JP2017052759A - Method for producing onium compound, and method for producing curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an onium compound which can produce a specific onium compound with a simple method and a high yield.SOLUTION: There is provided a method for producing an onium compound which is any of the following methods (A), (B) and (C). The method (A) includes a steps of mixing and reacting a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3) in at least any one solvent of water, alcohol and acetonitrile to obtain a sulfonium compound represented by general formula (4). The method (B) includes a step of mixing and reacting a compound represented by general formula (11), the compound represented by general formula (2), and the compound represented by general formula (3) in water to obtain an ammonium compound represented by general formula (14). The method (C) includes a step of mixing and reacting a compound represented by general formula (21), the compound represented by general formula (2), and the compound represented by general formula (3) in water to obtain a phosphonium compound represented by general formula (24).SELECTED DRAWING: None

Description

  The present invention particularly relates to a method for producing an onium compound useful as a polymerization catalyst for curing by at least one of light and heat, and a method for producing a curable resin composition using the production method.

  Many onium salt compounds used as cationic curing catalysts for cationic curing components such as epoxy resins, typically sulfonium salts having dissociated species of benzyl structure or cinnamyl structure useful as thermal cationic curing are known.

A typical method for producing a sulfonium salt will be introduced on behalf of an onium salt (see, for example, Patent Documents 1 to 4). First, thioether is reacted with a halide compound having a benzyl structure or a cinnamyl structure to synthesize a corresponding sulfonium halide. Thereafter, anion exchange is performed with strong acid anions in water, in an organic solvent, or in a two-phase system of water and an organic solvent.
However, in this method, in the method for producing a sulfonium compound intended for thermosetting at a lower temperature, there is a problem that synthesis of the corresponding sulfonium halide becomes difficult and the yield is deteriorated.

  Therefore, a method for producing a sulfonium salt which can be cured at a lower temperature by first synthesizing a specific sulfonium salt having a p-hydroxyphenyl group and then modifying the p-hydroxy group with a specific carbonyl halide compound or an isocyanate compound. (For example, refer to Patent Documents 5 and 6). However, this manufacturing method requires two stages of manufacturing, which is disadvantageous in terms of process costs. In addition, this manufacturing method requires strict management of the manufacturing process and is a burden. Furthermore, this production method can be applied to highly reactive substances such as carbonyl halides and isocyanates. However, in the production of the sulfonium compounds described in Patent Documents 1 to 4, the reaction hardly proceeds and the temperature is high. Alternatively, there is a problem that a long-time reaction is forced, resulting in excessive decomposition of the sulfonium compound.

Japanese Patent Laid-Open No. 8-188869 JP-A-4-210673 Japanese Patent Laid-Open No. 11-255739 Japanese Patent No. 5561199 JP-A-3-47164 JP 2011-231243 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a method for producing an onium compound capable of producing a specific onium compound in a simple method and in a high yield, and a method for producing a curable resin composition using the production method. To do.

Means for solving the problems are as follows. That is,
<1> A method for producing an onium compound, which is any of the following (A), (B), and (C).
(A) In at least one solvent of water, alcohol, and acetonitrile, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula (3) After mixing with a compound represented by the formula (1), the reaction is carried out to obtain a sulfonium compound represented by the following general formula (4).
(B) In water, the compound represented by the following general formula (11), the compound represented by the following general formula (2), and the compound represented by the following general formula (3) are mixed and reacted. The ammonium compound represented by the following general formula (14) is obtained.
(C) In water, the compound represented by the following general formula (21), the compound represented by the following general formula (2), and the compound represented by the following general formula (3) are mixed and reacted. A phosphonium compound represented by the following general formula (24) is obtained.
However, the general formula (1) and general formula (4), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms.
In the general formula (1) and the general formula (4), R ² represents a phenyl group having 0 to 5 substituents (provided that when the solvent contains water as a main component, the R ² in the R ² represents The sum of the substituent constants of Hammett's substituents is 0.30 or less, and when the solvent does not contain water as the main component, R ² is a group represented by the following general formula (A)).
In the general formulas (2) and (4), R ³ is an α-naphthylmethyl group in which an aromatic ring hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, or an aromatic ring hydrogen. A cinnamyl group in which an atom may be substituted with an alkyl group having 1 to 4 carbon atoms, a group represented by the following general formula (B), a group represented by the following general formula (C), and the following general formula (D) Any one of the groups represented by
In the general formula (2), Z represents a halogen atom.
In the general formula (3), X ⁺ represents any of Li ⁺ , Na ⁺ , and K ⁺ .
In the general formulas (3) and (4), Y ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , PF ₃ (C ₂ F _{^{5) 3 -, C 3 F}} 6 NO 4 S 2 -, (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.
In the general formula (A), R ⁴ is a hydrogen atom, and represent an alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a benzyl group which may have a substituent, a naphthylmethyl group which may have a substituent, or an alkylcarbonylmethyl. A group, an arylcarbonylmethyl group which may have a substituent, an alkoxycarbonylmethyl group, and an aryloxycarbonylmethyl group which may have a substituent;
In the general formula (B), R ⁶ represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group.
In the general formula (C), R ⁷ represents any one of a hydrogen atom, a methyl group, and a phenyl group.
In the general formula (D), R ⁸ represents any of an alkyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
However, in said general formula (11) and general formula (14), R < ¹¹ > and R < ¹² > represent a C1-C4 alkyl group each independently.
In General Formula (11) and General Formula (14), R ¹³ represents a phenyl group having 0 to 5 substituents, and the sum of Hammett's substituent constants of the substituents in R ¹³ is 0. 60 or less.
In the general formula (14), R ³ represents an α-naphthylmethyl group in which the hydrogen atom of the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the aromatic ring has 1 to carbon atoms. A cinnamyl group optionally substituted with an alkyl group of 4, a group represented by the general formula (B), a group represented by the general formula (C), and a group represented by the general formula (D) Represents either.
In the general formula (14), Y ^{- _{is, B (C 6 F 5)}} 4 -, SbF 6 -, AsF 6 -, PF 6 -, BF 4 -, PF 3 (C 2 F 5) 3 -, C ^{_{3 F 6 NO 4 S 2 -}} , (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.
However, in said general formula (21) and general formula (24), R <^21> , R < ²² > and R < ²³ > represent the phenyl group which has 0-5 substituents each independently. The sum total of Hammett's substituent constants of the substituent in R ²¹ is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²² is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²³ is 0.70 or less.
In the general formula (24), R ³ represents an α-naphthylmethyl group in which the hydrogen atom of the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the aromatic ring represents 1 to carbon atoms. A cinnamyl group optionally substituted with an alkyl group of 4, a group represented by the general formula (B), a group represented by the general formula (C), and a group represented by the general formula (D) Represents either.
In the general formula (24), Y ^{- _{is, B (C 6 F 5)}} 4 -, SbF 6 -, AsF 6 -, PF 6 -, BF 4 -, PF 3 (C 2 F 5) 3 -, C ^{_{3 F 6 NO 4 S 2 -}} , (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.
<2> In the general formula (3), the general formula (4), the general formula (14), and the general formula (24), Y ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ^−. , PF ₆ ⁻ , PF ₃ (C ₂ F ₅ ) ₃ ⁻ , and C (CF ₃ SO ₂ ) ₃ ^— .
<3> The method for producing an onium compound according to any one of <1> to <2>, wherein the alcohol is at least one of methanol and ethanol.
<4> In the general formula (3), the general formula (4), the general formula (14), and the general formula (24), R ³ is a benzyl group, an o-methylbenzyl group, or α-naphthylmethyl. The method for producing an onium compound according to any one of <1> to <3>, wherein the group is any one of a group, a cinnamyl group, an allyl group, a methallyl group, and a 2-ethoxycarbonylpropenyl group.
<5> A method for producing a curable resin composition containing an onium compound,
The method for producing a curable resin composition, wherein the onium compound is obtained by the method for producing an onium compound according to any one of <1> to <4>.
<6> The method for producing a curable resin composition according to <5>, wherein the curable resin composition further contains an epoxy compound.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and a production method capable of producing a specific onium compound in a simple method and high yield, and the production method are used. A method for producing a curable resin composition can be provided.

(Method for producing onium compound)
The method for producing an onium compound of the present invention is any of the following (A), (B), and (C).
(A) In at least one solvent of water, alcohol, and acetonitrile, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula (3) After mixing with a compound represented by the formula (1), the reaction is carried out to obtain a sulfonium compound represented by the following general formula (4).
(B) In water, the compound represented by the following general formula (11), the compound represented by the following general formula (2), and the compound represented by the following general formula (3) are mixed and reacted. The ammonium compound represented by the following general formula (14) is obtained.
(C) In water, the compound represented by the following general formula (21), the compound represented by the following general formula (2), and the compound represented by the following general formula (3) are mixed and reacted. A phosphonium compound represented by the following general formula (24) is obtained.

<Method for producing sulfonium compound (A)>
In the method for producing a sulfonium compound of one embodiment of the method for producing an onium compound of the present invention, the compound represented by the following general formula (1) in the solvent of water, alcohol, and acetonitrile, The compound represented by the formula (2) and the compound represented by the following general formula (3) are mixed and reacted to obtain a sulfonium compound represented by the following general formula (4).

