Method for producing 1,1,2-trisubstituted ethane and method for producing 1,1-disubstituted olefin

Abstract

A method for producing a 1,1,2-trisubstituted ethane according to the present disclosure includes a reduction reaction step in which a 1,1,2-trisubstituted olefin represented by formula (I) is reduced to obtain a 1,1,2-trisubstituted ethane represented by formula (II), as shown in the reaction scheme. The reduction reaction step is performed in the presence of a hydrogenation catalyst. In formulae (I) and (II), A and D each independently represent CN, CO2R1, etc., R1 represents a linear or branched, C1 to C20 (un)saturated alkyl group, etc., and R represents a linear, branched, or alicyclic, C1 to C20 (un)saturated alkoxy group, a carboxy group, etc.

Description

Process for producing 1,1,2-trisubstituted ethane and process for producing 1,1-disubstituted olefin

[0001] The present disclosure relates to a process for producing 1,1,2-trisubstituted ethanes and a process for producing 1,1-disubstituted olefins.

[0002] Cyanoacrylates have traditionally been used in a variety of applications (for example, adhesives, coating agents, sealants, etc.).

[0003] Cyanoacrylates are generally produced by condensing cyanoacetate and formaldehyde in an organic solvent and then depolymerizing the resulting polymer at high temperature and reduced pressure. The resulting cyanoacrylate (hereinafter also referred to as "crude cyanoacrylate") contains impurities (e.g., cyanoacrylate raw materials, catalysts, by-products, etc.). Therefore, the crude cyanoacrylate is distilled to obtain a highly pure cyanoacrylate (hereinafter also referred to as "purified cyanoacrylate") (see, for example, Patent Document 1).

[0004] Patent Document 1: International Publication No. 2004 / 106284

[0005] However, distillation may not be sufficient to remove impurities from crude cyanoacrylates. Therefore, there is a need for a method for producing anionically polymerizable 1,1-disubstituted olefins (e.g., cyanoacrylates) (hereinafter also referred to as "anionically polymerizable disubstituted olefins") in high yields by separating impurities without distillation.

[0006] The present disclosure has been made in consideration of the above circumstances. An object of one embodiment of the present disclosure is to provide a method for producing 1,1,2-trisubstituted ethane that can be used as a raw material in a production method that can produce anionically polymerizable disubstituted olefins in high yield without performing distillation. An object of another embodiment of the present disclosure is to provide a method for producing 1,1-disubstituted olefins that can produce anionically polymerizable disubstituted olefins in high yield without performing distillation.

[0007] Specific means for solving the above problems include the following aspects.

[0008] <1> A method for producing 1,1,2-trisubstituted ethane, comprising a reduction reaction step of reducing a 1,1,2-trisubstituted olefin represented by formula (I) to obtain a 1,1,2-trisubstituted ethane represented by formula (II), as shown in the following reaction formula, wherein the reduction reaction step is carried out in the presence of a hydrogenation catalyst.

[0009]

[0010] In formula (I) and formula (II), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２ R represents one selected from the group consisting of １ is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ Cycloalkyl, alkylcycloalkyl, C ３ -C ２０In formula (I) and formula (II), R represents a linear, branched, or alicyclic saturated or unsaturated C １ -C ２０ <2> The method for producing 1,1,2-trisubstituted ethane according to <1>, wherein the hydrogenation catalyst contains at least one metal selected from the group consisting of palladium, nickel, platinum, rhodium, ruthenium, iridium, copper, chromium, iron, aluminum, and zinc. <3> The hydrogenation catalyst is Pd(OH) ２<4> The method for producing 1,1,2-trisubstituted ethane according to any one of <1> to <3>, wherein the reduction reaction step is carried out in the presence of a reducing agent, and the reducing agent comprises hydrogen or a metal hydride. <5> The method for producing 1,1,2-trisubstituted ethane according to <4>, wherein the reducing agent comprises hydrogen, and the hydrogen pressure in the reduction reaction step is 0.1 MPa to 20 MPa. <6> The method for producing 1,1,2-trisubstituted ethane according to any one of <1> to <5>, wherein the reduction reaction step is carried out in the presence of a water scavenger. <7> The method for producing 1,1,2-trisubstituted ethane according to <6>, wherein the water scavenger comprises crystalline zeolite and a carboxylic acid anhydride. <8> The method for producing 1,1,2-trisubstituted ethane according to any one of <1> to <7> above, wherein the reduction reaction step is carried out in the presence of a solvent, and the solvent comprises at least one selected from the group consisting of aromatic hydrocarbons, hydrocarbons, ethers, ketones, alcohols, carboxylic acids, and esters. <9> The method for producing 1,1,2-trisubstituted ethane according to any one of <1> to <8> above, wherein the reduction reaction step is carried out at a reaction temperature of 0°C to 150°C. <10> A method for producing 1,1-disubstituted olefins, comprising: a step of obtaining 1,1,2-trisubstituted ethane by the production method according to any one of <1> to <9> above; and an elimination reaction step of eliminating the functional group R from the 1,1,2-trisubstituted ethane as shown in the following reaction formula (III), wherein the elimination reaction step is carried out in the presence of at least one catalyst selected from the group consisting of an acid catalyst, a base catalyst, and an acid-base catalyst.

[0011]

[0012] A in (III) is the same as A in formula (I) and formula (II), and D in (III) is the same as D in formula (I) and formula (II). <11> A method for producing a 1,1-disubstituted olefin, comprising: an elimination reaction step of eliminating a functional group R from a 1,1,2-trisubstituted ethane represented by formula (II) to obtain a 1,1-disubstituted olefin represented by formula (III), as shown in the following reaction formula: The elimination reaction step is carried out in the presence of at least one catalyst selected from the group consisting of an acid catalyst, a base catalyst, and an acid-base catalyst.

[0013]

[0014] In formula (II) and formula (III), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２ R represents one selected from the group consisting of １ is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ Cycloalkyl, alkylcycloalkyl, C ３ -C ２０In formulas (II) and (III), R represents a linear, branched, or alicyclic saturated or unsaturated C １ -C ２０R represents an alkoxy group, a carboxy group, a hydroxy group, a fluoroalkylsulfone group, a fluorosulfone group, an alkylsulfone group, an arylsulfone group, a halogen atom, a phenoxy group, or a selenoxy group. <12> The method for producing a 1,1-disubstituted olefin according to <10> or <11> above, wherein the elimination reaction step is carried out in the presence of the acid catalyst, and the acid catalyst contains at least one compound selected from the group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid. <13> The method for producing a 1,1-disubstituted olefin according to any one of <10> to <12> above, wherein R represents the alkoxy group, and the elimination reaction step is carried out in the presence of an alcohol scavenger. <14> The method for producing a 1,1-disubstituted olefin according to <13> above, wherein the alcohol scavenger contains a carboxylic acid anhydride. <15> The method for producing a 1,1-disubstituted olefin according to <14>, wherein the carboxylic acid anhydride includes at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, maleic anhydride, and succinic anhydride.<16> The acid catalyst is sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, a strongly acidic ion exchange resin, a solid catalyst in which a sulfonic acid group is chemically bonded to a support, a solid catalyst in which a compound having a sulfonic acid group is supported on a support, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monobenzyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monododecyl phosphate, monobutoxyethyl phosphate, mono-2-ethylhexyl phosphate, monoisotridecyl phosphate, monohexyl phosphate <16>. The method for producing a 1,1-disubstituted olefin according to any one of <10> to <15>, wherein the phosphate group contains at least one selected from the group consisting of didecyl phosphate, monooleyl phosphate, monotetracosyl phosphate, monophenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, dihexyl phosphate, dibenzyl phosphate, didecyl phosphate, diisodecyl phosphate, didodecyl phosphate, dibutoxyethyl phosphate, di-2-ethylhexyl phosphate, diisotridecyl phosphate, dihexadecyl phosphate, dioleyl phosphate, ditetracosyl phosphate, and diphenyl phosphate.

[0015] According to one embodiment of the present disclosure, there is provided a method for producing 1,1,2-trisubstituted ethane, which can be used as a raw material in a production process that can produce anionically polymerizable disubstituted olefins in high yield without distillation. According to another embodiment of the present disclosure, there is provided a method for producing 1,1-disubstituted olefins that can produce anionically polymerizable disubstituted olefins in high yield without distillation.

