting α-halogenoacrylate ester can be effectively improved. On the other hand, if the amount of basic compound used is below the above upper limit, the risk of polymerization reactions and other processes occurring in the resulting α-halogenoacrylate ester can be effectively reduced.

[0059] <Contact conditions> The temperature at which α-halogenoacrylic anhydride (1) is brought into contact with the hydroxyl group-containing compound (hereinafter sometimes referred to as "reaction temperature B") is preferably -10°C or higher, more preferably 0°C or higher, preferably 50°C or lower, and more preferably 25°C or lower. If the reaction temperature B is above the lower limit mentioned above, the reaction time can be effectively shortened. On the other hand, if the reaction temperature B is below the above upper limit, the risk of polymerization reactions of the resulting α-halogenoacrylate ester proceeding can be effectively reduced. Since the contact (esterification reaction) between α-halogenoacrylic anhydride (1) and a hydroxyl group-containing compound may be exothermic, the esterification reaction may be carried out while cooling.

[0060] The time for contacting α-halogenoacrylic anhydride (1) with the hydroxyl group-containing compound (hereinafter sometimes referred to as "reaction time B") is preferably 0.5 hours or more, more preferably 1 hour or more, preferably 20 hours or less, and more preferably 10 hours or less. If the reaction time B is above the lower limit mentioned above, the reaction will not be completed, and the decrease in the yield of the resulting α-halogenoacrylate ester can be effectively suppressed. On the other hand, if the reaction time B is below the above upper limit, the risk of the polymerization reaction of the resulting α-halogenoacrylate ester proceeding can be effectively reduced.

[0061] <Specific example of manufacturing method B of the present invention> The following describes a specific example of manufacturing method B of the present invention, but manufacturing method B of the present invention is not limited thereto.

[0062] As a specific example of the manufacturing method B of the present invention, first, α-halogenoacrylic anhydride (1), a hydroxyl group-containing compound, and a polymerization inhibitor as needed are added to an organic solvent and cooled to a predetermined temperature. Next, a basic compound is added dropwise while stirring the contents. After the addition is complete, the mixture is stirred at that temperature (cooling temperature) for a predetermined time. Next, the mixture is heated to room temperature (approximately 15°C to 25°C) while continuing to stir. Then, the contents are analyzed by gas chromatography or the like, and after confirming that the hydroxyl group-containing compound of the raw materials has disappeared, stirring is stopped and the esterification reaction is completed. [Examples]

[0063] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited by the following examples. Unless otherwise specified, "%" represents "mass%". Furthermore, the measurement conditions for the analysis performed were as follows:

[0064] <Gas chromatography analysis (GC)> • Equipment: Agilent-7890 (manufactured by Agilent Corporation) • Column: Inert Cap-1 (GL Sciences Co., Ltd., length 60m, inner diameter 0.25mm, film thickness 1.5μm) • Column temperature: Hold at 60°C for 10 minutes, then increase temperature to 260°C at a rate of 20°C / min, and hold at 260°C for 10 minutes. Injection temperature: 250℃ Detector temperature: 250℃ • Carrier gas: Nitrogen • Split ratio: 100 / 1 • Detector: FID

[0065] <Nuclear magnetic resonance analysis (NMR)> • Nuclear magnetic resonance spectrometer "Bruker Avance III 400" (manufactured by Bruker BioSpin) • Solvent used for measurement: Deuterated chloroform (CDCl3) • Reference substance: Tetramethylsilane (TMS)

[0066] <Infrared Spectroscopy (IR)> • "FTIR-8700" (manufactured by Shimadzu Corporation) ·Window plate: NaCl (liquid film method)

[0067] <Gel Permeation Chromatography (GPC) Analysis> • "HLC-8220" (manufactured by Tosoh) • Developing solvent: tetrahydrofuran

[0068] (Synthesis Example 1) <Synthesis of α-chloroacrylic acid> 150 ml of water was added to a 500 ml round-bottom flask and cooled with ice water. 20 g (0.5 mol) of sodium hydroxide was added to the flask and stirred until dissolved. Using a dropping funnel, 31.6 g (0.2 mol, manufactured by Alpha-Acer) of methyl 2,3-dichloropropionate was added to the flask dropwise over approximately 15 minutes. The flask was allowed to return to room temperature, and the contents were stirred for approximately 7 hours before being cooled again with ice water. 80 ml of 20% hydrochloric acid was added to the flask to acidify the aqueous solution. Sodium chloride was then added to the solution to saturate it, and the contents were transferred to a separatory funnel. The solution was extracted three times with diethyl ether (50 ml) and dried over magnesium sulfate. The solution was transferred to a flask, and the diethyl ether was removed under reduced pressure using an evaporator. Further reduction of the pressure using a vacuum pump yielded 20.2 g (yield: 94%) of α-chloroacrylic acid as a white solid. The process was repeated several times, and the resulting product was used as a raw material for the following alkali metal salts of α-chloroacrylate.