However, the general formula (1) and general formula (4), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms.
In the general formula (1) and the general formula (4), R ² represents a phenyl group having 0 to 5 substituents (provided that when the solvent contains water as a main component, the R ² in the R ² represents The sum of the substituent constants of Hammett's substituents is 0.30 or less, and when the solvent does not contain water as the main component, R ² is a group represented by the following general formula (A)).
In the general formulas (2) and (4), R ³ is an α-naphthylmethyl group in which an aromatic ring hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, or an aromatic ring hydrogen. A cinnamyl group in which an atom may be substituted with an alkyl group having 1 to 4 carbon atoms, a group represented by the following general formula (B), a group represented by the following general formula (C), and the following general formula (D) Any one of the groups represented by
In the general formula (2), Z represents a halogen atom.
In the general formula (3), X ⁺ represents any of Li ⁺ , Na ⁺ , and K ⁺ .
In the general formulas (3) and (4), Y ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , PF ₃ (C ₂ F _{^{5) 3 -, C 3 F}} 6 NO 4 S 2 -, (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.
In the general formula (A), R ⁴ is a hydrogen atom, and represent an alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a benzyl group which may have a substituent, a naphthylmethyl group which may have a substituent, or an alkylcarbonylmethyl. A group, an arylcarbonylmethyl group which may have a substituent, an alkoxycarbonylmethyl group, and an aryloxycarbonylmethyl group which may have a substituent;
In the general formula (B), R ⁶ represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group.
In the general formula (C), R ⁷ represents any one of a hydrogen atom, a methyl group, and a phenyl group.
In the general formula (D), R ⁸ represents any of an alkyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

  As a result of intensive studies, the present inventors have found that a combination of a specific solvent and a specific raw material can be used as a cation curing catalyst without requiring isolation and purification of an intermediate (sulfonium halide) during the reaction. It has been found that specific usable sulfonium compounds can be synthesized.

That is, when the present inventors produce a sulfonium compound that can be used as a cationic curing catalyst at a time without isolation and purification of intermediates, It has been found that the electron withdrawing property or electron donating property of the substituent of the phenyl group of R ^{2 in} the compound represented by the formula (1) is important in terms of reactivity. Therefore, the present inventors examined various substituents and investigated the relationship between Hammett's substituent constant and manufacturability. As a result, in the production of sulfonium compounds, the solvent is mainly composed of water. It was found that when the sum of Hammett's substituent constants of the substituent in R ² is 0.30 or less, a sulfonium compound can be produced and the yield is high. In addition, the total of Hammett's substituent constants of the substituent in R ² is preferably −0.40 to 0.20, in view of obtaining a sulfonium compound having an appropriate thermosetting property, and −0.30. 0.00 is more preferable.
When the sum of Hammett's substituent constants of the substituent in R ² exceeds 0.30, it becomes difficult to produce a sulfonium compound. This is thought to be due to a decrease in reactivity due to a decrease in nucleophilicity of the thioether and a decrease in the stability of the target product.

In addition, when the present inventors produce a sulfonium compound that can be used as a cationic curing catalyst at a time without isolation and purification of an intermediate, when the solvent does not contain water as a main component, It was noticed that the structure of R ^{2 in} the compound represented by the formula (1) is important in terms of reactivity. Therefore, as a result of various studies on the structure of R ² , the present inventors can produce a sulfonium compound when the structure of R ² is a group represented by the general formula (A). Moreover, it discovered that the yield was also high.

Here, the Hammett's substituent constant is a numerical value representing the effect of the substituent on the acid dissociation equilibrium constant of the substituted benzoic acid. This constant is a parameter indicating the strength of the electron withdrawing property and electron donating property of the substituent.
The substituent of the phenyl group generally has a Hammett's substituent constant as follows.

In Table 1, “Me” represents a methyl group. “Et” represents an ethyl group. “Ph” and “C ₆ H ₅ ” represent a phenyl group.
Hammett's substituent constants are described in, for example, “Chemical Domain”, No. 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, Vol. 91, pages 165 to 195, and the like. Although it depends on the type of substituent, it can also be calculated by calculation using ChemBioDraw or the like.

  In the present invention, “the solvent is mainly water” means that 50% by mass or more of the solvent is water. “The solvent does not contain water as a main component” means that less than 50% by mass of the solvent is water.

<< Compound Represented by Formula (1) >>
In the general formula (1), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms.
In the general formula (1), R ² represents a phenyl group having 0 to 5 substituents (provided that when the solvent contains water as a main component, Hammett substitution of the substituents in the R ²⁾ The sum of the base constants is 0.30 or less, and when the solvent does not contain water as the main component, R ² is a group represented by the following general formula (A)).
In the general formula (A), R ⁴ is a hydrogen atom, and represent an alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a benzyl group which may have a substituent, a naphthylmethyl group which may have a substituent, or an alkylcarbonylmethyl. A group, an arylcarbonylmethyl group which may have a substituent, an alkoxycarbonylmethyl group, and an aryloxycarbonylmethyl group which may have a substituent;

<<< R ¹ >>>
Examples of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

<<< R ² >>>
R ² represents a phenyl group having 0 to 5 substituents. However, when the solvent contains water as a main component, the sum total of Hammett's substituent constants of the substituent in R ² is 0.30 or less. When the solvent does not contain water as a main component, R ² is a group represented by the general formula (A).
Examples of the substituents that are subject to calculation of the Hammett's substituent constant include substituents having 1 to 10 carbon atoms and the substituents described in Table 1 above.

-Group represented by general formula (A)-
--R ⁴ ---
R ⁴ in the group represented by the general formula (A) represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl, t-butyl group and the like.

--R ⁵ ---
R ⁵ in the group represented by the general formula (A) has a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a benzyl group which may have a substituent, or a substituent. Any of an optionally substituted naphthylmethyl group, an alkylcarbonylmethyl group, an optionally substituted arylcarbonylmethyl group, an alkoxycarbonylmethyl group, and an optionally substituted aryloxycarbonylmethyl group Represents

Examples of the alkyl group in R ^5, for example, an alkyl group having 18 or less carbon atoms. Examples of the alkyl group having 18 or less carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, and neo-pentyl group. , N-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

Examples of the aryl group in the aryl group which may have a substituent for R ⁵ include a phenyl group and a naphthyl group. Examples of the naphthyl group include 1-naphthyl group and 2-naphthyl group.

Examples of the naphthylmethyl group in the naphthylmethyl group which may have a substituent for R ⁵ include a 1-naphthylmethyl group and a 2-naphthylmethyl group. Here, the substituent is bonded to a naphthyl group.

Examples of the alkyl group in the alkylcarbonylmethyl group in R ⁵ include an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, and neo-pentyl. Group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

Examples of the arylcarbonylmethyl group in the arylcarbonylmethyl group which may have a substituent for R ⁵ include a phenylcarbonylmethyl group and a naphthylcarbonylmethyl group. Here, the substituent is bonded to the aryl group.

Examples of the alkoxy group in the alkoxycarbonylmethyl group for R ⁵ include an alkoxy group having 1 to 10 carbon atoms.

Examples of the aryl group in the aryloxycarbonylmethyl group which may have a substituent for R ⁵ include a phenyl group and a naphthyl group. Here, the substituent is bonded to the aryl group.

  The aryl group which may have the substituent, the naphthyl group which may have the substituent, the benzyl group which may have the substituent, the naphthyl which may have the substituent Examples of the substituent in the methyl group, the arylcarbonylmethyl group which may have the substituent, and the aryloxycarbonylmethyl group which may have the substituent include, for example, a hydroxyl group, an alkyl group, an alkoxy group, Examples include alkanoyl groups, carboxy groups, alkoxycarbonyl groups, amino groups, halogen atoms, nitro groups, and cyano groups. Further, the number of the substituents may be one or plural.

Here, when the solvent does not contain water as a main component, when R ² is a group other than the group represented by the general formula (A), for example, a group represented by the following general formula (AA) In this case, no sulfonium compound is produced even when the method for producing a sulfonium compound of the present invention is applied. This is presumably because the solubility of the sulfonium compound in alcohol and acetonitrile is high, and the equilibrium of the reaction does not shift to the formation of the sulfonium compound.
Here, in the general formula (AA), R ¹⁵ represents any of an alkyl group, an alkoxyl group, and a phenylamino group.

<< Compound Represented by Formula (2) >>
In the general formula (2), R ³ represents an α-naphthylmethyl group in which the hydrogen atom of the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the aromatic ring has 1 to carbon atoms. A cinnamyl group optionally substituted with an alkyl group of 4, a group represented by the following general formula (B), a group represented by the following general formula (C), and a group represented by the following general formula (D) Represents either. Z represents a halogen atom.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
One of the alkyl groups having 1 to 4 carbon atoms may be substituted on the aromatic ring, or a plurality of them may be substituted.
In the general formula (B), R ⁶ represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group.

As said C1-C4 alkyl group in said R < ⁶ >, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group etc. are mentioned, for example.
Examples of the alkoxy group having 1 to 4 carbon atoms in R ⁶ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
In the general formula (C), R ⁷ represents any one of a hydrogen atom, a methyl group, and a phenyl group.
When R ⁷ is a hydrogen atom, the group represented by the general formula (C) is an allyl group.
In the general formula (D), R ⁸ represents any of an alkyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
When R ⁸ is a methyl group, the group represented by the general formula (D) is a methallyl group.
When R ⁸ is an ethoxycarbonyl group, the group represented by the general formula (D) is a 2-ethoxycarbonylpropenyl group.

As said alkyl group in said R < ⁸ >, a C1-C4 alkyl group etc. are mentioned, for example. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
Examples of the alkoxycarbonyl group in R ⁸ include the alkoxycarbonyl group having 2 to 5 carbon atoms.
Examples of the aryloxycarbonyl group for R ⁸ include a phenoxycarbonyl group and a naphthyloxycarbonyl group.

