WO2025110241A1 - Method for producing 1,1,2-trisubstituted ethane and method for producing 1,1-disubstituted olefin - Google Patents

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

This disclosure relates to a method for producing 1,1,2-trisubstituted ethane and a method for producing 1,1-disubstituted olefins.

Cyanoacrylates have traditionally been used for a variety of purposes (e.g., adhesives, coatings, sealants, etc.).

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

Patent document 1: International Publication No. 2004/106284

However, distillation may not be able to sufficiently remove impurities from crude cyanoacrylate. Therefore, there is a need for a method for producing anionically polymerizable disubstituted olefins that can separate impurities without performing distillation and produce 1,1-disubstituted olefins (e.g., cyanoacrylates) that have anionically polymerizable properties (hereinafter also referred to as "anionically polymerizable disubstituted olefins") in high yields.

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 capable of producing anionically polymerizable disubstituted olefins in high yield without performing distillation.
Another problem to be solved by 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.

Specific means for solving the above problems include the following:

<1> As shown in the following reaction formula, the method includes 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),
The method for producing 1,1,2-trisubstituted ethane, wherein the reduction reaction step is carried out in the presence of a hydrogenation catalyst.

In formula (I) and formula (II), A and D each independently represent one selected from the group consisting of ^CN , _CO2R1 , ^COR1 , CON( ^R1 ) ₂ , _SO2R1 , ^SO3R1 , COPO ⁽ _OR1 ) ² , COP( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a C1- _C20 acetoxy silane, a _C2 - _C20 alkoxy alkyl, a _C2 - _C20 alkenyl, a _C2 - _C20 alkynyl, a _C2 - _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkyl cycloalkyl, a _{C3 - C20} cycloalkenyl, an alkyl cycloalkenyl, an aryl, an alkyl moiety bonded to an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic ring, an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (I) and formula (II), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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 <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 method for producing 1,1,2-trisubstituted ethane according to <1> or <2>, wherein the hydrogenation catalyst contains at least one of Pd(OH) ₂ /C and Pd/C.
<4> The reduction reaction step is carried out in the presence of a reducing agent,
The method for producing 1,1,2-trisubstituted ethane according to any one of <1> to <3>, wherein the reducing agent contains hydrogen or a metal hydride.
<5> The reducing agent contains hydrogen,
The method for producing 1,1,2-trisubstituted ethane according to <4> above, wherein 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 contains a crystalline zeolite and a carboxylic acid anhydride.
<8> The reduction reaction step is carried out in the presence of a solvent,
The method for producing 1,1,2-trisubstituted ethane according to any one of <1> to <7>, wherein 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 any one of <1> to <8>, wherein in the reduction reaction step, the reaction temperature is 0° C. to 150° C.
<10> 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 of the 1,1,2-trisubstituted ethane to obtain a 1,1-disubstituted olefin represented by the following formula (III), as shown in the following reaction formula:
The present invention relates to a method for producing a 1,1-disubstituted olefin, 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.

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> As shown in the following reaction formula, the method includes 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),
The present invention relates to a method for producing a 1,1-disubstituted olefin, 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 each independently represent one selected from the group consisting of ^CN , _CO2R1 , ^COR1 , CON( ^R1 ) ₂ , _SO2R1 , ^SO3R1 , COPO ⁽ _OR1 ) ² , COP( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a C1- _C20 acetoxy silane, a _C2 - _C20 alkoxy alkyl, a _C2 - _C20 alkenyl, a _C2 - _C20 alkynyl, a C2- _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkyl cycloalkyl, a _{C3 - C20} cycloalkenyl, an alkyl cycloalkenyl, an aryl, an alkyl moiety bonded to an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic _ring , an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (II) and formula (III), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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 elimination reaction step is carried out in the presence of the acid catalyst,
The method for producing a 1,1-disubstituted olefin according to <10> or <11>, wherein 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 R represents the alkoxy group,
The method for producing a 1,1-disubstituted olefin according to any one of <10> to <12>, wherein 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>, 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. 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, 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.

According to one embodiment of the present disclosure, a method for producing 1,1,2-trisubstituted ethane that can be used as a feedstock in a process capable of producing anionically polymerizable disubstituted olefins in high yield without distillation is provided.
Another embodiment of the present disclosure provides a process for the preparation of 1,1-disubstituted olefins that can produce anionically polymerizable disubstituted olefins in high yield without the need for distillation.