[0069] (Synthesis Example 2) <Synthesis of α-bromoacrylic acid> 150 ml of water was added to a 500 ml round-bottom flask and cooled with ice water. 20 g (0.5 mol) of sodium hydroxide was added to the flask and stirred until dissolved. Using a dropping funnel, 49.2 g (0.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of methyl 2,3-dibromopropionate was added to the flask dropwise over approximately 15 minutes. The flask was allowed to return to room temperature, and the contents were stirred for approximately 10 hours before being cooled again with ice water. 80 ml of 20% hydrochloric acid was added to the flask to acidify the aqueous solution. Sodium chloride was then added to the aqueous solution to saturate it, and the contents were transferred to a separatory funnel. The solution was extracted four times with diethyl ether (50 ml) and dried over magnesium sulfate. The solution was transferred to a flask, and the diethyl ether was removed under reduced pressure using an evaporator. Further reduction of the pressure using a vacuum pump yielded 29.4 g (yield: 97%) of α-bromoacrylic acid as a brown solid.

[0070] (Synthesis Example 3) <Synthesis of sodium α-chloroacrylate> 160 ml of methanol was placed in a 500 ml round-bottom flask, then 8.4 g (0.21 mol) of sodium hydroxide was added and the mixture was stirred at room temperature to dissolve the sodium hydroxide. 21.2 g (0.2 mol) of α-chloroacrylic acid synthesized in Synthesis Example 1 was gradually added to the flask, and the contents were stirred for approximately 4 hours. Methanol was removed under reduced pressure using an evaporator, and the pressure was further reduced using a vacuum pump. The resulting solid was dried in a vacuum dryer (45°C) for 24 hours, yielding 25.6 g (quantitatively) of α-chloroacrylate sodium as a white powder.

[0071] (Synthesis Example 4) <Synthesis of potassium alpha-chloroacrylate> 150 ml of methanol was placed in a 300 ml round-bottom flask, then 13.5 g (0.205 mol) of potassium hydroxide (purity: 85%) was added, and the mixture was stirred at room temperature to dissolve the potassium hydroxide. 21.3 g (0.2 mol) of α-chloroacrylic acid synthesized in Synthesis Example 1 was gradually added to the flask, and the contents were stirred for approximately 4 hours. Methanol was removed under reduced pressure using an evaporator, and the pressure was further reduced using a vacuum pump. The resulting solid was dried in a vacuum dryer (45°C) for 24 hours, yielding 29.3 g (quantitatively) of potassium α-chloroacrylate as a slightly yellowish powder.

[0072] (Synthesis Example 5) <Synthesis of lithium alpha-chloroacrylate> 20 ml of methanol was placed in a 100 ml round-bottom flask, then 19.3 g (0.051 mol) of a 10% methanol solution of lithium methoxide was added and stirred, and the mixture was cooled with ice water. 5.32 g (0.05 mol) of α-chloroacrylic acid synthesized in Synthesis Example 1 was gradually added to the round-bottom flask, and the contents were stirred for approximately 5 hours. Methanol was removed under reduced pressure using an evaporator, and the pressure was further reduced using a vacuum pump. The resulting solid was dried in a vacuum dryer (45°C) for 24 hours, yielding 5.6 g (quantitatively) of lithium α-chloroacrylate as a slightly yellowish powder.

[0073] (Synthesis Example 6) <Synthesis of sodium α-bromoacrylate> 100 ml of methanol was placed in a 300 ml round-bottom flask, then 4.2 g (0.105 mol) of sodium hydroxide was added and stirred at room temperature to dissolve the sodium hydroxide. 24.6 g (0.1 mol) of α-bromoacrylic acid synthesized in Synthesis Example 2 was gradually added to the flask, and the contents were stirred for approximately 3 hours. Methanol was removed under reduced pressure using an evaporator, and the pressure was further reduced using a vacuum pump. The resulting solid was dried in a vacuum dryer (45°C) for 24 hours, yielding 26.5 g (quantitatively) of α-bromoacrylate sodium as a pale pink powder.