[0016] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present disclosure, when a composition contains multiple substances corresponding to each component, the amount of each component refers to the total amount of the multiple substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, a combination of preferred embodiments is a more preferred embodiment. In the description of groups (atomic groups) in the present disclosure, a description that does not specify whether substituted or unsubstituted includes both unsubstituted and substituted groups.

[0017] (1) First Embodiment (1.1) Method for Producing 1,1,2-Trisubstituted Ethane A method for producing 1,1,2-trisubstituted ethane according to a first embodiment of the present disclosure includes a reduction reaction step of reducing a 1,1,2-trisubstituted olefin represented by formula (I) (hereinafter also referred to as "trisubstituted olefin (I)") to obtain a 1,1,2-trisubstituted ethane represented by formula (II) (hereinafter also referred to as "trisubstituted ethane (II)"), as shown in the following reaction formula. The reduction reaction step is carried out in the presence of a hydrogenation catalyst.

[0018]

[0019] In formula (I) and formula (II), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２ R represents one selected from the group consisting of １is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ In formula (I) and formula (II), R represents a linear, branched, or alicyclic saturated or unsaturated C １ -C ２０ It represents an alkoxy group, a carboxy group, a hydroxy group, a fluoroalkylsulfone group, a fluorosulfone group, an alkylsulfone group, an arylsulfone group, a halogen atom, a phenoxy group, or a selenoxy group.

[0020] The term "hydrogenation catalyst" refers to a solid catalyst for a hydrogenation reaction. The term "hydrogenation reaction" refers to a reaction in which hydrogen is added to the unsaturated bond of an unsaturated organic compound.

[0021] The method for producing 1,1,2-trisubstituted ethane of the first embodiment has the above-described configuration, and therefore can produce 1,1,2-trisubstituted ethane that can be used as a raw material in a production method that can produce anionically polymerizable disubstituted olefins in high yield without performing distillation.

[0022] The anionically polymerizable disubstituted olefin is represented by the following formula (III):

[0023]

[0024] A in formula (III) is the same as A in formulas (I) and (II). D in formula (III) is the same as D in formulas (I) and (II).

[0025] According to the method for producing 1,1,2-trisubstituted ethane of the first embodiment, even if the trisubstituted ethane (II) is a specific trisubstituted ethane (II), the specific trisubstituted ethane (II) can be produced in high yield. The "specific trisubstituted ethane (II)" refers to a trisubstituted ethane in which at least one of A and D is a highly electron-withdrawing functional group (for example, a cyano group (CN) or a carbonyl group (CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , COPO (OR １ ) ２ and COP(OR １ ) ２ ) and side reactions (e.g., elimination reactions with bases, etc.) readily occur. This is presumably due to the ease with which the solid hydrogenation catalyst can be removed by filtration.

[0026] (1.1.1) Reduction Reaction Step In the reduction reaction step, the tri-substituted olefin (I) is reduced in the presence of a hydrogenation catalyst to obtain the tri-substituted ethane (II).

[0027] (1.1.1.1) 1,1,2-Trisubstituted Olefins Trisubstituted olefins (I) are represented by the following formula (I):

[0028]

[0029] In formula (I), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２R represents one selected from the group consisting of １ is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ Cycloalkyl, alkylcycloalkyl, C ３ -C ２０ In formula (I), R represents a linear, branched, or alicyclic saturated or unsaturated C １ -C ２０ It represents an alkoxy group, a carboxylic acid, a fluoroalkylsulfonic acid, a fluorosulfonic acid, an alkylsulfonic acid, an arylsulfonic acid, a halogen atom, a phenoxy group, or a selenoxy group.

[0030] (1.1.1.1.1) A and D A and D in formula (I) are explained below. A and D are electron-withdrawing groups attached to the same carbon atom. A and D may be the same or different.

[0031] Linear or branched saturated or unsaturated C １ -C ２０Examples of alkyl include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, cyclobutyl, n-hexyl, cyclohexyl, 2-octyl, 2-ethylhexyl, hexadecyl, and stearyl. １ -C ２０ In the halogenated alkyl, the hydrogen atoms of the alkyl may be partially or completely halogenated, and the carbon chain of the alkyl may be linear or branched. ４ -C ２０ Examples of alkylsilanes include methyltrimethylsilane, ethyltrimethylsilane, and propyltrimethylsilane. １ -C ２０ Examples of the acetoxysilane include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, and tetraacetoxysilane. ２ -C ２０ Examples of alkoxyalkyl include 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-methoxypropyl, and 2-(1-methoxy)propyl. ２ -C ２０ Alkenyl includes, for example, allyl and propenyl groups. ２ -C ２０ Examples of the alkynyl include a propargyl group. ２ -C １０ Examples of alkylene include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-(ethyl)trimethylene, and 1-(methyl)tetramethylene. ３ -C ２０ Examples of cycloalkyl include cyclobutyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of alkylcycloalkyl include methylcycloalkyl, isopropylcycloalkyl, and isobornyl. ３ -C ２０Examples of cycloalkenyl include cyclohexenyl groups. Examples of alkylcycloalkenyl include terpinyl. Examples of aryl include phenyl and naphthyl. Examples of alkyl moieties bonded to aryl include benzyl. Examples of aliphatic heterocyclic moieties include tetrahydrofuryl and tetrahydrothiophene groups. Examples of alkyl moieties bonded to aliphatic heterocyclic rings include 2,3-epoxypropyl, oxetanylmethyl, and tetrahydrofurfuryl. Examples of aromatic heterocyclic moieties include furyl and thiophenyl groups. Examples of alkyl moieties bonded to aromatic heterocyclic rings include furfuryl. The acrylate moiety is represented by formula (a1).

[0032]

[0033] In formula (a1), T is -(CH ２ ) ｚ - (where z is 2 to 12), branch C ３ -C １２ Alkylene chain, cyclohexylene, optionally substituted biphenylene, optionally substituted -C ６ H ４ C (Me) ２ C ６ H ４ -, optionally substituted -C ６ H ４ CH ２ C ６ H ４ -, or optionally substituted phenylene. ２ is H, Me, CN or CO ２ R ３ (However, R ３ is C １ -C １０ R is an alkyl group. ２ When R is H or Me, this corresponds to an acrylate or methacrylate moiety, respectively. ２ When R is CN, it corresponds to a cyanoacrylate moiety. ２ CO ２ R３ This corresponds to a malonic acid methylidene ester moiety. The glycolic acid moiety is -CH ２ CO ２ R ４ It indicates that ４ is C １ -C ４ The carboxylic acid ester moiety is an alkyl group. ２ ) ｋ CO ２ R ５ k is preferably 2 to 18, more preferably 2 to 12, and even more preferably 2 to 8. ５ is C １ -C ４ The halogen-substituted alkyl moiety is, for example, 2,2,2-trifluoroethanol, and 1,1,1,3,3,3-hexafluoropropyl.

[0034] (1.1.1.1.2) R R in formula (I) will be explained.

[0035] Linear, branched or alicyclic saturated or unsaturated C １ -C ２０Examples of alkoxy groups include ethoxy groups, methoxy groups, and propoxy groups. Examples of carboxy groups include acetoxy groups. Examples of fluoroalkylsulfone groups include trifluoromethanesulfonyl groups. Examples of fluorosulfone groups include fluorosulfonyl. Examples of alkylsulfone groups include methanesulfonyl, ethanesulfonyl, n-propanesulfonyl, and isopropanesulfonyl. Examples of arylsulfone groups include benzenesulfonyl, p-toluenesulfonyl, naphthalenesulfonyl, and indenesulfonyl. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of phenoxy groups include phenoxy groups, methylphenoxy groups, ethylphenoxy groups, propylphenoxy groups, methoxyphenoxy groups, ethoxyphenoxy groups, and propoxyphenoxy groups. Examples of the selenoxy group include a selenomethyl group, a selenoethyl group, a selenopropyl group, a selenobutyl group, and a selenohexyl group.

[0036] (1.1.1.1.3) Specific Examples Examples of the trisubstituted olefin (I) include compounds represented by the following formula (I-1).