  Examples of the halogen atom in Z include F (fluorine atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom), and the like.

<< Compound Represented by Formula (3) >>
In the general formula (3), X ⁺ represents any of Li ⁺ , Na ⁺ , and K ⁺ . Y ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , PF ₃ (C ₂ F ₅ ) ₃ ⁻ , C ₃ F ₆ NO ₄ S ₂ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , and C (CF ₃ SO ₂ ) ₃ ^— .

X ⁺ is preferably K ⁺ or Na ^{+ in} that the compound represented by the general formula (3) can be used as a cheaper raw material.

In order to allow the cationic curing component to be polymerized at a lower temperature, the Y ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ⁻ , PF ₃ (C ₂ F ₅ ) ₃ ⁻ , C (CF ₃ SO ₂ ) ₃ ⁻ is preferable, and B (C ₆ F ₅ ) ₄ ⁻ and SbF ₆ ^— are more preferable.
Further, from the viewpoint of the crystallinity of the salt can be easily obtained, wherein Y ^{- _{is, B (C 6 F 5)}} 4 -, SbF 6 -, PF 6 -, PF 3 (C 2 F 5) 3 -, C (CF ₃ SO _{2) 3} ^- is preferably.

<< Compound Represented by General Formula (4) >>
In the general formula (4), R ¹ is the same as R ¹ in the general formula (1). R ² is the same as R ² in the general formula (1). R ³ is the same as R ³ in the general formula (2). Y ⁻ is the same as Y ⁻ in the general formula (3).

<< Mixed >>
A mixing ratio when the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) are mixed in the solvent. There is no restriction | limiting in particular, According to the objective, it can select suitably.
As the mixing ratio, the compound represented by the general formula (2) is preferably 0.8 mol to 3.0 mol with respect to 1 mol of the compound represented by the general formula (1), 0.8 Mole to 1.5 mol is more preferable. When the mixing ratio of the compound represented by the general formula (2) is less than 0.8 mol with respect to 1 mol of the compound represented by the general formula (1), the progress of the reaction is reduced and the yield is reduced. The rate may decrease, and if it exceeds 3.0 moles, the raw material is excessive, resulting in an increase in cost and extra time for purification of unreacted materials.
As the mixing ratio, the compound represented by the general formula (3) is preferably 0.8 mol to 1.5 mol with respect to 1 mol of the compound represented by the general formula (1). Mole to 1.2 mol is more preferable. When the mixing ratio of the compound represented by the general formula (3) is less than 0.8 mol with respect to 1 mol of the compound represented by the general formula (1), the progress of the reaction is reduced and the yield is reduced. The rate may decrease, and if it exceeds 1.5 moles, the raw material is excessive and waste is generated, and the unreacted product may be further refined.

<< solvent >>
There is no restriction | limiting in particular as said solvent if it is at least any one of water, alcohol, and acetonitrile, According to the objective, it can select suitably.
However, when the solvent contains water as a main component, the sum total of Hammett's substituent constants of the substituent in R ² is 0.30 or less. When the solvent does not contain water as a main component, R ² is a group represented by the general formula (A).

  Examples of the alcohol include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and the like.

  There is no restriction | limiting in particular as the quantity of the said solvent in the system at the time of performing said reaction, Although it can select suitably according to the objective, 30 mass%-95 mass% are preferable.

  When the solvent contains water as a main component, alcohol may be used in combination. In this case, the proportion of the alcohol is preferably 0% by mass to 50% by mass and more preferably 0% by mass to 20% by mass with respect to water.

  When the solvent does not contain water as a main component, the solvent preferably does not contain water. For example, when the solvent is alcohol or acetonitrile, the solvent is preferably alcohol alone or acetonitrile alone.

<< Reaction >>
There is no restriction | limiting in particular as reaction temperature in the said reaction, Although it can select suitably according to the objective, 60 degrees C or less is preferable and 10 to 45 degreeC is more preferable. When the reaction temperature is less than 10 ° C., the progress of the reaction may be slow, and when it exceeds 45 ° C., dissociation may proceed simultaneously with the reaction, and the yield may not be sufficiently increased.

  There is no restriction | limiting in particular as reaction time in the said reaction, Although it can select suitably according to the objective, 2 hours-48 hours are preferable, and 5 hours-24 hours are more preferable.

  In the reaction, a reaction catalyst, an acid (eg, sulfuric acid, hydrochloric acid, etc.), a base (eg, caustic soda, caustic potash, sodium carbonate, etc.), a silver salt (eg, silver carbonate, silver nitrate, etc.), etc. May coexist.

Below, an example of the compound represented by the said General formula (4) is shown.
The following example is an example of a sulfonium compound in which the sum of Hammett's substituent constants of the substituent in R ² is 0.30 or less.

The following example is an example of a sulfonium compound in which R ² is a group represented by the general formula (A).

<Method for producing ammonium compound (B)>
In the method for producing an ammonium compound of one embodiment of the method for producing an onium compound of the present invention, in water, a compound represented by the following general formula (11), a compound represented by the above general formula (2), The compound represented by the general formula (3) is mixed and reacted to obtain an ammonium compound represented by the following general formula (14).
However, in said general formula (11) and general formula (14), R < ¹¹ > and R < ¹² > represent a C1-C4 alkyl group each independently.
In General Formula (11) and General Formula (14), R ¹³ represents a phenyl group having 0 to 5 substituents, and the sum of Hammett's substituent constants of the substituents in R ¹³ is 0. 60 or less.
In the general formula (14), R ³ represents an α-naphthylmethyl group in which the hydrogen atom of the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the aromatic ring has 1 to carbon atoms. A cinnamyl group optionally substituted with an alkyl group of 4, a group represented by the general formula (B), a group represented by the general formula (C), and a group represented by the general formula (D) Represents either.
In the general formula (14), Y ^{- _{is, B (C 6 F 5)}} 4 -, SbF 6 -, AsF 6 -, PF 6 -, BF 4 -, PF 3 (C 2 F 5) 3 -, C ^{_{3 F 6 NO 4 S 2 -}} , (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.

As described above, the inventors of the present invention have sought to synthesize a specific sulfonium compound that can be used as a cationic curing catalyst without requiring isolation and purification of an intermediate (sulfonium halide) during the reaction. I found it.
The present inventors have further studied and found that a specific ammonium compound that can be used as a cationic curing catalyst can be synthesized without requiring isolation and purification of an intermediate (ammonium halide) during the reaction.

<< Compound Represented by Formula (11) >>
However, in said general formula (11), R < ¹¹ > and R < ¹² > represent a C1-C4 alkyl group each independently.
In the general formula (11), R ¹³ represents a phenyl group having 0 to 5 substituents, and the sum of Hammett's substituent constants of the substituents in R ¹³ is 0.60 or less.
When the sum of Hammett's substituent constants of the substituent in R ¹³ exceeds 0.60, it is difficult to produce an ammonium compound. This is thought to be due to a decrease in reactivity due to a decrease in nucleophilicity of the nitrogen atoms bonded to R ¹¹ , R ¹² , and R ¹³ and a decrease in the stability of the target product.

<<< R ¹¹ and R ¹² >>>
Examples of R ¹¹ and R ¹² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

<<< R ¹³ >>>
In R ¹³ , examples of the substituent that is a target for calculating the Hammett's substituent constant include a substituent having 1 to 10 carbon atoms and the substituents described in Table 1 above.
The total of Hammett's substituent constants of the substituent in R ¹³ is preferably −0.30 to 0.55, and preferably −0.20 to 0.005 in terms of obtaining an ammonium compound having an appropriate thermosetting property. 50 is more preferable.

<< Compound Represented by Formula (14) >>
In the general formula (14), R ¹¹ is the same as R ¹¹ in the general formula (11). R ¹² is the same as R ¹² in the general formula (11). R ¹³ is the same as R ¹³ in the general formula (11). R ³ is the same as R ³ in the general formula (2). Y ⁻ is the same as Y ⁻ in the general formula (3).

<< Mixed >>
As a mixing ratio when the compound represented by the general formula (11), the compound represented by the general formula (2), and the compound represented by the general formula (3) are mixed in the water. There is no restriction | limiting in particular, According to the objective, it can select suitably.
As the mixing ratio, the compound represented by the general formula (2) is preferably 0.8 mol to 3.0 mol with respect to 1 mol of the compound represented by the general formula (11). Mole to 1.5 mol is more preferable. When the mixing ratio of the compound represented by the general formula (2) is less than 0.8 mol with respect to 1 mol of the compound represented by the general formula (11), the progress of the reaction is reduced and the yield is reduced. The rate may decrease, and if it exceeds 3.0 moles, the raw material is excessive, resulting in an increase in cost and extra time for purification of unreacted materials.
As the mixing ratio, the compound represented by the general formula (3) is preferably 0.8 mol to 1.5 mol with respect to 1 mol of the compound represented by the general formula (11). Mole to 1.2 mol is more preferable. When the mixing ratio of the compound represented by the general formula (3) is less than 0.8 mol with respect to 1 mol of the compound represented by the general formula (11), the progress of the reaction is reduced and the yield is reduced. The rate may decrease, and if it exceeds 1.5 moles, the raw material is excessive and waste is generated, and the unreacted product may be further refined.

<< Water >>
The reaction system may contain a solvent other than water. Examples of such a solvent include alcohol and acetonitrile.

  Examples of the alcohol include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and the like.

  There is no restriction | limiting in particular as the quantity of the said solvent in the system at the time of performing said reaction, Although it can select suitably according to the objective, 30 mass%-95 mass% are preferable.