In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.
In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In the numerical ranges described in this disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
In this disclosure, combinations of preferred aspects are more preferred aspects.
In the description of groups (atomic groups) in the present disclosure, a description without specifying whether substituted or unsubstituted encompasses both groups having no substituents and groups having a substituent.

(1) First embodiment (1.1) Method for producing 1,1,2-trisubstituted ethane The method for producing 1,1,2-trisubstituted ethane according to the 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 "tri-substituted olefin (I)") to obtain a 1,1,2-trisubstituted ethane represented by formula (II) (hereinafter also referred to as "tri-substituted ethane (II)"), as shown in the following reaction formula. The reduction reaction step is carried out in the presence of a hydrogenation catalyst.

In formula (I) and formula (II), A and D each independently represent one selected from the group consisting of ^CN , _CO2R1 , ^COR1 , CON( ^R1 ) ₂ , _SO2R1 , ^SO3R1 , COPO ⁽ _OR1 ) ² , COP( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a C1- _C20 acetoxy silane, a _C2 - _C20 alkoxy alkyl, a _C2 - _C20 alkenyl, a _C2 - _C20 alkynyl, a _C2 - _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkyl cycloalkyl, a C3 _- C20 cycloalkenyl, an alkyl cycloalkenyl, an aryl, an alkyl moiety bonded to an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic ring, an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (I) and formula (II), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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.

"Hydrogenation catalyst" refers to a solid catalyst for hydrogenation reactions. "Hydrogenation reaction" refers to a reaction in which hydrogen is added to the unsaturated bonds of unsaturated organic compounds.

The method for producing 1,1,2-trisubstituted ethane in the first embodiment has the above 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.

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

A in formula (III) is the same as A in formula (I) and formula (II). D in formula (III) is the same as D in formula (I) and formula (II).

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 a high yield. The "specific trisubstituted ethane (II)" refers to a trisubstituted ethane (II) in which at least one of A and D has a highly electron-withdrawing functional group (e.g., a cyano group (CN) and a carbonyl group (CO ₂ R ¹ , COR ¹ , CON(R ¹ ) ₂ , COPO(OR ¹ ) ₂ and COP(OR ¹ ) ₂ )) and in which a side reaction (e.g., an elimination reaction by a base, etc.) easily occurs. It is presumed that the main reason for this is that the solid hydrogenation catalyst can be easily removed by filtration.

(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 a tri-substituted ethane (II).

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

In formula (I), A and D each independently represent one selected from ^the _{group consisting of CN, CO2R1, COR1, CON(R1)2, SO2R1, SO3R1 ,} ^{COPO (} _{OR1 )} ^{2 , COP} ( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a C1- _C20 acetoxy silane, a _C2 - _C20 alkoxy alkyl, a _C2 - _C20 alkenyl, a _C2 - _C20 alkynyl, a C2- _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkyl cycloalkyl, a _{C3 - C20} cycloalkenyl, an alkyl cycloalkenyl, an aryl, an alkyl moiety bonded to an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic _ring , an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (I), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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.

(1.1.1.1.1) A and D
The following describes A and D in formula (I). A and D are electron-withdrawing groups attached to the same carbon atom. A and D may be the same or different.

Examples of linear or branched, saturated or unsaturated C ₁ -C ₂₀ 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.
In the C ₁ -C ₂₀ halogenated alkyl, the hydrogens of the alkyl may be partially or fully halogenated, and the carbon chain of the alkyl may be linear or branched.
Examples of C ₄ -C ₂₀ alkyl silanes include methyltrimethylsilane, ethyltrimethylsilane, and propyltrimethylsilane.
Examples of _C1 - _C20 acetoxysilanes include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, and tetraacetoxysilane.
C ₂ -C ₂₀ alkoxyalkyl, for example, includes 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-methoxypropyl, and 2-(1-methoxy)propyl.
_C2 - _C20 alkenyl includes, for example, allyl and propenyl groups.
Examples of C ₂ -C ₂₀ alkynyl include a propargyl group.
C ₂ -C ₁₀ alkylene includes, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-(ethyl)trimethylene, and 1-(methyl)tetramethylene.
C ₃ -C ₂₀ cycloalkyl includes, for example, cyclobutyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
Alkylcycloalkyl includes, for example, methylcycloalkyl, isopropylcycloalkyl, isobornyl, and the like.
Examples of C ₃ -C ₂₀ cycloalkenyl include cyclohexenyl groups.
Alkylcycloalkenyl includes, for example, terpinyl and the like.
Aryl includes, for example, phenyl, naphthyl, and the like.
An example of an alkyl moiety bound to an aryl is benzyl.
Examples of the aliphatic heterocyclic moiety include tetrahydrofuryl and tetrahydrothiophene groups.
Examples of alkyl moieties bonded to an aliphatic heterocycle include 2,3-epoxypropyl, oxetanylmethyl, and tetrahydrofurfuryl.
Examples of the aromatic heterocyclic moiety include furyl and thiophenyl groups.
Examples of alkyl moieties bonded to aromatic heterocycles include furfuryl.
The acrylate portion is represented by formula (a1).