[0074] (Example 1-1) <Preparation of α-halogenoacrylic anhydride> In a 300 ml four-necked round-bottom flask equipped with a Liebig condenser and a stirring bar, 9.63 g (0.075 mol) of sodium α-chloroacrylate synthesized in Synthesis Example 3, 30 mg (0.242 mmol) of hydroquinone monomethyl ether and 30 mg (0.151 mmol) of phenothiazine were added as polymerization inhibitors, and then 120 ml of dry acetone (anhydrous acetone) was added and the mixture was stirred under a nitrogen atmosphere. After adding 5.22 g (0.03 mol) of methanesulfonic acid anhydride to the flask, the flask was immersed in an oil bath and stirred at 35°C for 10 hours. After the flask was cooled to room temperature, the solids produced under reduced pressure were filtered. The filtrate was evaporated under reduced pressure using an evaporator to remove the acetone, and then the pressure was reduced using a vacuum pump to obtain 5.41 g (yield: 92%) of α-chloroacrylate anhydride as a brownish, viscous oily substance. 1 H-NMR (400MHz, CDCl3, TMS, δppm): 6.21(d,1H), 6.52(d,1H) FT-IR (liquid film method): 1810cm -1 , 1733cm -1 (νCO-O), 1606cm -1 (νC=C)

[0075] (Examples 1-2) <Preparation of α-halogenoacrylic anhydride> In a 100 ml three-necked round-bottom flask equipped with a Liebig condenser and a stirring bar, 6.70 g (0.025 mol) of sodium α-bromoacrylate synthesized in Synthesis Example 6, 20 mg (0.161 mmol) of hydroquinone monomethyl ether and 20 mg (0.100 mmol) of phenothiazine were added as polymerization inhibitors, and 50 ml of dry acetone (anhydrous acetone) was added and the mixture was stirred under a nitrogen atmosphere. After adding 1.74 g (0.01 mol) of methanesulfonic acid anhydride to the flask, the mixture was stirred at 25°C for 20 hours. The solids produced under reduced pressure were filtered, and the acetone was removed from the filtrate under reduced pressure using an evaporator. Further reduction of the pressure using a vacuum pump yielded 4.22 g (yield: 89%) of α-bromoacrylate anhydride as a brown, viscous oily substance. 1 H-NMR (400MHz, CDCl3, TMS, δppm): 5.95(d,1H), 6.43(d,1H) FT-IR (liquid film method): 1816cm -1 , 1720cm -1 (νCO-O), 1606cm -1 (νC=C)

[0076] (Examples 1-3) <Preparation of α-halogenoacrylic anhydride> In a 200 ml three-necked round-bottom flask equipped with a Liebig condenser and a stirring bar, 3.26 g (0.025 mol) of sodium α-chloroacrylate synthesized in Synthesis Example 3, 20 mg (0.161 mmol) of hydroquinone monomethyl ether and 20 mg (0.100 mmol) of phenothiazine were added as polymerization inhibitors, and 70 ml of dry acetone (anhydrous acetone) was added and the mixture was stirred under a nitrogen atmosphere. After adding 3.26 g (0.01 mol) of p-toluenesulfonic acid anhydride to the flask, the mixture was stirred at 25°C for 24 hours. The solids produced under reduced pressure were filtered, and the acetone was removed from the filtrate under reduced pressure using an evaporator. Further reduction of the pressure using a vacuum pump yielded 1.86 g (yield: 95%) of α-chloroacrylate anhydride as a brown, viscous oily substance.

[0077] (Examples 1-4) <Preparation of α-halogenoacrylic anhydride> In Examples 1-3, the same procedures were followed except that 3.26 g of p-toluenesulfonic anhydride was replaced with 2.82 g (0.01 mol) of trifluoromethanesulfonic anhydride. As a result, 1.80 g (yield: 92%) of α-chloroacrylic anhydride, as α-halogenoacrylic anhydride, was obtained as a brown, viscous oily substance.