  There is no restriction | limiting in particular as the quantity of the water in the said solvent, Although it can select suitably according to the objective, 50 mass%-100 mass% are preferable, and 70 mass%-99 mass% are more preferable.

  When water and alcohol are used in combination as the solvent, the proportion of the alcohol is preferably 0% by mass to 50% by mass and more preferably 0% by mass to 20% by mass with respect to water.

<< Reaction >>
There is no restriction | limiting in particular as reaction temperature in the said reaction, Although it can select suitably according to the objective, 60 degrees C or less is preferable and 10 to 45 degreeC is more preferable. When the reaction temperature is less than 10 ° C., the progress of the reaction may be slow, and when it exceeds 45 ° C., dissociation may proceed simultaneously with the reaction, and the yield may not be sufficiently increased.

  There is no restriction | limiting in particular as reaction time in the said reaction, Although it can select suitably according to the objective, 2 hours-48 hours are preferable, and 5 hours-24 hours are more preferable.

  In the reaction, a reaction catalyst, an acid (eg, sulfuric acid, hydrochloric acid, etc.), a base (eg, caustic soda, caustic potash, sodium carbonate, etc.), a silver salt (eg, silver carbonate, silver nitrate, etc.), etc. May coexist.

<Method for producing phosphonium compound (C)>
In the method for producing a phosphonium compound of one embodiment of the method for producing an onium compound of the present invention, in water, a compound represented by the following general formula (21), a compound represented by the above general formula (2), The compound represented by the general formula (3) is mixed and reacted to obtain an ammonium compound represented by the following general formula (24).
However, in said general formula (21) and general formula (24), R <^21> , R < ²² > and R < ²³ > represent the phenyl group which has 0-5 substituents each independently. The sum total of Hammett's substituent constants of the substituent in R ²¹ is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²² is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²³ is 0.70 or less.
In the general formula (24), R ³ represents an α-naphthylmethyl group in which the hydrogen atom of the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the aromatic ring represents 1 to carbon atoms. A cinnamyl group optionally substituted with an alkyl group of 4, a group represented by the general formula (B), a group represented by the general formula (C), and a group represented by the general formula (D) Represents either.
In the general formula (24), Y ^{- _{is, B (C 6 F 5)}} 4 -, SbF 6 -, AsF 6 -, PF 6 -, BF 4 -, PF 3 (C 2 F 5) 3 -, C ^{_{3 F 6 NO 4 S 2 -}} , (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.

As described above, as a result of intensive studies, the present inventors have found that a specific sulfonium compound that can be used as a cationic curing catalyst without requiring isolation and purification of an intermediate (sulfonium halide, ammonium halide) during the reaction, It has been found that a specific ammonium compound can be synthesized.
The present inventors have further studied and found that a specific phosphonium compound that can be used as a cationic curing catalyst can be synthesized without requiring isolation and purification of an intermediate (phosphonium halide) during the reaction.

<< Compound Represented by Formula (21) >>
However, in said general formula (21), R <^21> , R < ²² > and R < ²³ > represent the phenyl group which has 0-5 substituents each independently. The sum total of Hammett's substituent constants of the substituent in R ²¹ is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²² is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²³ is 0.70 or less.
Any of the sum of Hammett's substituent constants of the substituent in R ^21, the sum of Hammett's substituent constants of the substituent in R ²² , and the sum of Hammett's substituent constants of the substituent in R ²³ When it exceeds 0.70, it becomes difficult to produce the phosphonium compound. This is thought to be due to a decrease in reactivity due to a decrease in the nucleophilicity of the phosphorus atom bonded to R ²¹ , R ²² , and R ²³ , and a decrease in the stability of the target product.

<<< R ²¹ , R ²² , and R ²³ >>>
In R ²¹ , R ²² , and R ²³ , examples of the substituent that is the target of calculation of the Hammett's substituent constant include a substituent having 1 to 10 carbon atoms, and the substituent described in Table 1 above. Is mentioned.
In each of R ²¹ , R ²² , and R ²³ , the sum of the Hammett's substituent constants of the substituent is −0.10 to 0.60 in that a phosphonium compound having appropriate thermosetting properties can be obtained. Is preferable, and -0.10 to 0.55 is more preferable.

<< Compound Represented by Formula (24) >>
In the general formula (24), R ²¹ is the same as R ²¹ in the general formula (21). R ²² is the same as R ²² in the general formula (21). R ²³ is the same as R ²³ in the general formula (21). R ³ is the same as R ³ in the general formula (2). Y ⁻ is the same as Y ⁻ in the general formula (3).

<< Mixed >>
As a mixing ratio when the compound represented by the general formula (21), the compound represented by the general formula (2), and the compound represented by the general formula (3) are mixed in the water. There is no restriction | limiting in particular, According to the objective, it can select suitably.
As the mixing ratio, the compound represented by the general formula (2) is preferably 0.8 mol to 3.0 mol with respect to 1 mol of the compound represented by the general formula (21). Mole to 1.5 mol is more preferable. When the mixing ratio of the compound represented by the general formula (2) is less than 0.8 mol with respect to 1 mol of the compound represented by the general formula (21), the progress of the reaction is lowered and the yield is reduced. The rate may decrease, and if it exceeds 3.0 moles, the raw material is excessive, resulting in an increase in cost and extra time for purification of unreacted materials.
As the mixing ratio, the compound represented by the general formula (3) is preferably 0.8 mol to 1.5 mol with respect to 1 mol of the compound represented by the general formula (21). Mole to 1.2 mol is more preferable. When the mixing ratio of the compound represented by the general formula (3) is less than 0.8 mol with respect to 1 mol of the compound represented by the general formula (21), the progress of the reaction is reduced and the yield is reduced. The rate may decrease, and if it exceeds 1.5 moles, the raw material is excessive and waste is generated, and the unreacted product may be further refined.

<< Water >>
The reaction system may contain a solvent other than water. Examples of such a solvent include alcohol and acetonitrile.

  Examples of the alcohol include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and the like.

  There is no restriction | limiting in particular as the quantity of the said solvent in the system at the time of performing said reaction, Although it can select suitably according to the objective, 30 mass%-95 mass% are preferable.

  There is no restriction | limiting in particular as the quantity of the water in the said solvent, Although it can select suitably according to the objective, 50 mass%-100 mass% are preferable, and 70 mass%-99 mass% are more preferable.

  When water and alcohol are used in combination as the solvent, the proportion of the alcohol is preferably 0% by mass to 50% by mass and more preferably 0% by mass to 20% by mass with respect to water.

<< Reaction >>
There is no restriction | limiting in particular as reaction temperature in the said reaction, Although it can select suitably according to the objective, 60 degrees C or less is preferable and 10 to 45 degreeC is more preferable. When the reaction temperature is less than 10 ° C., the progress of the reaction may be slow, and when it exceeds 45 ° C., dissociation may proceed simultaneously with the reaction, and the yield may not be sufficiently increased.

  There is no restriction | limiting in particular as reaction time in the said reaction, Although it can select suitably according to the objective, 2 hours-48 hours are preferable, and 5 hours-24 hours are more preferable.

  In the reaction, a reaction catalyst, an acid (eg, sulfuric acid, hydrochloric acid, etc.), a base (eg, caustic soda, caustic potash, sodium carbonate, etc.), a silver salt (eg, silver carbonate, silver nitrate, etc.), etc. May coexist.

(Method for producing curable resin composition)
The manufacturing method of the curable resin composition of this invention includes the manufacturing method of the said onium compound of this invention, and also includes another process as needed.

The curable resin composition contains at least an onium compound, preferably contains a cationic curing component and a film-forming resin, and further contains other components as necessary.
The said onium compound is obtained by the manufacturing method of the said onium compound of this invention.
The curable resin composition is obtained, for example, by mixing the onium compound, preferably a cationic curable component, and a film-forming resin.

<Cationic curing component>
The cationic curing component is not particularly limited as long as it is a component that is cured by the action of the onium compound as a cationic curing agent, and can be appropriately selected according to the purpose. For example, an epoxy compound, a vinyl ether compound, Examples include oxetane compounds and cyclic ether compounds. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the epoxy compound include bisphenol type epoxy resin, polyglycidyl ether, polyglycidyl ester, aromatic epoxy compound, alicyclic epoxy compound, novolac type epoxy compound, glycidylamine type epoxy compound, glycidyl ester type epoxy compound, biphenyl. Examples thereof include diglycidyl ether, triglycidyl isocyanurate, polyglycidyl methacrylate, and a copolymer of glycidyl methacrylate and a vinyl monomer copolymerizable with the glycidyl methacrylate.

  Examples of the alicyclic epoxy compound include a cyclohexene oxide-containing compound and a cyclopentene oxide-containing compound.

  Examples of the vinyl ether compound include alkyl vinyl ether compounds, alkenyl vinyl ether compounds, alkynyl vinyl ether compounds, and aryl vinyl ether compounds.

  Examples of the oxetane compound include oxetane alcohols, aliphatic oxetane compounds, and aromatic oxetane compounds.

  There is no restriction | limiting in particular as content of the said cationic hardening component in the said curable resin composition, Although it can select suitably according to the objective, 10 mass% with respect to the non volatile matter of the said curable resin composition -98 mass% is preferable, and 20 mass% -90 mass% is more preferable.

<Onium compound>
The said onium compound is an onium compound manufactured by the manufacturing method of the said onium compound of this invention.
Examples of the onium compounds include sulfonium compounds, ammonium compounds, and phosphonium compounds.
The said sulfonium compound is a sulfonium compound manufactured by the manufacturing method of the said sulfonium compound of this invention.
The said ammonium compound is an ammonium compound manufactured by the manufacturing method of the said ammonium compound of this invention.
The phosphonium compound is a phosphonium compound produced by the method for producing a phosphonium compound of the present invention.