[0037]

[0038] In formula (I-1), p represents an integer of 0 to 5. １ are each independently —CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH(R ６ ) CH ２ - or -CH ２ CH (R ６ )-. ６ represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. ７ represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent. ８represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent.

[0039] In formula (I-1), p is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 2, from the viewpoint of production costs.

[0040] In formula (I-1), from the viewpoint of production cost, R ６ R preferably represents an alkyl group having 1 to 3 carbon atoms which may have a substituent. ６ R may be a linear alkyl group or a branched alkyl group. Examples of the substituent include an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, and an acyloxy group. ６ Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

[0041] In formula (I-1), from the viewpoint of production cost, R ７ R preferably represents an optionally substituted C1 to C6 alkyl group, more preferably an optionally substituted C1 to C3 alkyl group. ７ R may be a linear alkyl group or a branched alkyl group. Examples of the substituent include an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, and an acyloxy group. ７ Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

[0042] In formula (I-1), from the viewpoint of production cost and ease of removal after desorption, R ８ R preferably represents an optionally substituted C1 to C6 alkyl group, more preferably an optionally substituted C1 to C3 alkyl group. ８ R may be a linear alkyl group or a branched alkyl group. Examples of the substituent include an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, and an acyloxy group. ８Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group, with a methyl group or an ethyl group being preferred.

[0043] The trisubstituted olefin (I) may be prepared by any known method.

[0044] (1.1.1.2) Hydrogenation catalyst The hydrogenation catalyst is not particularly limited as long as it is a catalyst that promotes the progress of the hydrogenation reaction of adding hydrogen to the unsaturated bond of the trisubstituted olefin (I). The hydrogenation catalyst may be a known hydrogenation catalyst.

[0045] The hydrogenation catalyst may contain at least one metal selected from transition metals belonging to Groups 6 to 13 of the periodic table. Examples of transition metals belonging to Groups 6 to 13 include chromium, iron, ruthenium, osmium, cobalt, rhodium, iridium, palladium, nickel, platinum, copper, silver, gold, zinc, and aluminum.

[0046] The hydrogenation catalyst preferably contains at least one metal selected from the group consisting of palladium, nickel, platinum, rhodium, ruthenium, iridium, copper, chromium, iron, aluminum, and zinc. These transition metals may be used alone or in combination of two or more.

[0047] The mass ratio of the transition metal to the total amount of the trisubstituted olefin (I) (hereinafter also referred to as "catalyst amount") is not particularly limited, and from the viewpoints of economy and waste, it is preferably 0.1 mass% to 20 mass%, more preferably 0.1 mass% to 10 mass%, and even more preferably 1 mass% to 5 mass%.

[0048] The hydrogenation catalyst preferably contains the transition metal and a carrier on which the transition metal is supported. This allows the hydrogenation catalyst to be easily removed by a separation operation (e.g., filtration) after the reaction is completed, and the catalyst can be reused. Examples of the carrier include activated carbon (C), alumina (Al ２ O ３ ), silicon dioxide, titanium dioxide, calcium carbonate, barium sulfate, diatomaceous earth, clay, etc. These carriers may be used alone or in combination of two or more.

[0049] The hydrogenation catalyst is Pd(OH) ２ It is preferable that the catalyst contains at least one selected from the group consisting of Pd(OH) / C (palladium hydroxide / carbon), Pd / C (palladium / carbon) and Pt / C (platinum / carbon), and Pd(OH) ２ It is more preferable that the hydrogenation catalyst contains at least one of palladium hydroxide / carbon (Pd / C) and palladium / carbon (Pd / C). This allows the production of trisubstituted ethane (II) in a higher reaction yield than when the hydrogenation catalyst does not contain at least one selected from the group consisting of the above-mentioned catalyst species.

[0050] The amount of the transition metal supported on the support is not particularly limited, and is preferably 1 mass % to 20 mass %, more preferably 5 mass % to 20 mass %, and even more preferably 10 mass % to 20 mass %, based on the total amount of the hydrogenation catalyst.

[0051] The amount of the hydrogenation catalyst used is not particularly limited, and may be adjusted so that the mass ratio of the transition metal to the total amount of the trisubstituted olefin (I) falls within the above range.

[0052] (1.1.1.3) Reduction Reaction The reduction reaction is carried out by charging the trisubstituted olefin (I) and a hydrogenation catalyst into a reaction vessel. The reaction vessel may be operated batchwise or continuously.

[0053] In the reduction reaction step, the reaction temperature is preferably 0°C to 150°C. This makes it possible to suppress side reactions (such as decomposition of the product) more effectively than when the reaction temperature is outside the range of 0°C to 150°C. The reaction temperature is more preferably 0°C to 80°C, and even more preferably 10°C to 30°C.

[0054] The reaction time is not particularly limited and is appropriately selected depending on the type and amount of the trisubstituted olefin (I), etc. The reaction time may be 1 hour to 10 hours.

[0055] (1.1.1.4) Reducing Agent The reduction reaction step may be carried out in the presence of a reducing agent. In other words, a reducing agent may be further added to the reaction vessel to cause the reduction reaction to proceed.

[0056] The term "reducing agent" refers to a source of hydrogen to be added to the unsaturated bond of the trisubstituted olefin (I).

[0057] Reducing agents include, for example, hydrogen and metal hydrides (e.g., NaBH ４ , K.B.H. ４ , and LiAlH ４ These reducing agents may be used alone or in combination of two or more. The reducing agent may be a known reducing agent.

[0058] The reduction reaction step is carried out in the presence of a reducing agent, and the reducing agent preferably contains hydrogen or a metal hydride.

[0059] When the reduction reaction step is carried out in the presence of a reducing agent, the amount of the reducing agent used is not particularly limited and is appropriately selected depending on the type of reducing agent and the like.

[0060] When the reduction reaction step is carried out in the presence of a reducing agent, the reducing agent preferably contains hydrogen, and the hydrogen pressure in the reduction reaction step is preferably 0.1 MPa to 20 MPa. From the viewpoints of safety and the economy of production facilities, the hydrogen pressure is more preferably 0.1 MPa to 0.9 MPa, and even more preferably 0.1 MPa to 0.5 MPa.

[0061] (1.1.1.5) Water Scavenger The reduction reaction step may be carried out in the presence of a water scavenger. In other words, a water scavenger may be further added to the reaction vessel to allow the reduction reaction to proceed. The reduction reaction step may be carried out in the absence of a water scavenger.

[0062] The term "water scavenger" refers to a solid that has the property of absorbing moisture.

[0063] The reduction reaction step is preferably carried out in the presence of a water scavenger. When synthesizing the trisubstituted ethane (II), a compound having a highly electron-withdrawing functional group (e.g., a cyano group) at the carbon at the first position of the carbon-carbon multiple bond is prone to side reactions (e.g., elimination of a substituent at the carbon at the second position of the carbon-carbon multiple bond). The presence of a basic atmosphere or a Lewis basic compound can cause an elimination reaction. By carrying out the reduction reaction step in the presence of a water scavenger (i.e., a dehydrating agent), water, which can become a Lewis base, is removed. This makes it difficult for side reactions to proceed. As a result, the method for producing 1,1,2-trisubstituted ethane of the first embodiment can produce the trisubstituted ethane (II) in a higher yield than when the reduction reaction step is not carried out in the presence of a water scavenger.

[0064] Examples of water scavenger agents include crystalline zeolites (e.g., molecular sieves), carboxylic acid anhydrides (e.g., acetic anhydride, propionic anhydride, and butyric anhydride), and oxides (e.g., phosphorus pentoxide, calcium oxide, barium oxide, and magnesium oxide). These water scavenger agents may be used alone or in combination of two or more. The water scavenger agent may be a known water scavenger.

[0065] When the reduction reaction step is carried out in the presence of a water scavenger, the water scavenger preferably contains a crystalline zeolite and a carboxylic acid anhydride. This makes it easier to remove water, which can become a Lewis base. As a result, the method for producing 1,1,2-trisubstituted ethane of the first embodiment can produce trisubstituted ethane (II) in a higher yield than in a configuration in which the water scavenger does not contain a crystalline zeolite or a carboxylic acid anhydride.