[0078] (Examples 1-5) <Preparation of α-halogenoacrylic anhydride> In a 200 ml three-necked round-bottom flask equipped with a Liebig condenser and a stirring bar, 3.61 g (0.025 mol) of potassium α-chloroacrylate synthesized in Synthesis Example 4, 30 mg (0.242 mmol) of hydroquinone monomethyl ether and 30 mg (0.151 mmol) of phenothiazine were added as polymerization inhibitors, and 80 ml of dry acetone (anhydrous acetone) was added and the mixture was stirred under a nitrogen atmosphere. After adding 1.74 g (0.01 mol) of methanesulfonic acid anhydride to the flask, the flask was immersed in an oil bath and stirred at 35°C for 15 hours. After the flask was cooled to room temperature, the solids produced under reduced pressure were filtered. The filtrate was evaporated under reduced pressure to remove acetone, and then the pressure was reduced using a vacuum pump to obtain 1.84 g (yield: 94%) of α-chloroacrylate anhydride as a brownish, viscous oily substance.

[0079] (Examples 1-6) <Preparation of α-halogenoacrylic anhydride> In Examples 1-5, the same procedures were followed as in Examples 1-5, except that 3.61 g (0.025 mol) of potassium α-chloroacrylate was replaced with 2.81 g (0.025 mol) of lithium α-chloroacrylate synthesized in Synthesis Example 5. As a result, 1.77 g (yield: 90%) of α-chloroacrylate anhydride was obtained as a brown, viscous oily substance.

[0080] (Examples 1-7) <Preparation of α-halogenoacrylic anhydride> In Examples 1-3, the same procedures were followed except that 80 ml of dry acetone (anhydrous acetone) was replaced with 70 ml of dry tetrahydrofuran (anhydrous tetrahydrofuran), and 3.26 g (0.01 mol) of p-toluenesulfonic acid anhydride was replaced with 1.74 g (0.01 mol) of methanesulfonic acid anhydride. As a result, 1.71 g (yield: 87%) of α-chloroacrylic acid anhydride was obtained as a brown, viscous oily substance.

[0081] (Examples 1-8) <Preparation of α-halogeno acrylic anhydride> In Examples 1-2, various operations were carried out in the same manner as in Example 1-2, except that 1.74 g (0.01 mol) of methanesulfonic anhydride was changed to 3.26 g (0.01 mol) of p-toluenesulfonic anhydride. As a result, 4.19 g (yield: 88%) of α-bromoacrylic anhydride as α-halogeno acrylic anhydride was obtained as a brown viscous oily substance.

[0082] (Example 2-1) <Preparation of α-halogeno acrylate> Into a 100 mL round-bottom flask equipped with a Dimroth condenser, a dropping funnel with a side tube and a stirring bar, 1.76 g (0.01 mol) of 2,2,2-trifluoro-1-phenylethanol, 2.92 g (0.015 mol) of α-chloroacrylic anhydride synthesized in Example 1-1, and 0.01 g of hydroquinone monomethyl ether were charged, 30 mL of dichloromethane was added, the atmosphere inside the flask was replaced with nitrogen, and then the contents were stirred. After cooling the flask with ice water, 1.18 g (0.015 mol) of pyridine was added dropwise from the dropping funnel over about 5 minutes. After 30 minutes, the flask was warmed to room temperature and further stirred for 6 hours. The contents were transferred to a separatory funnel, and the solution in the separatory funnel was washed with 5% hydrochloric acid, saturated aqueous sodium bicarbonate solution and saturated brine, and dried over magnesium sulfate. The solution was concentrated by an evaporator to obtain a dark brown oily substance. The obtained oily substance was purified by silica gel column chromatography (developing solvent: n-hexane:ethyl acetate=20:1 (volume ratio)), and 2.47 g of 1-phenyl-2,2,2-trifluoroethyl α-chloroacrylate as an α-halogeno acrylate was recovered as an oily substance (yield: 82%). 1 H-NMR (400 MHz, CDCl3, TMS, δppm): 4.96 (m, 1H), 6.28 (s, 1H), 6.85 (s, 1H), 7.36 (m, 5H)