  There is no restriction | limiting in particular as content of the said onium compound in the said curable resin composition, Although it can select suitably according to the objective, 0.5 mass with respect to the non volatile matter of the said curable resin composition % To 20% by mass is preferable, and 2% to 15% by mass is more preferable.

<Film forming resin>
The film-forming resin is not particularly limited and can be appropriately selected depending on the purpose. For example, polyacrylic resin, phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, polyvinyl butyral resin, polyvinyl formal resin, Examples thereof include polyamide resin and polyimide resin. These may be used individually by 1 type and may use 2 or more types together. Among these, a phenoxy resin is particularly preferable from the viewpoint of film formability and processability.

Examples of the phenoxy resin include those obtained by reacting a bifunctional phenol with epichlorohydrin to increase the molecular weight, or a resin obtained by polyaddition of a bifunctional epoxy resin and a bifunctional phenol.
Examples of the bifunctional epoxy resin used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, and methyl-substituted biphenyl diglycidyl ether. It is done.
Examples of the bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluorene, methyl-substituted bisphenol fluorene, bisphenols such as dihydroxybiphenyl and methyl-substituted dihydroxybiphenyl.

  There is no restriction | limiting in particular as content of the said film formation resin in the said curable resin composition, Although it can select suitably according to the objective, 10 mass% with respect to the non volatile matter of the said curable resin composition -90 mass% is preferable, 20 mass%-80 mass% is more preferable, 30 mass%-60 mass% is especially preferable.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents, fillers, leveling agents, antioxidants, colorants, conductivity-imparting agents, and adhesion-imparting agents. Is mentioned.

  The curable resin composition can be suitably used, for example, as a thermosetting resin composition that is cured by heat or a photocurable resin composition that is cured by light.

(Curable sheet)
The said curable sheet regarding this invention contains the said curable resin composition of this invention, and also contains another component as needed.

The curable sheet is formed, for example, by forming a curable adhesive layer made of the curable resin composition on a base film (peeling base). Examples of the base film include a polyethylene terephthalate film and a polyimide film.
The said curable sheet consists of the said curable resin composition to the base film which carried out the peeling process with the silicone etc. as needed to the polyethylene terephthalate film, the polyimide film, etc. from viewpoints, such as storage property and handling property at the time of use. The curable adhesive layer is preferably formed with an average thickness of 5 μm to 50 μm.

  The curable resin composition and the curable sheet can be preferably applied to the field of electronic components. In particular, the curable sheet is used for bonding and fixing a terminal portion of a flexible printed wiring board and a reinforcing sheet having a thickness of 50 μm to 2 mm such as polyethylene terephthalate, polyimide, glass epoxy, stainless steel, and aluminum for backing the flexible printed wiring board. Reinforced flexible print in which the terminal portion of the flexible printed wiring board and the reinforcing sheet are bonded and fixed with a cured product of a curable adhesive layer excluding the base film of the curable sheet. A wiring board is obtained.

When using the said curable sheet as an adhesive sheet, it is preferable that the composition contains a thermoplastic resin. As the thermoplastic resin used, the polyacryl resin, phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyimide resin described in the section of <Film-forming resin> And epoxy resin. Among these, as described above, the phenoxy resin is preferably contained from the viewpoints of film formability, compatibility, and heat resistance.
When used as an adhesive sheet for bonding metals, it is preferable that a silane coupling agent is contained in the composition. There is no restriction | limiting in particular as a kind of silane coupling agent, According to the objective, it can select suitably, For example, an epoxy-type silane coupling agent, an acrylic-type silane coupling agent, a thiol-type silane coupling agent, an amine-type silane A coupling agent etc. are mentioned.
When used as an adhesive sheet that imparts conductivity, it is preferable to contain conductive particles in the composition. The type of the conductive particles is not particularly limited and can be appropriately selected according to the purpose. For example, metal particles such as gold, silver, copper, tin, and nickel, metal particles, or inorganic particles such as silica are subjected to metal plating or Examples thereof include particles coated with metal by vapor deposition and the like, and particles coated with metal by metal plating or vapor deposition on resin particles. The shape of the particle is not particularly limited, and examples thereof include a spherical shape, a needle shape, an irregular shape, and a shape having fine protrusions.

  The curable sheet can be suitably used as, for example, a thermosetting sheet that is cured by heat or a photocurable sheet that is cured by light.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
<Synthesis of Compound (B)>
A 100 mL three-necked flask containing 6 g (42.8 mmol) of 4-methylthiophenol manufactured by Tokyo Chemical Industry Co., Ltd., 20 mL of acetonitrile and 7.09 g (51.4 mmol) of potassium carbonate was stirred at 70 ° C. for 30 minutes, and then Tokyo Chemical Industry Co., Ltd. 6.91 g (51.4 mmol) of 1-chloropinacholine manufactured by the company was added dropwise. The mixture was stirred at 70 ° C. for 6 hours to remove the salt, washed with water and extracted, and the solvent was distilled off to obtain 9.12 g (yield 89%) of the compound (B) represented by the following structural formula. .

(Synthesis Example 2)
<Synthesis of Compound (C)>
Synthesis was performed in the same manner as in Synthesis Example 1 except that 1-chloropinacholine was changed to 4.76 g (51.4 mmol) of chloroacetone manufactured by Tokyo Chemical Industry Co., Ltd., and represented by the following structural formula. Compound (C) 7.36g (yield 87.6%) was obtained.

(Synthesis Example 3)
<Synthesis of Compound (D)>
Synthesis was performed in the same manner as in Synthesis Example 1 except that 1-chloropinacholine was changed to 7.95 g (51.4 mmol) of phenacyl chloride manufactured by Tokyo Chemical Industry Co., Ltd., and represented by the following structural formula. Compound (D) (9.12 g, yield 82.5%) was obtained.

(Synthesis Example 4)
<Synthesis of Compound (E)>
Synthesis was performed in the same manner as in Synthesis Example 1 except that 1-chloropinacholine was changed to 4.76 g (51.4 mmol) of methyl chloroacetate manufactured by Tokyo Chemical Industry Co., Ltd., and represented by the following structural formula. 7.57 g (yield 90.1%) of the compound (E) was obtained.

(Synthesis Example 5)
<Synthesis of Compound (F)>
4 g (28.5 mmol) of 4-methylthiophenol and 8 g (78.4 mmol) of acetic anhydride were placed in a 100 ml three-necked flask, a small amount of concentrated sulfuric acid was added in a nitrogen gas atmosphere, and the mixture was stirred and reacted at room temperature for 3 hours. Thereafter, 40 g of a saturated aqueous sodium hydrogen carbonate solution and 20 g of ethyl acetate are added. After stirring, the mixture is transferred to a separatory funnel, the oil phase is taken out, and the oil phase is further washed with water. Yielded 5.091 g of light yellow liquid compound (F) (yield 97.9%).

(Synthesis Example 6)
<Synthesis of Compound (G)>
Place 1.5 g (10.7 mmol) of 4-methylthiophenol and 20 g of acetonitrile in a 100 ml three-necked flask, cool to 10 ° C., add 1.137 g (11.2 mmol) of triethylamine, and stir for 10 minutes. However, 1.220 g (11.2 mmol) of ethyl chloroformate manufactured by Tokyo Chemical Industry Co., Ltd. was added dropwise over 10 minutes. Then, after reacting for 4 hours, the triethylamine hydrochloride precipitated by filtration was removed, the solvent was distilled off, and the residue was washed with water and dried under reduced pressure to obtain 2.04 g of the compound (G) represented by the following structural formula. Obtained (yield 89.7%).

(Synthesis Example 7)
<Synthesis of Compound (H)>
4-methylthiophenol 5.0 g (35.7 mmol), toluene 30 g, and triethylamine 0.05 g were put into a nitrogen-substituted 100 ml three-necked flask, and 5.098 g of phenyl isocyanate (Tokyo Kasei Kogyo Co., Ltd.) at 60 ° C. in a nitrogen atmosphere. 42.8 mmol) was added dropwise over 30 minutes while paying attention to heat generation. The mixture was then stirred and reacted for 60 minutes, allowed to cool, filtered, washed with toluene, and dried under reduced pressure to obtain 7.59 g of compound (H) represented by the following structural formula (yield 82 .1%).

Example 1
<Synthesis of sulfonium compound 1>
A 50 ml three-necked flask was charged with 1.000 g of the compound (A) represented by the following structural formula, 1.260 g of 1-naphthylmethyl chloride, 4.656 g of tetrakis (pentafluorophenyl) borate potassium salt, and 2.00 g of ethanol. The mixture was stirred and reacted for 24 hours. After completion of the reaction, 10 g of ethyl acetate was added, followed by stirring for a while, and then KCl precipitated by filtration was removed, and the filtrate was recovered. Since the crude crystals were obtained by distilling off the solvent from the filtrate, the crude crystals were washed with pure water, dried under reduced pressure, and recrystallized with ethanol / hexane to yield white crystals of sulfonium compound (1). Obtained at 82.3%.

The structure of the obtained sulfonium compound (1) was confirmed by LC / MS. As a result, it was confirmed that the obtained sulfonium compound (1) had a structure described later.
In addition, also in the following Examples 2-17 and Comparative Examples 1-7, the method of structure confirmation is the same.

