JP2014070020A - Method of producing triarylsulfonium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing, easily and with a high yield and high purity, a triarylsulfonium salt often used as a photoacid generator or a photo cation polymerization initiator.SOLUTION: There is provided a method of producing a triarylsulfonium salt represented by the formula (2), where R, Rand Rrepresent a monocyclic carbon ring group which may have a substituent group, a condensed polycyclic carbon ring group which may have a substituent group, or a monocyclic heterocyclic group which may have a substituent group, and Xrepresents an inorganic acid ion or an organic acid ion, including reacting diaryl sulfoxide of R-S(O)-R(a) and an aromatic compound (b) in the presence of Lewis acid (c), sulfonic acid and/or carboxylic acid (d) as well as sulphuric acid, and further reacting with an alkali metal salt of inorganic acid, an ammonium salt of inorganic acid, an alkali metal salt of organic acid or an ammonium salt of organic acid.

Description

  The present invention relates to a method for producing a triarylsulfonium salt useful as a photoacid generator for a chemically amplified resist in the field of semiconductor production or as a photocationic polymerization initiator in the field of ink, paint, adhesive or the like.

  As a method for producing a triarylsulfonium salt, a method in which a diaryl sulfoxide and an aromatic compound are reacted with each other, and a diaryl sulfoxide and an aromatic compound are reacted in the presence of a solution of phosphorus pentoxide and methanesulfonic acid (patent) Document 1), a process for producing polyarylsulfoxide and polyarylsulfide by contacting with strong acid in the presence of a dehydrating agent (Patent Document 2), by reacting diarylsulfoxide with an aromatic compound in the presence of aluminum chloride A manufacturing method (Non-patent Document 1) and the like are known.

  However, in the method of reacting diaryl sulfoxide and an aromatic compound in the presence of a solution of phosphorus pentoxide and methanesulfonic acid, phosphorus pentoxide is very hygroscopic and difficult to handle. In order to dissolve in methanesulfonic acid, it is necessary to stir for a long time under heating conditions, which is not an industrially advantageous production method. In addition, in the method for producing polyarylsulfoxide and polyarylsulfide by contacting them with a strong acid in the presence of a dehydrating agent, the substrate that can be used is limited, and there are many side reactions, which may reduce the production yield. There was a problem such as. In addition, in the method of reacting diaryl sulfoxide and an aromatic compound in the presence of aluminum chloride, not only is the yield low, but usually an equimolar amount or more of aluminum chloride is required with respect to diaryl sulfoxide. In addition, when an aromatic compound that forms a complex with aluminum chloride is used as a raw material, there is a problem that a large amount of aluminum chloride is required to further reduce the reactivity and the amount of waste water becomes very large.

JP 05-004996 A JP-A-61-100557

J. et al. Org. Chem. , 1968, 33, 2671

  The objective of this invention is providing the manufacturing method which can manufacture the triaryl sulfonium salt often used as a photo-acid generator or a photocationic polymerization initiator simply by a high yield and high purity.

  The present inventors examined that a triarylsulfonium salt can be produced by dropping sulfuric acid into a solution of diaryl sulfoxide (a), aromatic compound (b) and sulfonic acid and / or carboxylic acid (d). In this method, it was revealed that there was a large difference in reactivity depending on the substrate, and in some cases, the yield was very low. As a result of further diligent investigations, a large amount is used in the prior art in a system in which sulfuric acid is added to the diaryl sulfoxide (a), aromatic compound (b), and sulfonic acid and / or carboxylic acid (d) solution. The inventors have found that by adding a catalytic amount of Lewis acid such as aluminum chloride which has been required, the reactivity can be dramatically improved and the formation of by-products can be suppressed, and further improvements have been made to the present invention.

That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1.
Formula (1):

(Wherein R ¹ and R ² are each independently a monocyclic carbocyclic group which may have a substituent, a condensed polycyclic carbocyclic group which may have a substituent, or a substituent. A diaryl sulfoxide (a) represented by a monocyclic heterocyclic group which may have a group) and an aromatic compound (b), a Lewis acid (c), a sulfonic acid and / or a carboxylic acid ( d), as well as reacting in the presence of sulfuric acid,
Further reaction with an alkali metal salt of an inorganic acid, an ammonium salt of an inorganic acid, an alkali metal salt of an organic acid, or an ammonium salt of an organic acid, and the formula (2)
Formula (2):

(In the formula, R ¹ and R ² are the same as defined above, and R ³ independently has a monocyclic carbocyclic group, which may have a substituent, independently of R ¹ and R ^2. A condensed polycyclic carbocyclic group which may optionally be substituted or a monocyclic heterocyclic group which may have a substituent, wherein X ⁻ represents an inorganic acid ion or an organic acid ion. A method for producing a salt.