[0066] When the reduction reaction step is carried out in the presence of a water scavenger, the amount of the water scavenger used is not particularly limited. When the water scavenger contains a carboxylic acid anhydride, the amount of the water scavenger used is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 50 parts by mass, per 100 parts by mass of the tri-substituted olefin (I). When the water scavenger contains a molecular sieve, the amount of the water scavenger used is preferably 10 parts by mass to 500 parts by mass, more preferably 100 parts by mass to 200 parts by mass, per 100 parts by mass of the tri-substituted olefin (I).

[0067] (1.1.1.6) Solvent The reduction reaction step may be carried out in the presence of a solvent. In other words, the reduction reaction may be carried out by adding a solvent to the reaction vessel. The reduction reaction step may be carried out in the absence of a solvent.

[0068] Examples of the solvent include aromatic hydrocarbons (e.g., benzene, toluene, and ethylbenzene), ethers (e.g., diethyl ether, anisole, and tetrahydrofuran), ketones (e.g., acetone, methyl ethyl ketone, and acetophenone), alcohols (e.g., methanol, ethanol, and n-butanol), carboxylic acids (e.g., formic acid, acetic acid, and propionic acid), esters (e.g., methyl acetate, n-butyl acetate, and benzyl benzoate), aliphatic hydrocarbons (e.g., n-hexane, n-octane, and cyclohexane), halogenated hydrocarbons (e.g., dichloromethane, trichloroethane, and chlorobenzene), nitro compounds (e.g., nitromethane and nitrobenzene), and carboxylic acid amides (e.g., N,N-dimethyl formamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (e.g., N,N'-dimethylimidazolidone, and N,N,N,N-tetramethylurea, etc.), sulfones (e.g., dimethyl sulfone, and tetramethylene sulfone, etc.), sulfoxides (e.g., dimethyl sulfoxide, and diphenyl sulfoxide, etc.), lactones (e.g., γ-butyrolactone, and ε-caprolactone, etc.), polyethers (e.g., triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), and 18-crown-6, etc.), nitriles (e.g., acetonitrile, and benzonitrile, etc.), and carbonates (e.g., dimethyl carbonate, and ethylene carbonate, etc.). These solvents may be used alone or in combination of two or more.

[0069] The reduction reaction step is preferably carried out in the presence of a solvent, and the solvent preferably contains at least one selected from the group consisting of aromatic hydrocarbons, hydrocarbons, ethers, ketones, alcohols, carboxylic acids, and esters.

[0070] When the reduction reaction step is carried out in the presence of a solvent, the amount of the solvent used is not particularly limited, and is preferably 10 parts by mass to 2000 parts by mass, more preferably 50 parts by mass to 500 parts by mass, per 100 parts by mass of the trisubstituted olefin (I).

[0071] (1.1.1.7) 1,1,2-trisubstituted ethane By carrying out the reduction reaction step, trisubstituted ethane (II) is obtained. Trisubstituted ethane (II) is represented by the following formula (II).

[0072]

[0073] In formula (II), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２ R represents one selected from the group consisting of １ is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ Cycloalkyl, alkylcycloalkyl, C ３ -C ２０In formula (I) and formula (II), R represents a linear, branched, or alicyclic saturated or unsaturated C １ -C ２０ It represents an alkoxy group, a carboxy group, a hydroxy group, a fluoroalkylsulfone group, a fluorosulfone group, an alkylsulfone group, an arylsulfone group, a halogen atom, a phenoxy group, or a selenoxy group.

[0074] In formula (II), A, D, and R are the same as those exemplified as A, D, and R in formula (I). A in formula (II) is the same as A in formula (I). D in formula (II) is the same as D in formula (I). R in formula (II) is the same as R in formula (I).

[0075] The trisubstituted ethane (II) includes, for example, a compound represented by the following formula (II-1):

[0076]

[0077] In formula (II-1), p, L １ , R ７ , and R 8 is as described above in formula (I-1).

[0078] The use of the trisubstituted ethane (II) is not particularly limited, but examples thereof include a raw material for anionically polymerizable disubstituted olefins.

[0079] (1.1.2) Separation Step The method for producing 1,1,2-trisubstituted ethane of the first embodiment may include a separation step. In the separation step, the reaction solution after the reduction reaction step is filtered. The separation step is carried out after the reduction reaction step is carried out. As a result, the hydrogenation catalyst is separated from the reaction solution, and the target trisubstituted ethane (II) can be recovered. When the reduction reaction step is carried out in the presence of a water scavenger, the solid (insoluble) water scavenger is also separated from the reaction solution together with the hydrogenation catalyst by filtration. The filtration method is not particularly limited, and any known method may be used.

[0080] When the reduction reaction step is carried out in the presence of a solvent, the separation step may involve distilling off the solvent from the reaction solution after filtration. The boiling point of the impurity liquid (e.g., carboxylic acid produced from carboxylic acid anhydride and water) contained in the reaction solution after the reduction reaction step is close to the boiling point of the solvent. This separates impurities from the reaction solution in addition to the solvent. As a result, a reaction solution with a higher yield of trisubstituted ethane (II) can be obtained. Examples of distillation methods include evaporators, simple distillation, and thin-film distillation. The temperature during distillation may be 40°C to 120°C.

[0081] (1.2) Method for Producing 1,1-Disubstituted Olefin The method for producing a 1,1-disubstituted olefin according to the first embodiment of the present disclosure includes a step of obtaining a 1,1-disubstituted olefin represented by the following formula (III) (hereinafter also referred to as "disubstituted olefin (III)") using 1,1,2-trisubstituted ethane obtained by the method for producing 1,1,2-trisubstituted ethane according to the first embodiment.

[0082]

[0083] A in (III) is the same as A in formulas (I) and (II), and D in (III) is the same as D in formulas (I) and (II).

[0084] The method for producing a 1,1-disubstituted olefin of the first embodiment preferably includes an elimination reaction step of obtaining a trisubstituted ethane (II) by the method for producing a 1,1,2-trisubstituted ethane of the first embodiment, and an elimination reaction step of obtaining a 1,1-disubstituted olefin represented by the following formula (III) (i.e., a disubstituted olefin (III)) by eliminating the functional group R of the trisubstituted ethane (II), as shown in the following reaction formula: The elimination reaction step is carried out in the presence of at least one catalyst selected from the group consisting of an acid catalyst, a base catalyst, and an acid-base catalyst (hereinafter also referred to as an "elimination reaction catalyst").

[0085]

[0086] A in (III) is the same as A in formulas (I) and (II), and D in (III) is the same as D in formulas (I) and (II).

[0087] The term "acid-base catalyst" refers to a catalyst that is a mixture of an acid and a base.

[0088] The method for producing a 1,1-disubstituted olefin of the first embodiment has the above-mentioned configuration, and therefore can produce an anionically polymerizable disubstituted olefin in high yield without carrying out distillation.

[0089] In the method for producing a 1,1-disubstituted olefin of the first embodiment, trisubstituted ethane (II) is used as a raw material. Therefore, according to the method for producing a 1,1-disubstituted olefin of the first embodiment, an anionically polymerizable disubstituted olefin can be produced without high-temperature treatment (e.g., depolymerization, etc.). Due to its reactivity, the anionically polymerizable disubstituted olefin (III) is prone to polymerization reaction with the reactants, catalysts, and additives used during synthesis and purification. This may result in a decrease in the yield of the disubstituted olefin (III). According to the method for producing a 1,1-disubstituted olefin of the first embodiment, the disubstituted olefin (III) can be synthesized in an acidic atmosphere that stabilizes the disubstituted olefin (III). This allows the anionically polymerizable disubstituted olefin to be obtained in high yield. Furthermore, after the elimination reaction step, a purification method appropriate for the type of disubstituted olefin (III) can be adopted. According to the method for producing a 1,1-disubstituted olefin of the first embodiment, when the disubstituted olefin (III) is a polyfunctional monomer, the formation of a crosslinked oligomer is not required. Therefore, according to the method for producing a 1,1-disubstituted olefin of the first embodiment, it is possible to produce a polyfunctional monomer that has been difficult to synthesize by conventional methods. In the method for producing a 1,1-disubstituted olefin of the first embodiment, an alkoxy group is used as the leaving group of the trisubstituted olefin (I), a low-boiling carboxylic acid anhydride is used as the leaving alcohol scavenger, and a solid acid is used as the reaction catalyst, whereby the disubstituted olefin (III) is obtained by filtration and distillation of the low-boiling components. Therefore, according to the method for producing a 1,1-disubstituted olefin of the first embodiment, it is possible to produce the disubstituted olefin (III) even if the disubstituted olefin (III) is a monomer that is extremely difficult to distill (e.g., a solid monomer, a polyfunctional monomer, etc.).