(Examples 2 to 17)
In the same manner as in Example 1, the following sulfonium compounds (2) to (11) were synthesized. The structures of raw materials used in the synthesis, the amounts charged, the solvents used, and the yields are shown in Tables 2 to 3 below.

(Comparative Example 1)
<Synthesis of sulfonium compound 12>
4-methylcarbonyloxy-phenylmethyl sulfide 1.000 g, benzyl chloride 0.903 g, tetrakis (pentafluorophenyl) borate potassium 4.656 g, and ethanol 2.00 g were charged into a 50 ml three-necked flask and stirred at 25 ° C. for 24 hours. Went. After completion of the reaction, 10 g of ethyl acetate was added, followed by stirring for a while, and then KCl precipitated by filtration was removed, and the filtrate was recovered. Although the solvent was distilled off from the filtrate, crystals did not precipitate and became a yellow viscous liquid. When this viscous liquid was analyzed by LC / MS, the target sulfonium compound (12) was hardly produced.

(Comparative Examples 2 to 5)
In the same manner as in Comparative Example 1, the synthesis of sulfonium compounds (13) to (15) was attempted. The structure of raw materials used in the synthesis, the amount charged, the solvent used, and the yield are shown in Table 4 below.
When analyzed by LC / MS, the target sulfonium compounds (13) to (15) were hardly formed.
The sulfonium compound to be synthesized in Comparative Examples 1 to 4 is a similar compound described in JP-A-3-47164. The sulfonium compound to be synthesized in Comparative Example 5 is a compound described in JP2011-231243A.

The structures of the sulfonium compounds (12) to (15) to be synthesized in Comparative Examples 1 to 5 are as follows.

(Comparative Example 6)
<Synthesis of sulfonium compound (4)>
4- (3,3dimethyl-2-oxobutoxy) phenylmethylsulfide 1.000 g, 1-naphthylmethyl chloride 0.815 g and methanol 2 g were charged into a 50 ml three-necked flask and stirred and reacted at 25 ° C. for 24 hours. After the reaction, the solvent was distilled off to obtain a yellow viscous liquid. When this viscous product was analyzed by LC / MS, a sulfonium compound (sulfonium chloride) was hardly formed, and hence anion exchange to tetrakis (pentafluorophenyl) borate was not possible.

(Comparative Example 7)
<Synthesis of sulfonium compound (4)>
4- (3,3 dimethyl-2-oxobutoxy) phenylmethylsulfide 1.000 g, 1-naphthylmethyl chloride 0.815 g and water 10 g were charged into a 50 ml three-necked flask and stirred and reacted at 25 ° C. for 24 hours. After completion of the reaction, 10 g of ethyl acetate and 2.946 g of tetrakis (pentafluorophenyl) borate sodium were added to the reaction solution, and the mixture was stirred for 15 minutes. Thereafter, the ethyl acetate phase was recovered and the solvent was distilled off to recover a yellow viscous liquid. When this viscous product was analyzed by LC / MS, the sulfonium compound (4) was hardly formed.

In Tables 2 to 4, compounds (A) to (H) have the following structures.

The suppliers of the raw materials used in the examples and comparative examples are as follows.
Compound A is manufactured by Tokyo Chemical Industry Co., Ltd.
1-naphthylmethyl chloride is manufactured by Tokyo Chemical Industry Co., Ltd.
o-Methylbenzyl chloride is manufactured by Tokyo Chemical Industry Co., Ltd.
Cinnamilk chloride is manufactured by Tokyo Chemical Industry Co., Ltd.
1-naphthylmethyl bromide is manufactured by Alfa Aesar.
Benzyl chloride is manufactured by Tokyo Chemical Industry Co., Ltd.
Tetrakis (pentafluorophenyl) borate potassium is manufactured by Tosoh Finechem.
Tris (trifluoromethanesulfonyl) methide potassium is manufactured by Central Glass.
Tetrakis (pentafluorophenyl) borate sodium is manufactured by Nippon Shokubai Co., Ltd.
Tetrakis (pentafluorophenyl) borate lithium is manufactured by Tosoh Finechem.
Sodium hexafluoroantimonate is manufactured by Alfa Aesar.

(Example 18)
To 2.35 g (16.8 mmol) of 4- (methylthio) phenol, 2.96 g (16.8 mmol) of chloromethylnaphthalene (1-naphthylmethyl chloride), sodium tetrakis (pentafluorophenyl) borate (tetrakis (pentafluoro) 117.8 g (16.8 mmol) of a 10% by mass aqueous solution of (phenyl) borate sodium) (manufactured by Nippon Shokubai) was added and stirred at room temperature for 24 hours. After filtration, washing with water, and drying, washing with hexane and drying again were performed to obtain the target sulfonium compound. The yield was 90%.
The solvent used is only water. The sum total of Hammett's substituent constants of the substituent in R ² is −0.37.

The structure of the obtained sulfonium compound is as follows. The structure was confirmed by LC / MS.
In Examples 19 to 22 and Comparative Examples 8 to 12, the structure confirmation method is the same.

(Example 19)
To 2.35 g (16.8 mmol) of 4- (methylthio) phenol, 117.8 g (16.8 mmol) of a 10% by mass aqueous solution of tetrakis (pentafluorophenyl) borate sodium salt (manufactured by Nippon Shokubai Co., Ltd.) was added at room temperature. Stir. A solution prepared by dissolving 2.96 g (16.8 mmol) of chloromethylnaphthalene (1-naphthylmethyl chloride) with 10 g of ethanol was added dropwise thereto and stirred at room temperature for 24 hours. After filtration, washing with water, and drying, washing with hexane and drying again were performed to obtain the target sulfonium compound. The yield was 91%.
The solvent used was water: ethanol = 10: 1 (mass ratio). The sum total of Hammett's substituent constants of the substituent in R ² is −0.37.

The structure of the obtained sulfonium compound is as follows.

(Example 20)
A sulfonium compound was synthesized in the same manner as in Example 19 except that 4- (methylthio) phenol was changed to 2.59 g (16.8 mmol) of 4-methoxythioanisole [the compound (A)] in Example 19. did. The yield was 93%.
The solvent used was water: ethanol = 10: 1 (mass ratio). The sum total of Hammett's substituent constants of the substituent in R ² is −0.27.

The structure of the obtained sulfonium compound is as follows.

(Example 21)
In Example 19, 4- (methylthio) phenol was converted to 3,3-dimethyl-1- [4- (methylsulfanyl) phenoxy] butan-2-one [the compound (B)] (4.00 g, 16.8 mmol). A sulfonium compound was synthesized in the same manner as in Example 19 except for changing. The yield was 92%.
The solvent used was water: ethanol = 10: 1 (mass ratio). The sum total of Hammett's substituent constants of the substituents in R ² is 0.14.

The structure of the obtained sulfonium compound is as follows.

(Example 22)
A sulfonium compound was synthesized in the same manner as in Example 19 except that 4- (methylthio) phenol was changed to 2.08 g (16.8 mmol) of thioanisole in Example 19. The yield was 93%.
The solvent used was water: ethanol = 10: 1 (mass ratio). The sum of Hammett's substituent constants of the substituent in R ² is 0.

The structure of the obtained sulfonium compound is as follows.

(Comparative Example 8)
In Example 18, the synthesis was carried out without using the borate salt, and the isolation was carried out as a chloride. The yield of chloride was 70%. Then, the target sulfonium compound was obtained by making into borate salt by salt exchange. The yield was 56%.
The solvent used was water: ethanol = 10: 1 (mass ratio). The sum total of Hammett's substituent constants of the substituent in R ² is −0.37.

(Comparative Example 9)
In Example 20, the synthesis was performed without using the borate salt. However, no chloride was obtained, and the desired sulfonium compound was not obtained.

(Comparative Example 10)
In Example 21, the synthesis was performed without using the borate salt. However, no chloride was obtained, and the desired sulfonium compound was not obtained.

(Comparative Example 11)
In Example 22, the synthesis was performed without using the borate salt. However, no chloride was obtained, and the desired sulfonium compound was not obtained.

(Comparative Example 12)
Synthesis was performed in the same manner as in Example 18 except that 4- (methylthio) phenol was changed to 2.59 g (16.8 mmol) of 4- (methylsulfanyl) phenylacetate [the compound (F)]. Although it was carried out, the intended sulfonium compound was not obtained.
In addition, the structure of the target sulfonium compound is as follows, and the sum total of the Hammett substituent constants of the substituent in R ² is 0.31.

In addition, the purchase source of the raw material used in Examples 18-22 and Comparative Examples 8-12 is as follows except having mentioned above.
4- (Methylthio) phenol is manufactured by Tokyo Chemical Industry Co., Ltd.
Thioanisole is manufactured by Tokyo Chemical Industry Co., Ltd.

(Example 23)
<Synthesis of Compound (101)>
A 200 ml three-necked flask equipped with a stirrer and a thermometer was adjusted with a 10% by weight aqueous solution of tetrakis (pentafluorophenyl) borate (manufactured by Nippon Shokubai Co., Ltd.) so that the water: ethyl alcohol ratio was 10: 1. 128.6 g (16.8 mmol) of a 17% by mass solution, 2.35 g (16.8 mmol) of 4- (methylthio) phenol (manufactured by Tokyo Chemical Industry), and 4.09 g of 1-naphthylmethyl bromide (manufactured by Tokyo Chemical Industry) (18.5 mmol) was added and stirred at room temperature for 24 hours. After completion of the stirring, the precipitated crystals were removed by filtration, washed with pure water three times, water was removed by drying under reduced pressure, washed with hexane, and dried again under reduced pressure to give the following compound (101) ) The yield was 91%.