In formula (a1), T is -( _CH2 ) _z- (where z is 2 to 12), a branched _C3 - _C12 alkylene chain, cyclohexylene, optionally substituted biphenylene, optionally substituted _-C6H4C (Me) _{2C6H4- ,} optionally _{substituted -C6H4CH2C6H4-} , or optionally substituted phenylene _. ^R2 is H, Me, _CN , or _CO2R3 (wherein ^R3 is _{a C1} - _{C10 alkyl} group). When ^R2 is H or Me, it corresponds to _an acrylate or methacrylate moiety, ^{respectively. When R2 is} CN, it corresponds to a cyanoacrylate moiety. When ^R2 is _CO2R3 , it corresponds to ^a malonic acid methylidene ester moiety.
The glycolic acid moiety is designated _-CH2CO2R4 , where ^R4 is ^a _C1 - _{C4 alkyl} group.
The carboxylate moiety represents -(CH ₂ ) _k CO ₂ R ⁵ , where k is preferably 2 to 18, more preferably 2 to 12, and even more preferably 2 to 8. R ⁵ is a C ₁ -C ₄ alkyl group.
Examples of halogen-substituted alkyl moieties include 2,2,2-trifluoroethanol, and 1,1,1,3,3,3-hexafluoropropyl.

(1.1.1.1.2)R
R in formula (I) will be explained.

Examples of linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ alkoxy groups include ethoxy groups, methoxy groups, and propoxy groups.
An example of the carboxy group is an acetoxy group.
Examples of fluoroalkylsulfone groups include trifluoromethanesulfonyl.
Fluorosulfone groups include, for example, fluorosulfonyl.
Alkylsulfone groups include, for example, methanesulfonyl, ethanesulfonyl, n-propanesulfonyl, isopropanesulfonyl, and the like.
Arylsulfone groups include, for example, benzenesulfonyl, p-toluenesulfonyl, naphthalenesulfonyl, and indenesulfonyl.
Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the phenoxy group include a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a propylphenoxy group, a methoxyphenoxy group, an ethoxyphenoxy group, and a propoxyphenoxy group.
Examples of the selenoxy group include a selenomethyl group, a selenoethyl group, a selenopropyl group, a selenobutyl group, and a selenohexyl group.

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

In formula (I-1), p represents an integer of 0 to 5.
Each _L1 independently represents -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(R ⁶ )CH ₂ - or -CH ₂ CH(R ⁶ )-, where R ⁶ represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent.
^R7 represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent.
^R8 represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent.

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

In formula (I-1), from the viewpoint of production costs, R ⁶ preferably represents an alkyl group having 1 to 3 carbon atoms which may have a substituent. R ⁶ 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. Examples of R ⁶ include a methyl group, an ethyl group, and a propyl group.

In formula (I-1), from the viewpoint of production costs, R ⁷ preferably represents a carbon atom having 1 to 6 which may have a substituent, and more preferably represents an alkyl group having 1 to 3 carbon atoms. R ⁷ 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. Examples of R ⁷ include a methyl group, an ethyl group, and a propyl group.

In formula (I-1), from the viewpoint of production cost and ease of removal after elimination, R ⁸ preferably represents a carbon atom having 1 to 6 which may have a substituent, and more preferably represents an alkyl group having 1 to 3 carbon atoms. R ⁸ 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. Examples of R ⁸ include a methyl group, an ethyl group, and a propyl group, and a methyl group or an ethyl group is preferable.

The method for preparing the trisubstituted olefin (I) may be any known method.

(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 tri-substituted olefin (I). The hydrogenation catalyst may be a known hydrogenation catalyst.