[0090] (1.2.1) Elimination Reaction Step In the elimination reaction step, a reaction of eliminating the functional group R from the trisubstituted ethane (II) (hereinafter also referred to as "elimination reaction") proceeds in the presence of an elimination reaction catalyst to obtain a disubstituted olefin (III).

[0091] (1.2.1.1) Catalyst for Elimination Reaction The catalyst for the elimination reaction is at least one selected from the group consisting of acid catalysts, base catalysts, and acid-base catalysts, and is not particularly limited as long as it is a catalyst that promotes the elimination reaction of the trisubstituted ethane (II).

[0092] (1.2.1.1.1) Acid Catalyst Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, and strongly acidic ion exchange resins (e.g., "Catalyst Ion Exchange Resin" manufactured by Organo Corporation). Amberlyst 15 DRY"), solid catalysts in which sulfonic acid groups are chemically bonded to a carrier, solid catalysts in which a compound having a sulfonic acid group is supported on a carrier, phosphoric acid, phosphorous acid, pyrophosphoric acid, polyphosphoric acid, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monobenzyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monododecyl phosphate, monobutoxyethyl phosphate, mono-2-ethylhexyl phosphate, monoisotridecyl phosphate, monohexadecyl phosphate, monooleyl phosphate, monotetracosyl phosphate, monophenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, dihexyl phosphate, dibenzyl phosphate, didecyl phosphate, diisodecyl phosphate, didodecyl phosphate, dibutoxyethyl phosphate, di-2-ethylhexyl phosphate, diisotridecyl phosphate, dihexadecyl phosphate, dioleyl phosphate, ditetracosyl phosphate, and diphenyl phosphate. These acid catalysts may be used alone or in combination of two or more. Examples of the support for the solid catalyst include silica gel, alumina, magnesia, carbon, calcium carbonate, zirconium oxide, and titanium oxide.

[0093] Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resins, solid catalysts in which sulfonic acid groups are chemically bonded to a carrier, solid catalysts in which a compound having a sulfonic acid group is supported on a carrier, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monobenzyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monododecyl phosphate, monobutoxyethyl phosphate, mono-2-ethylhexyl phosphate, and phosphoric acid. It is preferable that the phosphate buffer solution contains at least one selected from the group consisting of monoisotridecyl phosphate, monohexadecyl phosphate, monooleyl phosphate, monotetracosyl phosphate, monophenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, dihexyl phosphate, dibenzyl phosphate, didecyl phosphate, diisodecyl phosphate, didodecyl phosphate, dibutoxyethyl phosphate, di-2-ethylhexyl phosphate, diisotridecyl phosphate, dihexadecyl phosphate, dioleyl phosphate, ditetracosyl phosphate, and diphenyl phosphate.

[0094] When the elimination reaction catalyst is an acid catalyst, the amount of the acid catalyst used is not particularly limited, and is preferably 1 mol % to 30 mol %, more preferably 10 mol % to 20 mol %, based on 100 mol % of the trisubstituted ethane (II).

[0095] (1.2.1.1.2) Base catalyst Examples of the base catalyst include nitrogen-containing heterocyclic compounds (e.g., piperazine, piperazine derivatives, piperidine, piperidine derivatives, imidazole, imidazole derivatives, morpholine, N-methylmorpholine, and 2-methylmorpholine), carbonates (e.g., calcium carbonate, potassium carbonate, sodium carbonate, barium carbonate, and magnesium carbonate), bicarbonates (e.g., calcium bicarbonate, potassium bicarbonate, sodium bicarbonate, and ammonium bicarbonate), alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide), ammonium compounds (e.g., ammonium hydroxide, ammonium fluoride, ammonium chloride, and ammonium bromide), basic sodium phosphates (e.g., sodium metaphosphate, sodium pyrophosphate, and sodium polyphosphate), aliphatic amines (e.g., allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, ethylamine, and diethylamine), and basic ion exchange resins. These base catalysts may be used alone or in combination of two or more.

[0096] When the elimination reaction catalyst is a base catalyst, the amount of the base catalyst used is not particularly limited, but is preferably 1 mol % to 20 mol %, more preferably 1 mol % to 5 mol %, based on 100 mol % of the trisubstituted ethane (II).

[0097] (1.2.1.1.3) Acid-Base Catalyst Examples of the acid-base catalyst include salts of the above-mentioned acid catalysts and the above-mentioned base catalysts, such as salts of methanesulfonic acid and nitrogen-containing heterocyclic compounds, salts of p-toluenesulfonic acid and nitrogen-containing heterocyclic compounds, salts of laurylbenzenesulfonic acid and nitrogen-containing heterocyclic compounds, and salts of methanesulfonic acid and alkali metals. These acid-base catalysts may be used alone or in combination of two or more.

[0098] When the elimination reaction catalyst is an acid-base catalyst, the amount of the acid catalyst used is not particularly limited, but is preferably 1 mol % to 30 mol %, more preferably 10 mol % to 20 mol %, based on 100 mol % of the tri-substituted ethane (II). The amount of the base catalyst used is not particularly limited, but is preferably 1 mol % to 20 mol %, more preferably 1 mol % to 5 mol %, based on 100 mol % of the tri-substituted ethane (II).

[0099] (1.2.1.1.4) Preferred Aspects The method for producing a 1,1-disubstituted olefin of the first embodiment is preferably the first aspect. In the first aspect, the elimination reaction step is carried out in the presence of the acid catalyst, and the acid catalyst contains at least one compound selected from the group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid (hereinafter also referred to as the "specific compound"). This allows the method for producing a 1,1-disubstituted olefin of the first embodiment to produce the disubstituted olefin (III) more efficiently than a configuration in which the acid catalyst does not contain the specific compound.

[0100] (1.2.1.2) Elimination Reaction The elimination reaction is carried out by charging the trisubstituted ethane (II) and the elimination reaction catalyst into a reaction vessel. The reaction vessel may be operated batchwise or continuously.

[0101] The reaction temperature is not particularly limited and may be 60° C. to 160° C. or 80° C. to 120° C. The reaction time is not particularly limited and may be appropriately selected depending on the type and amount of the trisubstituted ethane (II), etc. The reaction time may be 1 hour to 12 hours.

[0102] (1.2.1.3) Alcohol Scavenger The elimination reaction step may be carried out in the presence of an alcohol scavenger. In other words, an alcohol scavenger may be further added to the reaction vessel to allow the elimination reaction to proceed. The elimination reaction step may be carried out in the absence of an alcohol scavenger.

[0103] The term "alcohol scavenger" refers to a substance that has the property of absorbing alcohol by forming a chemical bond or by physical adsorption. The alcohol scavenger may be either liquid or solid.

[0104] Examples of alcohol scavengers include carboxylic acid anhydrides (e.g., succinic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, maleic anhydride, and phthalic anhydride), crystalline zeolites (e.g., molecular sieves), and oxides (e.g., phosphorus pentoxide, calcium oxide, barium oxide, and magnesium oxide). These alcohol scavengers may be used alone or in combination of two or more.

[0105] It is preferable that R represents the alkoxy group and the elimination reaction step is carried out in the presence of an alcohol scavenger. This makes it possible to suppress the polymerization reaction of the disubstituted olefin (III) caused by the alcohol and to obtain the disubstituted olefin (III) in a higher reaction yield than in a configuration in which the elimination reaction step is carried out in the absence of an alcohol scavenger.