(Example 24)
<Synthesis of Compound (102)>
In Example 23, the following compound (102) was prepared in the same manner as in Example 23 except that 4- (methylthiophenol) was replaced with 2.59 g (16.8 mmol) of 4-methoxythioanisole (manufactured by Tokyo Chemical Industry). Obtained. The yield was 87%.

(Example 25)
<Synthesis of Compound (103)>
In Example 23, the following compound (103) was obtained in the same manner as in Example 23, except that 4- (methylthiophenol) was replaced with 2.09 g (16.8 mmol) of thioanisole (manufactured by Tokyo Chemical Industry). The yield was 89%.

(Example 26)
<Synthesis of Compound (104)>
In Example 23, the following compound (104) was prepared in the same manner as in Example 23, except that 4- (methylthiophenol) was replaced with 2.59 g (16.8 mmol) of 3-methoxythioanisole (manufactured by Tokyo Chemical Industry). Obtained. The yield was 82%.

(Example 27)
<Synthesis of Compound (102)>
In Example 24, a 9.17% by mass water: ethyl alcohol 10: 1 mass ratio solution of sodium tetrakis (pentafluorophenyl) borate was obtained by adding a solid content of lithium tetrakis (pentafluorophenyl) borate to 92% by mass (Tosoh Corporation). Compound (102) was obtained in the same manner as in Example 24 except that Finechem) was changed to 115.2 g (16.8 mmol) of a solution adjusted to 10% by mass with a 10: 1 mass ratio of water: ethanol. It was. The yield was 81%.

(Example 28)
<Synthesis of Compound (102)>
In Example 24, a solution of 9.17% by mass of water: ethyl alcohol in sodium tetrakis (pentafluorophenyl) borate in a 10: 1 mass ratio was prepared by adding potassium tetrakis (pentafluorophenyl) borate (Tosoh Finechem) to water: ethyl. Compound (102) was obtained in the same manner as in Example 24, except that 120.6 g (16.8 mmol) of the solution adjusted to 10% by mass with a 10: 2 mass ratio solution of alcohol was used. The yield was 78%.

(Example 29)
<Synthesis of Compound (105)>
The following compound (105) was obtained in the same manner as in Example 24 except that 1-naphthylmethyl bromide was changed to 2.34 g (18.5 mmol) of benzyl chloride (manufactured by Tokyo Chemical Industry) in Example 24. The yield was 82%.

(Example 30)
<Synthesis of Compound (106)>
In Example 24, except that 1-naphthylmethyl bromide was changed to 2.60 g (18.5 mmol) of o-methylbenzyl chloride (manufactured by Tokyo Chemical Industry), the following compound (106) was obtained in the same manner as in Example 24. It was. The yield was 75%.

(Example 31)
<Synthesis of Compound (107)>
In Example 24, a 10: 1 weight ratio solution of 9.17% by weight water: ethyl alcohol of sodium tetrakis (pentafluorophenyl) borate was added to 10% by weight water of tris (trifluoromethanesulfonyl) methide lithium (manufactured by Central Glass). The following compound (107) was obtained in the same manner as in Example 24 except that 70.3 g (16.8 mmol) of a 10: 1 mass ratio solution of ethyl alcohol was used. The yield was 71%.

(Example 32)
<Synthesis of Compound (108)>
In Example 24, a 10: 1 mass ratio solution of 9.17% by mass water: ethyl alcohol of sodium tetrakis (pentafluorophenyl) borate was added to 2.5% by mass of sodium hexafluorophosphate (manufactured by Tokyo Chemical Industry). The following compound (108) was obtained in the same manner as in Example 24 except that 112.9 g (16.8 mmol) of a 10: 1 mass ratio solution of ethyl alcohol was used. The yield was 73%.

(Example 33)
<Synthesis of Compound (109)>
In Example 23, the following compound was obtained in the same manner as in Example 23 except that 4- (methylthio) phenol was changed to 2.27 g (16.8 mmol) of N, N-dimethyl-p-toluidine (manufactured by Tokyo Chemical Industry). (109) was obtained. The yield was 87%.

(Example 34)
<Synthesis of Compound (110)>
In Example 23, except that 4- (methylthio) phenol was replaced with 2.04 g (16.8 mmol) of N, N-dimethylaniline (manufactured by Tokyo Chemical Industry), the following compound (110) was obtained in the same manner as in Example 23. Got. The yield was 82%.

(Example 35)
<Synthesis of Compound (111)>
In Example 23, the following compound (111) was prepared in the same manner as in Example 23, except that 4- (methylthio) phenol was changed to 3.25 g (16.8 mmol) of ethyl 4-dimethylaminobenzoate (manufactured by Tokyo Chemical Industry). ) The yield was 84%.

(Example 36)
<Synthesis of Compound (112)>
In Example 23, the following compound (112) was obtained in the same manner as in Example 23 except that 4- (methylthio) phenol was changed to 2.74 g (16.8 mmol) of 4′-dimethylaminoacetophenone (manufactured by Tokyo Chemical Industry). Got. The yield was 78%.

(Example 37)
<Synthesis of Compound (113)>
In Example 35, the following compound (113) was obtained in the same manner as in Example 35 except that 1-naphthylmethyl bromide was changed to 2.34 g (18.5 mmol) of benzyl chloride. The yield was 75%.

(Example 38)
<Synthesis of Compound (114)>
In Example 35, the following compound (114) was obtained in the same manner as in Example 35 except that 1-naphthylmethyl bromide was changed to 2.24 g (18.5 mmol) of allyl bromide (manufactured by Tokyo Chemical Industry). The yield was 75%.

(Example 39)
<Synthesis of Compound (115)>
In Example 35, the following compound (115) was obtained in the same manner as in Example 35 except that 1-naphthylmethyl bromide was changed to 2.50 g (18.5 mmol) of methallyl bromide (manufactured by Tokyo Chemical Industry). The yield was 87%.

(Example 40)
<Synthesis of Compound (116)>
In Example 35, the following compound (116) was prepared in the same manner as in Example 35 except that 1-naphthylmethyl bromide was replaced with 3.59 g (18.5 mmol) of ethyl 2- (bromomethyl) acrylate (manufactured by Tokyo Chemical Industry). ) The yield was 90%.

(Example 41)
<Synthesis of Compound (117)>
In Example 39, 9.17 wt% water: ethyl alcohol 10: 1 wt ratio solution of sodium tetrakis (pentafluorophenyl) borate was added 10 wt% water of tris (trifluoromethanesulfonyl) methide lithium (manufactured by Central Glass). The following compound (117) was obtained in the same manner as in Example 39, except that 70.3 g (16.8 mmol) of a 10: 1 mass ratio solution of ethyl alcohol was used. The yield was 70%.

(Example 42)
<Synthesis of Compound (118)>
In Example 39, a 9.17% by mass water: ethyl alcohol 10: 1 mass ratio solution of sodium tetrakis (pentafluorophenyl) borate was added to 2.5% by mass of sodium hexafluorophosphate (manufactured by Tokyo Chemical Industry). The following compound (118) was obtained in the same manner as in Example 39 except that 112.9 g (16.8 mmol) of a 10: 1 mass ratio solution of water: ethyl alcohol was used. The yield was 68%.

(Example 43)
<Synthesis of Compound (119)>
5% by mass of a 10% by mass aqueous solution of sodium tetrakis (pentafluorophenyl) borate (manufactured by Nippon Shokubai) in a 500 ml three-necked flask equipped with a stirrer and a thermometer so that the mass ratio of water: ethyl alcohol is 1: 1. 235.9 g (16.8 mmol) of the solution, 4.41 g (16.8 mmol) of triphenylphosphine (manufactured by Tokyo Chemical Industry) and 4.09 g (18.5 mmol) of 1-naphthylmethyl bromide (manufactured by Tokyo Chemical Industry) The mixture was added and stirred at room temperature for 24 hours. After completion of the stirring, the precipitated crystals were removed by filtration, washed with pure water three times, water was removed by drying under reduced pressure, washed with hexane, and dried again under reduced pressure to give the following compound (119) ) The yield was 91%.

(Example 44)
<Synthesis of Compound (120)>
In Example 43, except that triphenylphosphine was changed to 7.83 g (16.8 mmol) of tris (p-trifluoromethyl) phenylphosphine (manufactured by Tokyo Chemical Industry), the following compound (120 ) The yield was 81%.

(Example 45)
<Synthesis of Compound (121)>
The following compound (121) was obtained in the same manner as in Example 43 except that 1-naphthylmethyl bromide was changed to 2.50 g (18.5 mmol) of methallyl bromide (manufactured by Tokyo Chemical Industry) in Example 43. The yield was 83%.

(Example 46)
<Synthesis of Compound (122)>
In Example 43, the following compound (122) was obtained in the same manner as in Example 43, except that 1-naphthylmethyl bromide was changed to 2.24 g (18.5 mmol) of allyl bromide (manufactured by Tokyo Chemical Industry). The yield was 74%.

(Example 47)
<Synthesis of Compound (123)>
In Example 43, except that triphenylphosphine was changed to 5.31 g (16.8 mmol) of tris (4-fluorophenyl) phosphine (manufactured by Tokyo Chemical Industry), the following compound (123) was prepared in the same manner as in Example 43. Obtained. The yield was 85%.