The structural formula of the aromatic compound (b) to be used can be expressed as “R ³ —H”.

Item 2.
Item 2. The aromatic compound (b) is at least one selected from the group consisting of arylalkyl ethers, polyaryl ethers, arylalkyl sulfides, polyaryl sulfides, and optionally substituted thiophenes. A method for producing a triarylsulfonium salt.
Item 3.
Item 3. The triarylsulfonium according to item 1 or 2, wherein the Lewis acid (c) is at least one selected from the group consisting of aluminum chloride, aluminum bromide, iron chloride, iron bromide, zinc chloride, and zinc bromide. A method for producing a salt.
Item 4.
Item 3. The triarylsulfonium according to any one of Items 1 to 3, wherein the sulfonic acid and / or carboxylic acid (d) is at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, acetic acid, and propionic acid. A method for producing a salt.
Item 5.
The triarylsulfonium salt according to any one of claims 1 to 4, wherein the use ratio of the Lewis acid (c) is 0.0001 to 0.1 mol with respect to 1 mol of the diaryl sulfoxide (a). Method.

  By using the method for producing a triarylsulfonium salt according to the present invention, a triarylsulfonium salt with high yield and high purity can be easily produced.

  The diaryl sulfoxide (a) used in the present invention is a compound represented by the following formula (1).

In the formula, each of R ¹ and R ² independently represents a monocyclic carbocyclic group which may have a substituent, a condensed polycyclic carbocyclic group which may have a substituent, or a substituent. The monocyclic heterocyclic group which may have is shown. Although not particularly limited, R ¹ and R ² are preferably the same group.

  The monocyclic carbocyclic group that may have a substituent, the condensed polycyclic carbocyclic group that may have a substituent, and the monocyclic heterocyclic group that may have a substituent, When each has a substituent, it may have one substituent or may have a plurality of substituents. In the case of having a plurality of substituents, the substituents may be the same substituent or different substituents. Although not particularly limited, when it has a substituent, the number of substituents is preferably 1, 2 or 3.

  Examples of the monocyclic carbocyclic group which may have a substituent include a phenyl group which may have a substituent (that is, a phenyl group and a phenyl group having a substituent).

  Examples of the condensed polycyclic carbocyclic group which may have a substituent include a naphthyl group (that is, a naphthyl group and a naphthyl group having a substituent) which may have a substituent.

  Examples of the monocyclic heterocyclic group that may have a substituent include a thienyl group that has a substituent (that is, a thienyl group and a thienyl group that has a substituent).

  Examples of the substituent include a hydroxyl group, an acetoxy group, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenoxy group, and phenylthio. Group, thienylthio group, halogen atom and the like.

  The alkyl group having 1 to 10 carbon atoms may be linear or branched, and is preferably linear. Moreover, carbon number becomes like this. More preferably, it is 1-8, More preferably, it is 1-6, More preferably, it is 1-4. Specific examples of the alkyl group having 1 to 10 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-octyl group. And n-decyl group and the like are preferable. Of these, a methyl group and an ethyl group are preferable.

  Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a methoxyethoxy group. Etc.

  Examples of the alkylthio group having 1 to 4 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, and an n-butylthio group.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.

In the formula (1), the group represented by R ¹ and the group represented by R ² may be a monocyclic carbocyclic group which may have a substituent or a monocyclic heterocycle which may have a substituent. A cyclic group is preferable, and among them, a phenyl group, a phenyl group having a substituent, a thienyl group, or a thienyl group having a substituent is more preferable. In addition, as a substituent in the phenyl group having a substituent and the thienyl group having a substituent, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxy group, an ethoxy group N-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, tert- A butylthio group, a hydroxy group, an acetoxy group, a phenoxy group, a phenylthio group, a thienylthio group or a fluorine atom is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group are more preferable A.