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.

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. Only one of these transition metals may be used, or two or more of them may be mixed and used.

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

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, etc.) 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, and clay. Only one of these carriers may be used, or two or more of them may be used in combination.

The hydrogenation catalyst preferably contains at least one selected from the group consisting of Pd(OH) ₂ /C (palladium hydroxide/carbon), Pd/C (palladium/carbon) and Pt/C (platinum/carbon), and more preferably contains at least one of Pd(OH) ₂ /C (palladium hydroxide/carbon) and Pd/C (palladium/carbon). This allows the production of tri-substituted 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 catalyst species.

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

The amount of 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 trisubstituted olefin (I) falls within the above range.

(1.1.1.3) Reduction Reaction The reduction reaction is carried out by charging the tri-substituted olefin (I) and a hydrogenation catalyst into a reaction vessel. The reaction vessel may be operated in a batch or continuous manner.

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 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 further preferably 10°C to 30°C.

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

(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.

"Reducing agent" refers to a source of hydrogen to be added to the unsaturated bond of the trisubstituted olefin (I).

Examples of the reducing agent include hydrogen and metal hydrides (e.g., _NaBH4 , _KBH4 , _LiAlH4 , etc.). These reducing agents may be used alone or in combination of two or more. The reducing agent may be a known reducing agent.

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.

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, etc.

When the reduction reaction step is carried out in the presence of a reducing agent, it is preferable that the reducing agent contains hydrogen, and the hydrogen pressure in the reduction reaction step is 0.1 MPa to 20 MPa.
From the viewpoints of safety and the economy of the production equipment, the hydrogen pressure is more preferably 0.1 MPa to 0.9 MPa, and further preferably 0.1 MPa to 0.5 MPa.

(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.

"Water scavenger" refers to a solid that has the property of absorbing moisture.

The reduction reaction step is preferably carried out in the presence of a water scavenger.
When synthesizing trisubstituted ethane (II), a compound having a highly electron-withdrawing functional group (e.g., a cyano group, etc.) at the carbon at the 1-position of a carbon-carbon multiple bond is likely to undergo a side reaction (e.g., elimination of a substituent at the carbon at the 2-position of a 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 that 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 trisubstituted ethane (II) in a higher yield than when the reduction reaction step is not carried out in the presence of a water scavenger.

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

When the reduction reaction step is carried out in the presence of a water scavenger, the water scavenger preferably contains crystalline zeolite and a carboxylic anhydride. This makes it easier to remove water that 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 a configuration in which the water scavenger does not contain crystalline zeolite and a carboxylic anhydride.

When the reduction reaction step is carried out in the presence of a water scavenger, the amount of the water scavenger is not particularly limited. When the water scavenger contains a carboxylic acid anhydride, the amount of the water scavenger is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 50 parts by mass, based on 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).

(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 further adding a solvent to the reaction vessel. The reduction reaction step may be carried out in the absence of a solvent.

Solvents include, for example, 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 Examples of the solvent include dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, ureas (e.g., N,N'-dimethylimidazolidone and N,N,N,N-tetramethylurea, etc.), sulfones (e.g., dimethylsulfone and tetramethylenesulfone, etc.), sulfoxides (e.g., dimethylsulfoxide and diphenylsulfoxide, 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., dimethylcarbonate and ethylene carbonate, etc.). These solvents may be used alone or in combination of two or more.

The reduction reaction step is 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.

When the reduction reaction step is carried out in the presence of a solvent, the amount of the solvent used is not particularly limited, but 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).

(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).

In formula (II), A and D each independently represent one selected from ^the _{group consisting of CN, CO2R1, COR1, CON(R1)2, SO2R1, SO3R1 ,} ^{COPO (} _{OR1 )} ^{2 , COP} ( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a _C1 - _C20 acetoxy silane, a C2- _C20 alkoxy alkyl, a _{C2 -C20 alkenyl} , a _C2 - _C20 alkynyl, a _C2 - _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkylcycloalkyl, a _C3 - _C20 cycloalkenyl, an alkylcycloalkenyl, an aryl, an alkyl moiety substituted with an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic ring, an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (I) and formula (II), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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.

In formula (II), A, D, and R are the same as those exemplified for 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).

An example of trisubstituted ethane (II) is the compound represented by the following formula (II-1):

In formula (II-1), p, L ₁ , R ⁷ and R ⁸ are as defined above in formula (I-1).