[0083] (Example 2-2) <Preparation of α-halogeno acrylate> A 100 ml round-bottom flask equipped with a Liebig condenser, a dropping funnel with a side tube, and a stirring bar was charged with 1.0 g (0.01 mol) of 2-phenyl-2-propanol, 2.92 g (0.015 mol) of α-chloroacrylic anhydride synthesized in Example 1-1, and 0.01 g of hydroquinone monomethyl ether. 30 ml of dichloromethane was added, and the flask was placed under a nitrogen atmosphere. The contents were then stirred. After cooling the flask with ice water, 1.52 g (0.015 mol) of triethylamine was added dropwise from the dropping funnel over approximately 5 minutes. After 30 minutes, the flask was heated to room temperature and stirred for a further 8 hours. The contents were transferred to a separatory funnel, and the solution in the separatory funnel was washed with 5% hydrochloric acid, saturated sodium bicarbonate solution, and saturated saline solution, and dried over magnesium sulfate. The solution was concentrated using an evaporator, yielding a brownish oily substance. The resulting oily substance was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate = 10:1 (volume ratio)), and 1.80 g of α-phenyl-2-propyl α-chloroacrylate as an α-halogenoacrylate ester was recovered as an oily substance (yield: 80%). 1 H-NMR (400MHz, CDCl3, TMS, δppm): 1.85(s,3H×2), 5.97(s,1H), 6.49(s,1H), 7.25(m,5H)

[0084] (Examples 2-3) <Preparation of α-halogenoacrylate esters> A 100 ml round-bottom flask equipped with a Liebig condenser, a dropping funnel with a side tube, and a stirring bar was charged with 1.36 g (0.01 mol) of 1-methylcyclopentanol, 2.92 g (0.015 mol) of α-chloroacrylic anhydride synthesized in Example 1-1, and 0.01 g of hydroquinone monomethyl ether. 30 ml of dichloromethane was added, and the flask was placed under a nitrogen atmosphere. The contents were then stirred. After cooling the flask with ice water, 1.52 g (0.015 mol) of triethylamine was added dropwise from the dropping funnel over approximately 5 minutes. After 30 minutes, the flask was heated to room temperature and stirred for a further 8 hours. The contents were transferred to a separatory funnel, and the solution in the separatory funnel was washed with 5% hydrochloric acid, saturated sodium bicarbonate solution, and saturated saline solution, and dried over magnesium sulfate. The solution was concentrated using an evaporator, yielding a brownish oily substance. The resulting oily substance was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate = 20:1 (volume ratio)), and 1.69 g of 1-methylcyclopentyl α-chloroacrylate as an α-halogenoacrylate ester was recovered as an oily substance (yield: 91%). 1 H-NMR (400MHz, CDCl3, TMS, δppm): δ1.64(m,9H), 5.93(s,1H),6.41(s,1H)

[0085] (Examples 2-4) <Preparation of α-halogenoacrylate esters> A 100 ml round-bottom flask equipped with a Liebig condenser, a dropping funnel with a side tube, and a stirring bar was charged with 2.44 g (0.01 mol) of 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, 7.11 g (0.015 mol) of α-bromoacrylic anhydride synthesized in Example 1-2, and 0.01 g of hydroquinone monomethyl ether. 40 ml of chloroform was added, and the flask was placed under a nitrogen atmosphere and the contents were stirred. After cooling the flask with ice water, 1.52 g (0.015 mol) of triethylamine was added dropwise from the dropping funnel over approximately 5 minutes. After 30 minutes, the flask was heated to 30°C and stirred for a further 8 hours. The flask was cooled to room temperature and the contents were transferred to a separatory funnel. The solution in the separatory funnel was washed with 5% hydrochloric acid, saturated sodium bicarbonate solution, and saturated saline solution, and dried over magnesium sulfate. The solution was concentrated using an evaporator to obtain a brown oily substance. This oily substance was purified by silica gel column chromatography (eluent, n-heptane:chloroform = 9:1 (volume ratio)), and 2.78 g of alpha-halogenoacrylate hexafluoro-2-phenyl-2-propyl alpha-bromoacrylate was recovered as an oily substance (yield: 74%). 1 H-NMR (400MHz, CDCl3, TMS, δppm): 1.85(s,3H×2), 6.26(s,1H),6.74(s,1H),7.45(m,5H)