(Comparative Example 13)
<Synthesis of 4-methylcarbonyloxy-phenylmethyl sulfide>
4 g (28.5 mmol) of 4-methylthiophenol and 8 g (78.4 mmol) of acetic anhydride were placed in a 100 ml three-necked flask, a small amount of concentrated sulfuric acid was added in a nitrogen gas atmosphere, and the mixture was stirred and reacted at room temperature for 3 hours. Thereafter, 40 g of a saturated aqueous sodium hydrogen carbonate solution and 20 g of ethyl acetate were added. After stirring, the mixture was transferred to a separatory funnel, the oil phase was taken out, the oil phase was further washed with water, the solvent was distilled off, and the residue was dried under reduced pressure. As a result, 5.091 g of 4-methylcarbonyloxy-phenylmethyl sulfide was obtained as a pale yellow liquid. (Yield 97.9%)

<Synthesis of Comparative Compound (101)>
Synthesis was performed in the same manner as in Example 23 except that 4- (methylthiophenol) was replaced with 2.52 g (16.8 mmol) of 4-methylcarbonyloxy-phenylmethyl sulfide synthesized above. However, after the synthesis, a viscous liquid precipitate was formed. This was taken out, washed with water, dried, and further washed with hexane, but no crystals were precipitated. When this viscous product was analyzed by LC / MS, the purity of the target product was 25%.

(Comparative Example 14)
<Synthesis of Comparative Compound (102)>
Synthesis was performed in the same manner as in Example 23, except that 4- (methylthiophenol) was replaced with 2.69 g (16.8 mmol) of 4 ′-(methylthio) acetophenone (manufactured by Tokyo Chemical Industry). However, after the synthesis, a viscous liquid precipitate was formed. This was taken out, washed with water, dried and further washed with hexane, but no crystals were precipitated as in Comparative Example 13. When this viscous product was analyzed by LC / MS, the purity of the target product was 11%.

(Comparative Example 15)
<Synthesis of Comparative Compound (103)>
Synthesis was performed in the same manner as in Example 23 except that 4- (methylthiophenol) was replaced with 2.46 g (16.8 mmol) of 4- (dimethylamino) benzonitrile (manufactured by Tokyo Chemical Industry). As a result, after the synthesis, a viscous liquid precipitate was formed. This was taken out, washed with water, dried and further washed with hexane, but no crystals were precipitated as in Comparative Example 13. When this viscous product was analyzed by LC / MS, the purity of the target product was 28%.

(Comparative Example 16)
<Synthesis of Comparative Compound (104)>
In Example 43, it replaced with tris [3,5-bis (trifluoromethyl) phenyl] phosphine (product made from Tokyo Chemical Industry) 11.26g (16.8mmol), and was carried out similarly to Example 43, and changed. As a result, after the synthesis, a viscous liquid precipitate was formed. This was taken out, washed with water, dried and further washed with hexane, but no crystals were precipitated as in Comparative Example 13. When this viscous product was analyzed by LC / MS, the purity of the target product was 32%.

  Examples 23 to 47 and Comparative Examples 13 to 16 are summarized below.

From the above results, the method for producing the sulfonium compound of the present invention is a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3). It can be seen that a sulfonium compound can be obtained in a very simple and high yield by using the combination of
On the other hand, when it is not a combination of the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3), the sulfonium compound is a similar method. Can not be produced at all, or the yield is very low.
Moreover, it turns out that a part of sulfonium compound obtained by the manufacturing method of the sulfonium compound of this invention cannot be manufactured by the conventional method from Comparative Examples 6 and 7.

From the above results, the production method of the ammonium compound of the present invention is the compound represented by the general formula (11), the compound represented by the general formula (2), and the compound represented by the general formula (3). It can be seen that an ammonium compound can be obtained in a very simple and high yield by using the combination of
On the other hand, when it is not a combination of the compound represented by the general formula (11), the compound represented by the general formula (2), and the compound represented by the general formula (3), the yield of the ammonium compound is It turns out that it is very low.

From the above results, the production method of the phosphonium compound of the present invention is the compound represented by the general formula (21), the compound represented by the general formula (2), and the compound represented by the general formula (3). It can be seen that a phosphonium compound can be obtained in a very simple and high yield by using the combination of
On the other hand, when it is not a combination of the compound represented by the general formula (21), the compound represented by the general formula (2), and the compound represented by the general formula (3), the yield of the phosphonium compound is It turns out that it is very low.

  Therefore, the usefulness of the present invention was proved.

  The present invention can be suitably used for producing an onium compound.

Claims (6)

One of the following (A), (B), and (C), The manufacturing method of the onium compound characterized by the above-mentioned.
(A) In at least one solvent of water, alcohol, and acetonitrile, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula (3) After mixing with a compound represented by the formula (1), the reaction is carried out to obtain a sulfonium compound represented by the following general formula (4).
(B) In water, the compound represented by the following general formula (11), the compound represented by the following general formula (2), and the compound represented by the following general formula (3) are mixed and reacted. The ammonium compound represented by the following general formula (14) is obtained.
(C) In water, the compound represented by the following general formula (21), the compound represented by the following general formula (2), and the compound represented by the following general formula (3) are mixed and reacted. A phosphonium compound represented by the following general formula (24) is obtained.
However, the general formula (1) and general formula (4), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms.
In the general formula (1) and the general formula (4), R ² represents a phenyl group having 0 to 5 substituents (provided that when the solvent contains water as a main component, the R ² in the R ² represents The sum of the substituent constants of Hammett's substituents is 0.30 or less, and when the solvent does not contain water as the main component, R ² is a group represented by the following general formula (A)).
In the general formulas (2) and (4), R ³ is an α-naphthylmethyl group in which an aromatic ring hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, or an aromatic ring hydrogen. A cinnamyl group in which an atom may be substituted with an alkyl group having 1 to 4 carbon atoms, a group represented by the following general formula (B), a group represented by the following general formula (C), and the following general formula (D) Any one of the groups represented by
In the general formula (2), Z represents a halogen atom.
In the general formula (3), X ⁺ represents any of Li ⁺ , Na ⁺ , and K ⁺ .
In the general formulas (3) and (4), Y ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , PF ₃ (C ₂ F _{^{5) 3 -, C 3 F}} 6 NO 4 S 2 -, (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.
In the general formula (A), R ⁴ is a hydrogen atom, and represent an alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a benzyl group which may have a substituent, a naphthylmethyl group which may have a substituent, or an alkylcarbonylmethyl. A group, an arylcarbonylmethyl group which may have a substituent, an alkoxycarbonylmethyl group, and an aryloxycarbonylmethyl group which may have a substituent;
In the general formula (B), R ⁶ represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group.
In the general formula (C), R ⁷ represents any one of a hydrogen atom, a methyl group, and a phenyl group.
In the general formula (D), R ⁸ represents any of an alkyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
However, in said general formula (11) and general formula (14), R < ¹¹ > and R < ¹² > represent a C1-C4 alkyl group each independently.
In General Formula (11) and General Formula (14), R ¹³ represents a phenyl group having 0 to 5 substituents, and the sum of Hammett's substituent constants of the substituents in R ¹³ is 0. 60 or less.
In the general formula (14), R ³ represents an α-naphthylmethyl group in which the hydrogen atom of the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the aromatic ring has 1 to carbon atoms. A cinnamyl group optionally substituted with an alkyl group of 4, a group represented by the general formula (B), a group represented by the general formula (C), and a group represented by the following general formula (D) Represents one of the following.
In the general formula (14), Y ^{- _{is, B (C 6 F 5)}} 4 -, SbF 6 -, AsF 6 -, PF 6 -, BF 4 -, PF 3 (C 2 F 5) 3 -, C ^{_{3 F 6 NO 4 S 2 -}} , (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either.
However, in said general formula (21) and general formula (24), R <^21> , R < ²² > and R < ²³ > represent the phenyl group which has 0-5 substituents each independently. The sum total of Hammett's substituent constants of the substituent in R ²¹ is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²² is 0.70 or less. The sum total of Hammett's substituent constants of the substituent in R ²³ is 0.70 or less.
In the general formula (24), R ³ represents an α-naphthylmethyl group in which the hydrogen atom of the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the aromatic ring represents 1 to carbon atoms. A cinnamyl group optionally substituted with an alkyl group of 4, a group represented by the general formula (B), a group represented by the general formula (C), and a group represented by the following general formula (D) Represents one of the following.
In the general formula (24), Y ^{- _{is, B (C 6 F 5)}} 4 -, SbF 6 -, AsF 6 -, PF 6 -, BF 4 -, PF 3 (C 2 F 5) 3 -, C ^{_{3 F 6 NO 4 S 2 -}} , (C 2 F 5 SO 2) 2 N -, and _{C (CF 3 SO 2) 3} - represents either. In the general formula (3), the general formula (4), the general formula (14), and the general formula (24), Y ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ⁻ , PF _{6. ^{-, PF 3 (C 2 F}} 5) 3 -, and _{C (CF 3 SO 2) 3} - the production method of the onium compound according to claim 1 is either.   The method for producing an onium compound according to claim 1, wherein the alcohol is at least one of methanol and ethanol. In the general formula (3), the general formula (4), the general formula (14), and the general formula (24), R ³ represents a benzyl group, an o-methylbenzyl group, an α-naphthylmethyl group, cinnamyl. The method for producing an onium compound according to any one of claims 1 to 3, which is any one of a group, an allyl group, a methallyl group, and a 2-ethoxycarbonylpropenyl group. A method for producing a curable resin composition containing an onium compound,
The said onium compound is obtained by the manufacturing method of the onium compound in any one of Claim 1 to 4, The manufacturing method of the curable resin composition characterized by the above-mentioned.   The method for producing a curable resin composition according to claim 5, wherein the curable resin composition further contains an epoxy compound.