　Applications of trisubstituted ethane (II) are not particularly limited, but include, for example, raw materials for anionically polymerizable disubstituted olefins.

(1.1.2) Separation step The method for producing 1,1,2-trisubstituted ethane of the first embodiment may have a separation step. In the separation step, the reaction liquid 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 liquid, 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 liquid together with the hydrogenation catalyst by filtration. The method of filtration is not particularly limited, and may be any known method.

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 anhydride and water) contained in the reaction solution after the reduction reaction step is close to the boiling point of the solvent. This allows impurities to be separated from the reaction solution in addition to the solvent. As a result, a reaction solution with a higher yield of tri-substituted ethane (II) is obtained. Examples of distillation methods include evaporators, simple distillation, and thin-film distillation. The temperature during distillation may be 40°C to 120°C.

(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.

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).

The method for producing 1,1-disubstituted olefins of the first embodiment preferably includes an elimination reaction step of obtaining trisubstituted ethane (II) by the method for producing 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., 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 acid catalysts, base catalysts, and acid-base catalysts (hereinafter also referred to as "elimination reaction catalyst").

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).

"Acid-base catalyst" refers to a catalyst that is a mixture of acid and base.

The method for producing 1,1-disubstituted olefins in the first embodiment has the above configuration, making it possible to produce anionically polymerizable disubstituted olefins in high yield without performing distillation.

In the method for producing 1,1-disubstituted olefins according to the first embodiment, trisubstituted ethane (II) is used as a raw material, and therefore, according to the method for producing 1,1-disubstituted olefins according to the first embodiment, it is possible to produce anionically polymerizable disubstituted olefins without carrying out high-temperature treatment (e.g., depolymerization, etc.).
Due to its reactivity, the disubstituted olefin (III) having anion polymerization properties is likely to undergo polymerization reaction due to 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 is performed, a purification method can be adopted according to the type of the disubstituted olefin (III).
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, and 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 first embodiment of the method for producing a 1,1-disubstituted olefin, an alkoxy group is used as the leaving group of the trisubstituted olefin (I), a low-boiling carboxylic acid anhydride is used as the alcohol scavenger to be eliminated, and a solid acid is used as the reaction catalyst, whereby a disubstituted olefin (III) is obtained by filtration and distillation of the low boiling point components. Therefore, according to the first embodiment of the method for producing a 1,1-disubstituted olefin, even if the disubstituted olefin (III) is a monomer that is extremely difficult to distill (e.g., a solid monomer, a polyfunctional monomer, etc.), the disubstituted olefin (III) can be produced.

(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") is carried out in the presence of an elimination reaction catalyst to obtain a disubstituted olefin (III).

(1.2.1.1) Catalyst for elimination reaction The catalyst for 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 tri-substituted ethane (II).

(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 (for example, "Ion Exchange Resin for Catalysts" manufactured by Organo Corporation). Amberlyst 15 DRY"), a solid catalyst in which a sulfonic acid group is chemically bonded to a carrier, a solid catalyst 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.

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 carrier, a solid catalyst 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, phosphoric acid It is preferable that the phosphate phosphate 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.

When the elimination reaction catalyst is an acid 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%, relative to 100 mol% of the trisubstituted ethane (II).

(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), hydrogen carbonates (e.g., calcium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, and ammonium hydrogen carbonate), 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.

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%, relative to 100 mol% of the trisubstituted ethane (II).

(1.2.1.1.3) Acid-base catalyst Examples of the acid-base catalyst include salts of the above-mentioned acid catalyst and the above-mentioned base catalyst, 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.

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%, relative to 100 mol% of the tri-substituted ethane (II), and 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%, relative to 100 mol% of the tri-substituted ethane (II).

(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"). As a result, the method for producing a 1,1-disubstituted olefin of the first embodiment can produce a disubstituted olefin (III) more efficiently than a configuration in which the acid catalyst does not contain the specific compound.

(1.2.1.2) Elimination reaction The elimination reaction is carried out by charging the tri-substituted ethane (II) and the elimination reaction catalyst into a reaction vessel. The operation method of the reaction vessel may be a batch method or a continuous method.

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

(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.

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.

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.