[0106] When R represents the alkoxy group and the elimination reaction step is carried out in the presence of an alcohol scavenger, the alcohol scavenger preferably contains a carboxylic acid anhydride. As a result, in the method for producing a 1,1-disubstituted olefin of the first embodiment, the elimination reaction can be carried out in an acidic atmosphere and the polymerization reaction of the produced disubstituted olefin (III) can be more effectively suppressed than in a configuration in which the alcohol scavenger does not contain a carboxylic acid anhydride.

[0107] When R represents the alkoxy group, the elimination reaction step is carried out in the presence of an alcohol scavenger, and the alcohol scavenger contains a carboxylic acid anhydride, the carboxylic acid anhydride preferably contains at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, maleic anhydride, and succinic anhydride (hereinafter also referred to as a "specific carboxylic acid anhydride"). As a result, in the method for producing a 1,1-disubstituted olefin of the first embodiment, by-products having lower boiling points are produced than in a configuration in which the carboxylic acid anhydride does not contain the specific carboxylic acid anhydride, and these by-products can be easily removed using an evaporator or the like in the purification step.

[0108] When the elimination reaction step is carried out in the presence of an alcohol scavenger, the amount of the alcohol scavenger used is not particularly limited, and is preferably 100 mol % to 500 mol %, more preferably 100 mol % to 200 mol %, relative to 100 mol % of the trisubstituted ethane (II).

[0109] (1.2.1.4) Solvent The elimination reaction step may be carried out in the presence of a solvent. In other words, the elimination reaction may be carried out by further adding a solvent to the reaction vessel. The elimination reaction step may be carried out in the absence of a solvent.

[0110] Examples of the solvent include aromatic hydrocarbons (e.g., benzene, toluene, and ethylbenzene), ethers (e.g., diethyl ether, anisole, and tetrahydrofuran), ketones (e.g., acetone, methyl ethyl ketone, and acetophenone), alcohols (e.g., methanol, ethanol, and n-butanol), carboxylic acids (e.g., formic acid, acetic acid, and propionic acid), esters (e.g., methyl acetate, n-butyl acetate, and benzyl benzoate), aliphatic hydrocarbons (e.g., n-hexane, n-octane, and cyclohexane), halogenated hydrocarbons (e.g., dichloromethane, trichloroethane, and chlorobenzene), nitro compounds (e.g., nitromethane and nitrobenzene), and carboxylic acid amides (e.g., N,N-dimethyl formamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (e.g., N,N'-dimethylimidazolidone, and N,N,N,N-tetramethylurea, etc.), sulfones (e.g., dimethyl sulfone, and tetramethylene sulfone, etc.), sulfoxides (e.g., dimethyl sulfoxide, and diphenyl sulfoxide, etc.), lactones (e.g., γ-butyrolactone, and ε-caprolactone, etc.), polyethers (e.g., triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), and 18-crown-6, etc.), nitriles (e.g., acetonitrile, and benzonitrile, etc.), and carbonates (e.g., dimethyl carbonate, and ethylene carbonate, etc.). These solvents may be used alone or in combination of two or more.

[0111] When the elimination reaction step is carried out in the presence of a solvent, the amount of the solvent used is not particularly limited, and is preferably 100 parts by mass to 1,000 parts by mass, more preferably 100 parts by mass to 200 parts by mass, relative to 100 parts by mass of the trisubstituted ethane (II).

[0112] (1.2.1.5) 1,1-Disubstituted Olefins By carrying out the elimination reaction step, disubstituted olefins (III) are obtained.

[0113] The disubstituted olefin (III) may, for example, be a cyanoacrylate ester represented by the following formula (III-1):

[0114]

[0115] In formula (III-1), p, L １ , and R ７ is as described above in formula (I-1).

[0116] The disubstituted olefin (III) is suitable for use in a variety of applications (for example, adhesives, coatings, sealants, etc.).

[0117] (1.2.2) Separation Step The method for producing a 1,1-disubstituted olefin of the first embodiment may include a separation step. When a solid catalyst is used, in the separation step, the reaction solution after the elimination reaction step is filtered. The separation step is carried out after the elimination reaction step is carried out. As a result, the elimination reaction catalyst is separated from the reaction solution, and the target disubstituted olefin (III) can be recovered. When the elimination reaction step is carried out in the presence of a solid (insoluble) alcohol scavenger, the water scavenger as well as the elimination reaction catalyst are separated from the reaction solution by filtration. The filtration method is not particularly limited, and any known method may be used.

[0118] When the elimination reaction step is carried out in the presence of a solvent, the solvent may be distilled off from the reaction solution after filtration in the separation step. The boiling point of impurities (e.g., the elimination alcohol, the carboxylic acid ester produced from the carboxylic acid anhydride, and the carboxylic acid) contained in the reaction solution after the elimination reaction step is close to the boiling point of the solvent. This separates impurities from the reaction solution in addition to the solvent. As a result, a reaction solution with a higher yield of disubstituted olefin (III) can be obtained. Examples of distillation methods include evaporators, simple distillation, and thin-film distillation. The temperature during distillation may be 40°C to 120°C.

[0119] According to the method for producing a 1,1-disubstituted olefin of the first embodiment, a disubstituted olefin (III) can be produced according to the following reaction formula:

[0120]

[0121] (2) Second Embodiment A method for producing a 1,1-disubstituted olefin according to a second embodiment of the present disclosure includes an elimination reaction step of eliminating the functional group R from 1,1,2-trisubstituted ethane represented by formula (II) (i.e., trisubstituted ethane (II)) to obtain a 1,1-disubstituted olefin represented by formula (III) (i.e., disubstituted olefin (III)), as shown in the following reaction formula: The elimination reaction step is carried out in the presence of at least one catalyst selected from the group consisting of an acid catalyst, a base catalyst, and an acid-base catalyst.

[0122]

[0123] In formula (II) and formula (III), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２ R represents one selected from the group consisting of １ is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ Cycloalkyl, alkylcycloalkyl, C ３ -C ２０In formulas (II) and (III), R represents a linear, branched, or alicyclic saturated or unsaturated C １ -C ２０ It represents an alkoxy group, a carboxy group, a hydroxy group, a fluoroalkylsulfone group, a fluorosulfone group, an alkylsulfone group, an arylsulfone group, a halogen atom, a phenoxy group, or a selenoxy group.

[0124] The method for producing a 1,1-disubstituted olefin of the second embodiment has the above-mentioned configuration, and therefore exhibits the same effects as the method for producing a 1,1-disubstituted olefin of the first embodiment.

[0125] The method for producing a 1,1-disubstituted olefin of the second embodiment is the same as the method for producing a 1,1-disubstituted olefin of the first embodiment, except that the trisubstituted ethane (II) may not be one produced by the method for producing a 1,1-disubstituted olefin of the first embodiment.

[0126] The method for producing a 1,1-disubstituted olefin of the second embodiment is preferably the second aspect. In the second aspect, the elimination reaction step is carried out in the presence of the acid catalyst, and the acid catalyst contains at least one compound selected from the group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid (hereinafter also referred to as the "specific compound"). As a result, the method for producing a 1,1-disubstituted olefin of the second embodiment can produce the disubstituted olefin (III) more efficiently than a configuration in which the acid catalyst does not contain the specific compound.

[0127] It is preferable that R represents the alkoxy group and the elimination reaction step is carried out in the presence of an alcohol scavenger. This makes it possible to suppress the polymerization reaction of the disubstituted olefin (III) caused by the alcohol and obtain the disubstituted olefin (III) in a higher reaction yield than in a configuration in which the elimination reaction step is carried out in the absence of an alcohol scavenger.

[0128] When R represents the alkoxy group and the elimination reaction step is carried out in the presence of an alcohol scavenger, the alcohol scavenger preferably contains a carboxylic acid anhydride. As a result, in the method for producing a 1,1-disubstituted olefin of the second embodiment, the elimination reaction can be carried out in an acidic atmosphere and the polymerization reaction of the produced disubstituted olefin (III) can be more effectively suppressed than in a configuration in which the alcohol scavenger does not contain a carboxylic acid anhydride.