In particular, when the group represented by R ¹ and / or the group represented by R ² is a phenyl group having a substituent, specific examples include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group ( That is, o-tolyl group, m-tolyl group, p-tolyl group), 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2-n-propylphenyl group, 3-n-propylphenyl Group, 4-n-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-n-butylphenyl group, 3-n-butylphenyl group, 4-n-butylphenyl Group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-n-propoxyphenyl group, 2 -Isopropoxyphenyl group, 3-isopropoxyphenyl group, 4-isopropoxyphenyl group, 2-n-butoxyphenyl group, 3-n-butoxyphenyl group, 4-n-butoxyphenyl group, 2-isobutoxyphenyl group 3-isobutoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 3-sec-butoxyphenyl group, 4-sec-butoxyphenyl group, 2-tert-butoxyphenyl group, 3-tert -Butoxyphenyl group, 4-tert-butoxyphenyl group, 2-methylthiophenyl Group, 3-methylthiophenyl group, 4-methylthiophenyl group, 2-ethylthiophenyl group, 3-ethylthiophenyl group, 4-ethylthiophenyl group, 2-n-propylthiophenyl group, 3-n-propylthio Phenyl group, 4-n-propylthiophenyl group, 2-isopropylthiophenyl group, 3-isopropylthiophenyl group, 4-isopropylthiophenyl group, 2-n-butylthiophenyl group, 3-n-butylthiophenyl group 4-n-butylthiophenyl group, 2-tert-butylthiophenyl group, 3-tert-butylthiophenyl group, 4-tert-butylthiophenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4 -Hydroxyphenyl group, 2-acetoxyphenyl group, 3-acetoxyphenyl group, 4-acetoxy group Phenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4- Preferred examples include bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, and 2,4,6-trimethylphenyl group. Among them, 4-methylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-tert-butylphenyl group, 4-methoxyphenyl Group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group, 4-isopropoxyphenyl group, -n- butoxyphenyl group, 4-methylthiophenyl group, 4-fluorophenyl group, 2,4-dimethylphenyl group is preferable.

When the group represented by R ¹ and / or the group represented by R ² is a biphenyl group, it may be a 2-biphenyl group, a 3-biphenyl group, or a 4-biphenyl group, and among them, a 4-biphenyl group. Is preferred. When it is a naphthyl group, it may be a 1-naphthyl group or a 2-naphthyl group, and among them, a 2-naphthyl group is preferable.

In addition, when the group represented by R ¹ and / or the group represented by R ² is a thienyl group, either a 2-thienyl group or a 3-thienyl group may be used, and a 2-thienyl group is preferable.

When the group represented by R ¹ and / or the group represented by R ² is a thienyl group having a substituent, specific examples include a 3-methylthienyl group, a 4-methylthienyl group, and a 5-methylthienyl group. A group (particularly 3-methylthiophen-2-yl group, 4-methylthiophen-2-yl group, 5-methylthiophen-2-yl group) is preferably exemplified.

Specific examples of the diaryl sulfoxide represented by the formula (1) include
Diphenyl sulfoxide, bis (4-methylphenyl) sulfoxide, bis (4-ethylphenyl) sulfoxide, bis (4-n-propylphenyl) sulfoxide, bis (4-isopropylphenyl) sulfoxide, bis (4-n-butylphenyl) Sulfoxide, bis (4-tert-butylphenyl) sulfoxide, bis (4-biphenyl) sulfoxide,
Bis (4-methoxyphenyl) sulfoxide, bis (4-ethoxyphenyl) sulfoxide, bis (4-n-propoxyphenyl) sulfoxide, bis (4-isopropoxyphenyl) sulfoxide, bis (4-n-butoxyphenyl) sulfoxide, Bis (4-isobutoxyphenyl) sulfoxide, bis (4-sec-butoxyphenyl) sulfoxide, bis (4-tert-butoxyphenyl) sulfoxide,
Bis (4-methylthiophenyl) sulfoxide, bis (4-ethylthiophenyl) sulfoxide, bis (4-n-propylthiophenyl) sulfoxide, bis (4-isopropylthiophenyl) sulfoxide, bis (4-n-butylthiophenyl) ) Sulfoxide, bis (4-tert-butylthiophenyl) sulfoxide, 4-methylphenyl- (2,4-dimethylphenyl) sulfoxide bis (4-hydroxyphenyl) sulfoxide, bis (4-acetoxyphenyl) sulfoxide,
Bis (4-fluorophenyl) sulfoxide, bis (4-chlorophenyl) sulfoxide, bis (4-bromophenyl) sulfoxide, bis (4-iodophenyl) sulfoxide,
Bis (2,4-dimethylphenyl) sulfoxide, bis (3,4-dimethylphenyl) sulfoxide, bis (2,4,6-trimethylphenyl) sulfoxide,
Examples include di- (2-thienyl) sulfoxide, di- (2-naphthyl) sulfoxide, and the like.