[0086] (Comparative Example 2-1) <Preparation of α-halogenoacrylate esters> A 200 ml round-bottom flask equipped with a Liebig condenser, a dropping funnel with a side tube, a septum, and a stirring bar was charged with 3.34 g (0.03 mol) of 1-methylcyclopentanol and 50 ml of dried tetrahydrofuran (anhydrous tetrahydrofuran), and the system was placed under a nitrogen atmosphere. The flask was cooled with ice water, and 23 ml of n-butyllithium (1.6 mol / L)-hexane solution was slowly added dropwise over 15 minutes using a syringe. After stirring the contents for 1 hour, 5.0 g (0.04 mol) of α-chloroacrylate chloride was added dropwise from the dropping funnel over approximately 15 minutes. After stirring for another hour, 45 ml of saturated sodium bicarbonate solution was added to the flask to stop the reaction. The contents were transferred to a separatory funnel and extracted with diethyl ether (45 ml x 2). The ether phase was washed with saturated saline solution and dried over magnesium sulfate. Diethyl ether was removed under reduced pressure using an evaporator, and 6.98 g of a very viscous, orange-colored oily substance was recovered. Analysis of the oily substance by GPC (gel permeation chromatography) confirmed the formation of a polymer. It is presumed that the formed target product, 1-methylcyclopentyl α-chloroacrylate, underwent anionic polymerization due to unreacted lithium alkoxide. This oily substance was purified by silica gel column chromatography (developing solvent, n-hexane:ethyl acetate = 20:1 (volume ratio)), and 1.64 g of 1-methylcyclopentyl α-chloroacrylate as an α-halogenoacrylate ester (yield: 29%) was recovered.

[0087] (Comparative Example 2-2) <Preparation of α-halogenoacrylate esters> In a 100 ml round-bottom flask equipped with a Liebig condenser, a dropping funnel with a side tube, and a stirring bar, 2.0 g (0.02 mol) of 2-phenyl-2-propanol, 4.26 g (0.04 mol) of α-chloroacrylic acid synthesized in Synthesis Example 1, and 0.01 g of hydroquinone monomethyl ether were charged. 40 ml of dichloromethane was added, and the flask was placed under a nitrogen atmosphere, after which the contents were stirred. After cooling the flask with ice water, 9.28 g (0.045 mol) of dicyclohexylcarbodimide was added in small amounts as a coupling agent. After 30 minutes, the flask was heated to room temperature, and stirring was continued for another 15 hours. After filtering off the precipitated solids, the filtrate was transferred to a separatory funnel, and the solution in the separatory funnel was washed with 5% hydrochloric acid, saturated sodium bicarbonate solution, and saturated saline solution, and then dried over magnesium sulfate. When the solution was concentrated using an evaporator, a brownish oily substance was obtained. Analysis of this oily substance by gas chromatography confirmed that a large amount of the raw material, 2-phenyl-2-propanol, remained.

[0088] As is clear from the results of the above examples and comparative examples, it can be seen that α-halogenoacrylate esters can be synthesized in high yield using the α-halogenoacrylate anhydride of the present invention. [Industrial applicability]

[0089] According to the present invention, it is possible to provide α-halogenoacrylate anhydride and a method for producing the same, which can be synthesized in high yield as α-halogenoacrylate esters. Furthermore, according to the present invention, a method for producing α-halogenoacrylate esters using the above-mentioned α-halogenoacrylate anhydride can be provided.

Claims

1. The following formula (1): 【Chemistry 1】 [In formula (1), X represents a chlorine atom or a bromine atom.] An α-halogenoacrylic anhydride represented by [the formula].

2. A method for producing α-halogenoacrylic anhydride according to claim 1, The following formula (2): 【Chemistry 2】 [In formula (2), X represents a chlorine atom or a bromine atom, and Y represents an alkali metal atom.] Alkali metal salts of α-halogenoacrylate represented by, Formula (3) below: (RSO ２ ) ２ O (3) [In formula (3), R represents an optionally substituted hydrocarbon group.] Organic sulfonic anhydride represented by and A method for producing α-halogenoacrylic anhydride by bringing into contact with [a certain substance].

3. The method for producing α-halogenoacrylic acid anhydride according to claim 2, wherein the organic sulfonic acid anhydride is methanesulfonic acid anhydride.

4. A method for producing an α-halogenoacrylate ester, comprising contacting the α-halogenoacrylate anhydride described in claim 1 with at least one hydroxyl group-containing compound of alcohols and phenols.

5. The method for producing an α-halogenoacrylate ester according to claim 4, wherein the hydroxyl group-containing compound is at least one of a secondary alcohol and a tertiary alcohol.

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