[0129] When R represents the alkoxy group, the elimination reaction step is carried out in the presence of an alcohol scavenger, and the alcohol scavenger contains a carboxylic acid anhydride, the carboxylic acid anhydride preferably contains at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, maleic anhydride, and succinic anhydride (hereinafter also referred to as a "specific carboxylic acid anhydride"). As a result, in the method for producing a 1,1-disubstituted olefin of the second embodiment, by-products having lower boiling points are produced than in a configuration in which the carboxylic acid anhydride does not contain the specific carboxylic acid anhydride, and these by-products can be easily removed using an evaporator or the like in the purification step.

[0130] Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, strongly acidic ion exchange resins, solid catalysts in which sulfonic acid groups are chemically bonded to a carrier, solid catalysts in which a compound having a sulfonic acid group is supported on a carrier, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monobenzyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monododecyl phosphate, monobutoxyethyl phosphate, mono-2-ethylhexyl phosphate, and phosphoric acid. It is preferable that the phosphate buffer solution contains at least one selected from the group consisting of monoisotridecyl phosphate, monohexadecyl phosphate, monooleyl phosphate, monotetracosyl phosphate, monophenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, dihexyl phosphate, dibenzyl phosphate, didecyl phosphate, diisodecyl phosphate, didodecyl phosphate, dibutoxyethyl phosphate, di-2-ethylhexyl phosphate, diisotridecyl phosphate, dihexadecyl phosphate, dioleyl phosphate, ditetracosyl phosphate, and diphenyl phosphate.

[0131] Hereinafter, the present disclosure will be described more specifically with reference to examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure.

[0132] [1] Examples 1 to 4 [1.1] Example 1 [1.1.1] Reduction Reaction Step Ethyl 2-cyano-3-ethoxyacrylate (I-1) (1.00 g) represented by the following formula (I-1), 20% palladium hydroxide-carbon (0.3 g), and toluene (5 mL) were added to a flask. A gas collection bag containing hydrogen was attached to the flask, and the flask was filled with hydrogen (0.1 MPa). The reaction solution was then stirred at room temperature. Six hours after the start of stirring, the reaction solution was analyzed by nuclear magnetic resonance (NMR). The analysis revealed that ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1) was obtained. The reaction yield of ethyl 2-cyano-3-ethoxypropionate (II-1) was 47%.

[0133]

[0134] The "reaction yield of ethyl 2-cyano-3-ethoxypropionate (II-1)" refers to the product of the consumption rate (mol %) of the raw material ethyl 2-cyano-3-ethoxyacrylate (I-1) at the time of reaction termination and the molar ratio of the target substance ethyl 2-cyano-3-ethoxypropionate (II-1) contained in the product. The molar ratio was calculated based on the integrated value of NMR (Nuclear Magnetic Resonance).

[0135] [1.1.2] Elimination Reaction Step (Volatile Carboxylic Acid Anhydride + High-Boiling Sulfonic Acid Catalyst) The reaction solution obtained in Example 1 was used as ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1). Ethyl 2-cyano-3-ethoxypropionate (II-1) (1.00 g, 5.84 mmol), toluene (5 mL), methanesulfonic acid (0.084 g, 0.87 mmol), and succinic anhydride (1.17 g, 11.7 mmol) were placed in a flask and heated with stirring at 120°C for 6.0 hours. The resulting solution was analyzed by NMR. The analysis revealed that ethyl cyanoacrylate (III-1) represented by the following formula (III-1) was obtained. The reaction yield of ethyl cyanoacrylate (III-1) was 96%.

[0136]

[0137] The "reaction yield of ethyl cyanoacrylate (III-1)" refers to the product of the consumption rate (mol %) of the raw material ethyl 2-cyano-3-ethoxypropionate (II-1) at the time of reaction termination and the molar ratio of the target substance, ethyl cyanoacrylate (III-1), contained in the product. The molar ratio was calculated based on the integrated value of NMR (Nuclear Magnetic Resonance).

[0138] [1.2] Example 2 [1.2.1] Reduction Reaction Step Ethyl 2-cyano-3-ethoxyacrylate (I-1) (1.00 g, 5.84 mmol), 20% palladium hydroxide on carbon (0.3 g), toluene (5 mL), and molecular sieves 4A (1.5 g) were added to a flask. A gas collection bag containing hydrogen was attached to the flask, and the flask was filled with hydrogen. The reaction solution was then stirred at room temperature. Six hours after the start of stirring, the reaction solution was analyzed by NMR. The analysis revealed that the target compound (i.e., ethyl 2-cyano-3-ethoxypropionate (II-1)) was obtained. The reaction yield of ethyl 2-cyano-3-ethoxypropionate (II-1) was 64%.

[0139] [1.2.2] Elimination reaction step (volatile carboxylic acid anhydride + high-boiling sulfonic acid catalyst) Ethyl cyanoacrylate (III-1) was produced in the same manner as in Example 1, except that the reaction solution obtained in Example 2 was used as ethyl 2-cyano-3-ethoxypropionate (II-1). The reaction yield of ethyl cyanoacrylate (III-1) was 96%.

[0140] [1.3] Example 3 [1.3.1] Reduction Reaction Step Ethyl 2-cyano-3-ethoxyacrylate (I-1) (1.00 g, 5.84 mmol), 20% palladium hydroxide on carbon (0.3 g), toluene (5 mL), acetic anhydride (0.3 g), and molecular sieves 4A (1.5 g) were added to a flask. A gas collection bag containing hydrogen was attached to the flask, and the flask was filled with hydrogen. The reaction solution was then stirred at room temperature. Six hours after the start of stirring, the reaction solution was analyzed by NMR. The analysis revealed that the target compound (ethyl 2-cyano-3-ethoxypropionate) was obtained. The reaction yield of ethyl 2-cyano-3-ethoxypropionate was 96%.

[0141] [1.3.2] Elimination reaction step (volatile carboxylic acid anhydride + high-boiling sulfonic acid catalyst) Ethyl cyanoacrylate (III-1) was produced in the same manner as in Example 1, except that the reaction solution obtained in Example 3 was used as ethyl 2-cyano-3-ethoxypropionate (II-1). The reaction yield of ethyl cyanoacrylate (III-1) was 96%.

[0142] [1.4] Example 4 [1.4.1] Reduction Reaction Step Ethyl 2-cyano-3-ethoxyacrylate (1.00 g), 10% palladium-carbon (0.3 g), toluene (5 mL), acetic anhydride (0.3 g), and molecular sieves 4A (1.5 g) were added to a flask. A gas collection bag containing hydrogen was attached to the flask, and the flask was filled with hydrogen. The reaction solution was then stirred at room temperature. Six hours after the start of stirring, the reaction solution was analyzed by NMR. The analysis revealed that the target compound (ethyl 2-cyano-3-ethoxypropionate) was obtained. The reaction yield of ethyl 2-cyano-3-ethoxypropionate was 85%.

[0143] [1.4.2] Elimination reaction step (volatile carboxylic acid anhydride + high-boiling sulfonic acid catalyst) Ethyl cyanoacrylate (III-1) was produced in the same manner as in Example 1, except that the reaction solution obtained in Example 4 was used as ethyl 2-cyano-3-ethoxypropionate (II-1). The reaction yield of ethyl cyanoacrylate (III-1) was 96%.

[0144] [1.5] Results

[0145] In Examples 1 to 4, the reaction yield of ethyl cyanoacrylate (III-1) was 80% or more. From these results, it was found that the methods for producing 1,2-trisubstituted ethane in Examples 1 to 4 are "methods for producing 1,1,2-trisubstituted ethane that can produce anionically polymerizable disubstituted olefins in high yield without distillation."

[0146] The yields of trisubstituted ethane (II) in Examples 1 to 4 were 47% or more. These results demonstrate that the methods for producing 1,2-trisubstituted ethane in Examples 1 to 4 can produce trisubstituted ethane (II) in high yield.

[0147] [2] Examples 1 and 5 to 7 [2.1] Example 5 (Solid Carboxylic Acid Anhydride + High-Boiling Sulfonic Acid Catalyst) Ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1) was prepared from the reaction solution obtained in Example 1, after removing solids by filtration. Ethyl 2-cyano-3-ethoxypropionate (II-1) (1.00 g, 5.84 mmol), toluene (5 mL), methanesulfonic acid (0.084 g, 0.87 mmol), and acetic anhydride (1.19 g, 11.7 mmol) were placed in a flask and heated with stirring at 120°C for 6.0 hours. The resulting solution was analyzed by NMR. The analysis revealed that ethyl cyanoacrylate (III-1) was obtained. The reaction yield of ethyl cyanoacrylate (III-1) was 86%.