  Among these, diphenyl sulfoxide, bis (4-methylphenyl) sulfoxide, bis (4-ethylphenyl) sulfoxide, bis (4-n-propylphenyl) sulfoxide, bis (4-isopropylphenyl) sulfoxide, bis (4-n -Butylphenyl) sulfoxide, bis (4-methoxyphenyl) sulfoxide, bis (4-ethoxyphenyl) sulfoxide, bis (4-n-propoxyphenyl) sulfoxide, bis (4-isopropoxyphenyl) sulfoxide, bis (4-n -Butoxyphenyl) sulfoxide, bis (4-methylthiophenyl) sulfoxide, bis (4-fluorophenyl) sulfoxide and bis (2,4-dimethylphenyl) sulfoxide are preferably used.

The diaryl sulfoxide is a known substance or can be easily produced by a known method. What is marketed may be used as it is, and what was manufactured suitably may be used. The method for producing diaryl sulfoxide is not particularly limited. For example, when diaryl sulfoxide is bis (4-methylphenyl) sulfoxide in which R ¹ and R ² in formula (1) are both 4-methylphenyl groups, A method of reacting toluene and thionyl chloride in the presence of trifluoromethanesulfonic acid (Synlett., 1999, 1397), or diaryl sulfoxide, wherein R ¹ in formula (1) is a 4-methylphenyl group, R ² Is 4-methylphenyl- (2,4-dimethylphenyl) sulfoxide in which is a 2,4-dimethylphenyl group, a method of reacting m-xylene and p-toluenesulfinyl chloride in the presence of aluminum chloride ( J. Org. Chem., 1974, 39, 1203) It can manufacture by the method of.

The aromatic compound (b) according to the present invention is a compound that functions to introduce the aryl group (R ³ ) in the formula (2). The aromatic compound (b) is a compound having at least one hydrogen atom on the aromatic ring. Examples of (b) include a monocyclic carbocyclic compound which may have a substituent, a condensed polycyclic carbocyclic compound which may have a substituent, or a monocyclic heterocycle which may have a substituent. A ring compound is mentioned.

  The monocyclic carbocyclic compound which may have the substituent, the condensed polycyclic carbocyclic compound which may have a substituent, and the monocyclic heterocyclic compound which may have a substituent, When each has a substituent, it may have one substituent or may have a plurality of substituents. In the case of having a plurality of substituents, the substituents may be the same type of substituents or different substituents. Although not particularly limited, when it has a substituent, the number of substituents is preferably 1, 2 or 3.

  Examples of the monocyclic carbocyclic compound which may have the substituent include benzene and benzene having a substituent.

  Examples of the condensed polycyclic carbocyclic compound which may have the substituent include naphthalene and naphthalene having a substituent.

  Examples of the monocyclic heterocyclic compound which may have a substituent include thiophene and thiophene having a substituent.

  Examples of the substituent include a hydroxyl group, an acetoxy group, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenoxy group, and phenylthio. Group, thienylthio group, halogen atom and the like.

  The alkyl group having 1 to 10 carbon atoms may be linear or branched, and is preferably linear. Moreover, carbon number becomes like this. More preferably, it is 1-8, More preferably, it is 1-6, More preferably, it is 1-4. Specific examples of the alkyl group having 1 to 10 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n- A hexyl group, n-octyl group, n-decyl group, etc. are mentioned preferably. Of these, a methyl group and an ethyl group are preferable.

  Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a methoxyethoxy group. Etc.

  Examples of the alkylthio group having 1 to 4 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, and an n-butylthio group.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.

  As the aromatic compound (b), a monocyclic carbocyclic compound which may have a substituent and a monocyclic heterocyclic compound which may have a substituent are preferable, and among them, benzene having a substituent (For example, arylalkyl ethers, polyaryl ethers, arylalkyl sulfides, polyaryl sulfides, etc.) and thiophene that may have a substituent (that is, thiophene and thiophene having a substituent) are more preferable.

  Moreover, as a substituent in benzene having a substituent and thiophene having a substituent, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxy group, an ethoxy group, n -Propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, methylthio group, ethylthio group, phenoxy group, phenylthio group, thienylthio group or fluorine atom are preferred, methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, methylthio group, phenylthio group or thienylthio group are more preferably used. It is done.