It is preferable that R represents the alkoxy group and the elimination reaction step is carried out in the presence of an alcohol scavenger. As a result, the method for producing 1,1-disubstituted olefins of the first embodiment can suppress the polymerization reaction of disubstituted olefin (III) caused by alcohol and obtain disubstituted olefin (III) with a higher reaction yield than a configuration in which the elimination reaction step is carried out in the absence of an alcohol scavenger.

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

When the R represents the alkoxy group, the elimination reaction step is carried out in the presence of an alcohol trapping agent, and the alcohol trapping agent contains a carboxylic acid anhydride, it is preferable that the carboxylic acid anhydride 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 the "specific carboxylic acid anhydride"). As a result, the method for producing 1,1-disubstituted olefins of the first embodiment produces by-products with lower boiling points than a configuration in which the carboxylic acid anhydride does not contain the specific carboxylic acid anhydride, and these by-products can be easily removed by an evaporator or the like in the purification step.

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, but is preferably 100 mol% to 500 mol%, more preferably 100 mol% to 200 mol%, relative to 100 mol% of the trisubstituted ethane (II).

(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.

Solvents include, for example, 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 Examples of the solvent include dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, ureas (e.g., N,N'-dimethylimidazolidone and N,N,N,N-tetramethylurea, etc.), sulfones (e.g., dimethylsulfone and tetramethylenesulfone, etc.), sulfoxides (e.g., dimethylsulfoxide and diphenylsulfoxide, 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., dimethylcarbonate and ethylene carbonate, etc.). These solvents may be used alone or in combination of two or more.

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

(1.2.1.5) 1,1-Disubstituted Olefins By carrying out the elimination reaction step, the disubstituted olefin (III) is obtained.

An example of the disubstituted olefin (III) is a cyanoacrylate ester represented by the following formula (III-1):

In formula (III-1), p, L ₁ and R ⁷ are as defined above in formula (I-1).

The disubstituted olefin (III) is suitable for a variety of applications (e.g., adhesives, coatings, sealants, etc.).

(1.2.2) Separation step The method for producing a 1,1-disubstituted olefin of the first embodiment may have a separation step. When a solid catalyst is used, in the separation step, the reaction liquid after the elimination reaction step is filtered. The separation step is carried out after the elimination reaction step. Thereby, the elimination reaction catalyst is separated from the reaction liquid, 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 is also separated from the reaction liquid together with the elimination reaction catalyst by filtration. The filtration method is not particularly limited, and may be any known method.

When the elimination 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., the alcohol that is eliminated, the carboxylic acid ester produced from the carboxylic acid anhydride, and the carboxylic acid, etc.) contained in the reaction solution after the elimination reaction step is close to the boiling point of the solvent. This allows impurities to be separated 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.

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

(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 a 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.

In formula (II) and formula (III), A and D each independently represent one selected from the group consisting of ^CN , _CO2R1 , ^COR1 , CON( ^R1 ) ₂ , _SO2R1 , ^SO3R1 , COPO ⁽ _OR1 ) ² , COP( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a C1- _C20 acetoxy silane, a _C2 - _C20 alkoxy alkyl, a _C2 - _C20 alkenyl, a _C2 - _C20 alkynyl, a _C2 - _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkyl cycloalkyl, a _{C3 - C20} cycloalkenyl, an alkyl cycloalkenyl, an aryl, an alkyl moiety bonded to an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic ring, an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (II) and formula (III), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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.

The method for producing 1,1-disubstituted olefins in the second embodiment has the above configuration, and therefore has the same effects as the method for producing 1,1-disubstituted olefins in the first embodiment.

The method for producing 1,1-disubstituted olefins in the second embodiment is the same as the method for producing 1,1-disubstituted olefins in the first embodiment, except that the trisubstituted ethane (II) does not have to be produced by the method for producing 1,1-disubstituted olefins in the first embodiment.

The method for producing 1,1-disubstituted olefins 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 (hereinafter also referred to as the "specific compound") selected from the group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid. As a result, the method for producing 1,1-disubstituted olefins of the second embodiment can produce disubstituted olefins (III) more efficiently than a configuration in which the acid catalyst does not contain the specific compound.

It is preferable that R represents the alkoxy group and the elimination reaction step is carried out in the presence of an alcohol scavenger. As a result, the method for producing 1,1-disubstituted olefins of the second embodiment can suppress the polymerization reaction of disubstituted olefin (III) caused by alcohol and obtain disubstituted olefin (III) with a higher reaction yield than a configuration in which the elimination reaction step is carried out in the absence of an alcohol scavenger.