[0148] [2.2] Example 6 (Volatile Carboxylic Acid Anhydride + Solid Sulfonic Acid Catalyst) Ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1) was prepared from the reaction solution obtained in Example 1, after removing solids by filtration. Ethyl 2-cyano-3-ethoxypropionate (II-1) (1.00 g, 5.84 mmol), toluene (5 mL), catalytic ion exchange resin Amberlyst 15 DRY (0.94 g), and acetic anhydride (1.19 g, 11.7 mmol) were placed in a flask and heated with stirring at 120°C for 6.0 hours. The resulting solution was analyzed by NMR. The analysis revealed that ethyl cyanoacrylate (III-1) was obtained. The reaction yield of ethyl cyanoacrylate (III-1) was 80%.

[0149] [2.3] Example 7 (Solid Carboxylic Acid Anhydride + High-Boiling Sulfonic Acid Catalyst + Solid Amine Catalyst) Ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1) was prepared from the reaction solution obtained in Example 1, after removing solids by filtration. Ethyl 2-cyano-3-ethoxypropionate (II-1) (1.00 g, 5.84 mmol), toluene (5 mL), piperazine (0.025 g, 0.29 mmol), methanesulfonic acid (0.084 g, 0.87 mmol), and succinic anhydride (1.17 g, 11.7 mmol) were placed in a flask and heated with stirring at 120°C for 3.0 hours. The resulting solution was analyzed by NMR. The analysis revealed that ethyl cyanoacrylate (III-1) was obtained. The reaction yield of ethyl cyanoacrylate (III-1) was 96%.

[0150] [2.4] Results The yields of ethyl cyanoacrylate (III-1) in Examples 1 and 5 to 7 were 80% or more. These results demonstrate that the methods for producing 1,1-disubstituted olefins in Examples 1 and 5 to 7 are "methods for producing 1,1-disubstituted olefins that can produce anionically polymerizable disubstituted olefins in high yield without distillation."

[0151] The disclosures of Japanese Patent Application No. 2023-198298, filed on November 22, 2023, and Japanese Patent Application No. 2023-198310, filed on November 22, 2023, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing 1,1,2-trisubstituted ethane, comprising a reduction reaction step of reducing a 1,1,2-trisubstituted olefin represented by formula (I) to obtain a 1,1,2-trisubstituted ethane represented by formula (II), as shown in the following reaction formula, in the presence of a hydrogenation catalyst. In formula (I) and formula (II), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２ R represents one selected from the group consisting of １ is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ Cycloalkyl, alkylcycloalkyl, C ３ -C ２０ In formula (I) and formula (II), R represents a linear, branched or alicyclic saturated or unsaturated C １ -C ２０ It represents an alkoxy group, a carboxy group, a hydroxy group, a fluoroalkylsulfone group, a fluorosulfone group, an alkylsulfone group, an arylsulfone group, a halogen atom, a phenoxy group, or a selenoxy group.

2. The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the hydrogenation catalyst contains at least one metal selected from the group consisting of palladium, nickel, platinum, rhodium, ruthenium, iridium, copper, chromium, iron, aluminum, and zinc.

3. The hydrogenation catalyst is Pd(OH) ２ The method for producing 1,1,2-trisubstituted ethane according to claim 1, further comprising at least one of Pd / C and Pd / C.

4. The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the reduction reaction step is carried out in the presence of a reducing agent, and the reducing agent comprises hydrogen or a metal hydride.

5. The method for producing 1,1,2-trisubstituted ethane according to claim 4, wherein the reducing agent contains hydrogen, and the hydrogen pressure in the reduction reaction step is 0.1 MPa to 20 MPa.

6. The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the reduction reaction step is carried out in the presence of a water scavenger.

7. The method for producing 1,1,2-trisubstituted ethane according to claim 6, wherein the water scavenger comprises a crystalline zeolite and a carboxylic acid anhydride.

8. The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the reduction reaction step is carried out in the presence of a solvent, and the solvent contains at least one selected from the group consisting of aromatic hydrocarbons, hydrocarbons, ethers, ketones, alcohols, carboxylic acids, and esters.

9. The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the reaction temperature in the reduction reaction step is 0°C to 150°C.

10. A method for producing a 1,1-disubstituted olefin, comprising: a step of obtaining 1,1,2-trisubstituted ethane by the production method according to claim 1; and an elimination reaction step of eliminating the functional group R of the 1,1,2-trisubstituted ethane as shown in the following reaction formula to obtain a 1,1-disubstituted olefin represented by the following formula (III), wherein the elimination reaction step is carried out in the presence of at least one catalyst selected from the group consisting of acid catalysts, base catalysts, and acid-base catalysts. A in (III) is the same as A in formulae (I) and (II), and D in (III) is the same as D in formulae (I) and (II).

11. A method for producing a 1,1-disubstituted olefin, comprising an elimination reaction step of eliminating a functional group R from a 1,1,2-trisubstituted ethane represented by formula (II) to obtain a 1,1-disubstituted olefin represented by formula (III), as shown in the reaction formula below, wherein the elimination reaction step is carried out in the presence of at least one catalyst selected from the group consisting of an acid catalyst, a base catalyst, and an acid-base catalyst. In formula (II) and formula (III), A and D are each independently CN, CO ２ R １ , C.O.R. １ , CON(R １ ) ２ , S.O. ２ R １ , S.O. ３ R １ , COPO (OR １ ) ２ , COP(OR １ ) ２ , and NO ２ R represents one selected from the group consisting of １ is a linear or branched saturated or unsaturated C １ -C ２０ Alkyl, C １ -C ２０ Alkyl halides, C ４ -C ２０ Alkylsilane, C １ -C ２０ Acetoxysilane, C ２ -C ２０ Alkoxyalkyl, C ２ -C ２０ Alkenyl, C ２ -C ２０ Alkynyl, C ２ -C １０ Alkylene, C ３ -C ２０ Cycloalkyl, alkylcycloalkyl, C ３ -C ２０ In formula (II) and formula (III), R represents a linear, branched or alicyclic saturated or unsaturated C １ -C ２０ It represents an alkoxy group, a carboxy group, a hydroxy group, a fluoroalkylsulfone group, a fluorosulfone group, an alkylsulfone group, an arylsulfone group, a halogen atom, a phenoxy group, or a selenoxy group.

12. The method for producing a 1,1-disubstituted olefin according to claim 10 or 11, wherein the elimination reaction step is carried out in the presence of the acid catalyst, and the acid catalyst contains at least one compound selected from the group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid.

13. The method for producing a 1,1-disubstituted olefin according to claim 10 or 11, wherein R represents an alkoxy group, and the elimination reaction step is carried out in the presence of an alcohol scavenger.

14. The method for producing 1,1-disubstituted olefins according to claim 13, wherein the alcohol scavenger comprises a carboxylic acid anhydride.

15. The method for producing a 1,1-disubstituted olefin according to claim 14, wherein the carboxylic acid anhydride comprises at least one member selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, maleic anhydride, and succinic anhydride.

16. The acid catalyst is sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, laurylbenzenesulfonic acid, a strongly acidic ion exchange resin, a solid catalyst in which a sulfonic acid group is chemically bonded to a support, a solid catalyst in which a compound having a sulfonic acid group is supported on a support, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monobenzyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monododecyl phosphate, monobutoxyethyl phosphate, mono-2-ethylhexyl phosphate, monoisotridecyl phosphate, monophosphate, The method for producing a 1,1-disubstituted olefin according to claim 10 or claim 11, comprising at least one selected from the group consisting of monohexadecyl phosphate, monooleyl phosphate, monotetracosyl phosphate, monophenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, dihexyl phosphate, dibenzyl phosphate, didecyl phosphate, diisodecyl phosphate, didodecyl phosphate, dibutoxyethyl phosphate, di-2-ethylhexyl phosphate, diisotridecyl phosphate, dihexadecyl phosphate, dioleyl phosphate, ditetracosyl phosphate, and diphenyl phosphate.

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