As an aromatic compound (b), specifically, for example,
Toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, tert-butylbenzene, anisole, ethoxybenzene, n-propoxybenzene, isopropoxybenzene, n-butoxybenzene, isobutoxybenzene, sec-butoxybenzene, tert-butoxybenzene, thioanisole, ethylthiobenzene, n-propylthiobenzene, i-propylthiobenzene, n-butylthiobenzene, t-butylthiobenzene, phenol, acetoxybenzene, fluorobenzene, chlorobenzene, bromobenzene, biphenyl , Diphenyl ether, 3-methyldiphenyl ether, 3-phenoxyphenol, p-phenoxyphenol, 3-phenoxybenzoyl alcohol, diphen Sulfide, phenyl-p-tolyl sulfide, 4-ethylphenylthiobenzene, 4-n-propylphenylthiobenzene, 4-i-propylphenylthiobenzene, 4-n-butylphenylthiobenzene, 4-t-butylphenylthio benzene,
Naphthalene, methylnaphthalene, methoxynaphthalene,
Thiophene, methylthiophene, ethylthiophene, n-propylthiophene, isopropylthiophene, n-butylthiophene, tert-butylthiophene, methoxythiophene, ethoxythiophene, n-propoxythiophene, isopropoxythiophene, n-butoxythiophene, isobutoxythiophene, sec-butoxythiophene, tert-butoxythiophene, methylthiothiophene, ethylthiothiophene, hydroxythiophene, acetoxythiophene, phenylthiophene, phenylthiothiophene, bithiophene, dithienyl ether (having a structure in which two thiophenes are linked by -O- Compounds, particularly those in which the 2-positions of both thiophenes are bonded by -O-), dithienyl sulfide (two thiophenes are Compounds having a combined structure S-; particularly those 2-position of the two thiophene joined by -S- is preferred), and the like.

  Of the compounds listed above as specific examples of (b), diphenyl ether, 3-methyldiphenyl ether, 3-phenoxyphenol, p-phenoxyphenol, 3-phenoxybenzoyl alcohol, and dithienyl ether are polyaryl ethers, Diphenyl sulfide, phenyl-p-tolyl sulfide, 4-ethylphenylthiobenzene, 4-n-propylphenylthiobenzene, 4-i-propylphenylthiobenzene, 4-n-butylphenylthiobenzene, 4-t-butylphenyl Thiobenzene, phenylthiothiophene, and dithienyl sulfide are polyaryl sulfides such as thioanisole, ethylthiobenzene, n-propylthiobenzene, i-propylthiobenzene, n-butylthiobenzene, and t-butyl. Lucio benzene is aryl alkyl sulfide.

Among these, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, anisole, ethoxybenzene, n-propoxybenzene, isopropoxybenzene, n-butoxybenzene, diphenyl ether, thioanisole, diphenyl sulfide,
Bithiophene, phenylthiophene, phenylthiothiophene, dithienyl sulfide are preferably used.

The Lewis acid (c) according to the present invention is not particularly limited. Specifically, aluminum chloride, aluminum bromide, aluminum iodide, iron chloride, iron bromide, iron iodide, zinc chloride, Metal halides such as zinc bromide, zinc iodide, titanium chloride, titanium bromide, tin chloride, tin bromide, tin iodide, boron trifluoride, boron trichloride, boron tribromide, boron triiodide, etc. Boron halide compounds, antimony halide compounds such as antimony chloride and antimony fluoride,
Dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride,
Organoboron compounds such as triphenylboron and tris (pentafluorophenyl) boron,
And metal triflates such as sodium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, copper trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, and scandium trifluoromethanesulfonate.

  Among these, metal halides such as aluminum chloride, aluminum bromide, iron chloride, iron bromide, zinc chloride, and zinc bromide are preferably used. These Lewis acids (c) may be used individually by 1 type, or may use 2 or more types together.

  Although a limited interpretation is not desired, it is considered that the sulfonic acid and / or carboxylic acid (d) according to the present invention serves not only as a reaction solvent but also as an acid component for promoting the reaction. . In addition, the sulfonic acid and / or carboxylic acid (d) serves as a buffer that prevents the sulfuric acid and the substrate such as the aromatic compound (b) used in the present invention from coming into direct contact and decomposing. Conceivable.

  Examples of the sulfonic acid include alkyl sulfonic acid and aromatic sulfonic acid. Among these, alkylsulfonic acid is preferable, and alkylsulfonic acid having 1 to 8 carbon atoms is more preferable. Specific examples include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, pentane sulfonic acid, and octane sulfonic acid.

  Examples of the carboxylic acid include alkyl carboxylic acids and aromatic carboxylic acids. Among these, alkyl carboxylic acids are preferable, and alkyl carboxylic acids having 1 to 8 carbon atoms are more preferable. Specific examples include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid and the like.