When R represents the alkoxy group and the elimination reaction step is carried out in the presence of an alcohol scavenger, it is preferable that the alcohol scavenger 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 resulting disubstituted olefin (III) can be more effectively suppressed than in a configuration in which the alcohol scavenger does not contain a carboxylic acid anhydride.

When the R represents the alkoxy group, the elimination reaction step is carried out in the presence of an alcohol trapping agent, and the alcohol trapping agent contains a carboxylic acid anhydride, it is preferable that the carboxylic acid anhydride 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 the "specific carboxylic acid anhydride"). As a result, the method for producing 1,1-disubstituted olefins of the second embodiment produces by-products with lower boiling points than a configuration in which the carboxylic acid anhydride does not contain the specific carboxylic acid anhydride, and these by-products can be easily removed by an evaporator or the like in the purification step.

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 carrier, a solid catalyst 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, phosphoric acid It is preferable that the phosphate phosphate 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.

The present disclosure will be explained in more detail below 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.

[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. After 6 hours had elapsed from the start of stirring, the reaction solution was analyzed by nuclear magnetic resonance (NMR). As a result of the analysis, it was found 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%.

"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 the reaction is stopped and the ratio (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 integral value of NMR (Nuclear Magnetic Resonance).

[1.1.2] Elimination reaction step (volatile carboxylic acid anhydride + high boiling point 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 and stirred at 120° C. for 6.0 hours. The resulting solution was analyzed by NMR. As a result of the analysis, it was found that ethyl cyanoacrylate (III-1) represented by the following formula (III-1) was obtained. The reaction yield of ethyl cyanoacrylate (III-1) was 96%.

"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 the reaction is stopped and the ratio (molar ratio) of the target substance ethyl cyanoacrylate (III-1) contained in the product. The molar ratio was calculated based on the integral value of NMR (Nuclear Magnetic Resonance).

[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-carbon (0.3 g), toluene (5 mL), and molecular sieve 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. After 6 hours had elapsed from the start of stirring, the reaction solution was analyzed by NMR. The analysis showed 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%.

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

[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-carbon (0.3 g), toluene (5 mL), acetic anhydride (0.3 g), and molecular sieve 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. After 6 hours had elapsed from the start of stirring, the reaction solution was analyzed by NMR. The analysis showed that the target compound (ethyl 2-cyano-3-ethoxypropionate) was obtained. The reaction yield of ethyl 2-cyano-3-ethoxypropionate was 96%.

[1.3.2] Elimination reaction step (volatile carboxylic acid anhydride + high boiling point 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%.

[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 sieve 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. After 6 hours had elapsed from the start of stirring, the reaction solution was analyzed by NMR. The analysis showed that the target compound (ethyl 2-cyano-3-ethoxypropionate) was obtained. The reaction yield of ethyl 2-cyano-3-ethoxypropionate was 85%.

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

[1.5] Results

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 1,2-trisubstituted ethane production methods 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 performing distillation."

The yield of tri-substituted ethane (II) in Examples 1 to 4 was 47% or more. This result shows that the 1,2-tri-substituted ethane production methods in Examples 1 to 4 can produce tri-substituted ethane (II) in high yield.

[2] Examples 1 and 5 to 7
[2.1] Example 5 (solid carboxylic acid anhydride + high boiling point sulfonic acid catalyst)
As ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1), a solution obtained by removing solids by filtration from the reaction solution obtained in Example 1 was used. 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 and stirred 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%.

[2.2] Example 6 (volatile carboxylic acid anhydride + solid sulfonic acid catalyst)
As ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1), a solution obtained by removing solids by filtration from the reaction solution obtained in Example 1 was used. 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 and stirred at 120° C. for 6.0 hours. The resulting solution was analyzed by NMR. The analysis showed that ethyl cyanoacrylate (III-1) was obtained. The reaction yield of ethyl cyanoacrylate (III-1) was 80%.

[2.3] Example 7 (solid carboxylic acid anhydride + high boiling point sulfonic acid catalyst + solid amine catalyst)
As ethyl 2-cyano-3-ethoxypropionate (II-1) represented by the following formula (II-1), a solution obtained by removing solids by filtration from the reaction solution obtained in Example 1 was used. 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 and stirred 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%.

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

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 entireties.
All publications, patent applications, and standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or standard was specifically and individually indicated to be incorporated by reference.

Claims (16)

As shown in the following reaction formula, the method includes 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),
The method for producing 1,1,2-trisubstituted ethane, wherein the reduction reaction step is carried out in the presence of a hydrogenation catalyst.

In formula (I) and formula (II), A and D each independently represent one selected from the group consisting of ^CN , _CO2R1 , ^COR1 , CON( ^R1 ) ₂ , _SO2R1 , ^SO3R1 , COPO ⁽ _OR1 ) ² , COP( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a C1- _C20 acetoxy silane, a _C2 - _C20 alkoxy alkyl, a _C2 - _C20 alkenyl, a _C2 - _C20 alkynyl, a _C2 - _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkyl cycloalkyl, a _{C3 - C20} cycloalkenyl, an alkyl cycloalkenyl, an aryl, an alkyl moiety bonded to an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic ring, an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (I) and formula (II), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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. 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. 2. The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the hydrogenation catalyst comprises at least one of Pd(OH) ₂ /C and Pd/C. The reduction reaction step is carried out in the presence of a reducing agent,
The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the reducing agent comprises hydrogen or a metal hydride. the reducing agent comprises hydrogen;
The method for producing 1,1,2-trisubstituted ethane according to claim 4, wherein the hydrogen pressure in the reduction reaction step is 0.1 MPa to 20 MPa. 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. 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. The reduction reaction step is carried out in the presence of a solvent,
The method for producing 1,1,2-trisubstituted ethane according to claim 1, wherein the solvent comprises at least one selected from the group consisting of aromatic hydrocarbons, hydrocarbons, ethers, ketones, alcohols, carboxylic acids, and esters. 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. obtaining 1,1,2-trisubstituted ethane by the process according to claim 1;
and an elimination reaction step of eliminating the functional group R of the 1,1,2-trisubstituted ethane to obtain a 1,1-disubstituted olefin represented by the following formula (III), as shown in the following reaction formula:
The present invention relates to a method for producing a 1,1-disubstituted olefin, 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.

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). As shown in the following reaction formula, the method includes 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),
The present invention relates to a method for producing a 1,1-disubstituted olefin, 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 each independently represent one selected from the group consisting of ^CN , _CO2R1 , ^COR1 , CON( ^R1 ) ₂ , _SO2R1 , ^SO3R1 , COPO ⁽ _OR1 ) ² , COP( ^OR1 ) _{2 ,} and _NO2 . ^R1 represents a linear or branched saturated or unsaturated _C1 - _C20 alkyl, a _C1 - _C20 alkyl halide, a _C4 - _C20 alkyl silane, a C1- _C20 acetoxy silane, a _C2 - _C20 alkoxy alkyl, a _C2 - _C20 alkenyl, a _C2 - _C20 alkynyl, a _C2 - _C10 alkylene, a _C3 - _C20 cycloalkyl, an alkyl cycloalkyl, a _{C3 - C20} cycloalkenyl, an alkyl cycloalkenyl, an aryl, an alkyl moiety bonded to an aryl, an aliphatic heterocyclic moiety, an alkyl moiety bonded to an aliphatic heterocyclic ring, an aromatic heterocyclic moiety, an alkyl moiety bonded to an aromatic heterocyclic ring, an acrylic ester moiety, a glycolic acid moiety, a carboxylic ester moiety, or a halogen-substituted alkyl moiety.
In formula (II) and formula (III), R represents a linear, branched or alicyclic saturated or unsaturated C ₁ -C ₂₀ 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. the elimination reaction step is carried out in the presence of the acid catalyst,
The method for producing a 1,1-disubstituted olefin according to claim 10 or 11, wherein the acid catalyst comprises at least one compound selected from the group consisting of sulfuric acid, sulfonic acid, phosphoric acid, and phosphorous acid. The R represents the alkoxy group,
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 an alcohol scavenger. The method for producing 1,1-disubstituted olefins according to claim 13, wherein the alcohol scavenger comprises a carboxylic acid anhydride. The method for producing 1,1-disubstituted olefins according to claim 14, wherein the carboxylic acid anhydride comprises at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, maleic anhydride, and succinic anhydride. 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 carrier, a solid catalyst 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, monoisotridecyl phosphate, phosphoric acid The method for producing a 1,1-disubstituted olefin according to claim 10 or 11, comprising at least one selected from the group consisting of monohexadecyl, 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.