  Among these, at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, acetic acid, and propionic acid is preferably used. These sulfonic acid and / or carboxylic acid (d) may be used alone or in combination of two or more. That is, as (d), at least one selected from the group consisting of the sulfonic acid and the carboxylic acid can be used.

  The use ratio of the aromatic compound (b) is not particularly limited, but from the viewpoint of improving the yield and economy, the diaryl sulfoxide (a) represented by the formula (1) is added to 1 mol. The amount is preferably 0.8 to 2 mol, more preferably 0.9 to 1.8 mol, and still more preferably 0.9 to 1.5 mol. If the use ratio of the aromatic compound (b) is 0.8 mol or more with respect to 1 mol of (a), it is possible to further reduce the possibility that the unreacted diaryl sulfoxide (a) increases and the yield decreases. . Moreover, it is more economical considering the usage-amount that the usage-amount of an aromatic compound (b) is 2 mol or less with respect to 1 mol of (a).

The use ratio of the Lewis acid (c) may be very small as compared with the prior art. (It is only necessary to use a so-called catalyst amount.) For this reason, it is advantageous in that the amount of drainage can be remarkably reduced as compared with the prior art. Although not particularly limited, from the viewpoint of improving the yield and economical efficiency, it is preferably 0.0001 to 0.1 mol with respect to 1 mol of diaryl sulfoxide (a), 0.001 to The amount is more preferably 0.05 mol, and further preferably 0.002 to 0.03 mol.
If the use ratio of the Lewis acid (c) is 0.0001 mol or more per 1 mol of (a), a higher yield can be obtained. Moreover, when the usage-amount of Lewis acid (c) is 0.1 mol or less with respect to 1 mol of (a), it is more economical.

  The ratio of the sulfonic acid and / or carboxylic acid (d) used is not particularly limited, but is preferably 1 to 50 mol, and preferably 2 to 30 mol, per 1 mol of diaryl sulfoxide (a). It is more preferable. When the use ratio of the sulfonic acid and / or carboxylic acid (d) is 1 mol or more per 1 mol of (a), the yield can be further improved. Moreover, when the usage-amount of a sulfonic acid and / or carboxylic acid (d) is 50 mol or less with respect to 1 mol of (a), it is more economical.

  Although the usage-amount of a sulfuric acid is not restrict | limited in particular, It is preferable that it is 1-20 mol with respect to 1 mol of diaryl sulfoxide (a), and it is more preferable that it is 2-10 mol. When the use ratio of sulfuric acid is 1 mol or more per 1 mol of (a), the yield may be reduced. Moreover, if the usage-amount of a sulfuric acid is 20 mol or less with respect to 1 mol of (a), it is more economical. Although not particularly limited, concentrated sulfuric acid is preferably used in order to efficiently achieve the above-described use ratio of sulfuric acid. Commercially available concentrated sulfuric acid can be preferably used. Commercially available concentrated sulfuric acid usually has a concentration of about 96 to 98% by mass.

  In the method of reacting diaryl sulfoxide (a) and aromatic compound (b) according to the present invention in the presence of Lewis acid (c), sulfonic acid and / or carboxylic acid (d), and sulfuric acid, stirring is carried out. For the purpose of improving efficiency, a solvent such as sulfolane, dichloromethane or chloroform may be used as a reaction solvent together with the sulfonic acid and / or carboxylic acid (d). The amount used when using these solvents (at least one selected from the group consisting of sulfolane, dichloromethane and chloroform) is preferably 30 to 2000 parts by mass with respect to 100 parts by mass of diaryl sulfoxide (a), More preferably, it is 50-1000 mass parts.

  The reaction temperature in the reaction is preferably -20 to 100 ° C, more preferably -15 to 70 ° C, and further preferably -10 to 50 ° C. When reaction temperature is -20 degreeC or more, the possibility that reaction may require a long time because reaction rate becomes slow is reduced more. Moreover, when reaction temperature is 100 degrees C or less, a side reaction tends to occur and a possibility that a yield and purity fall may be reduced more. Although reaction time changes with reaction temperature etc., it is 0.5 to 48 hours normally, Preferably it is 1 to 24 hours.

  The triarylsulfonium salt represented by the formula (2) is obtained after the reaction of the diaryl sulfoxide (a) with the aromatic compound (b) (preferably following the reaction), and the reaction product is converted to an alkali acid alkali salt. It can be produced by reacting with a metal salt, an ammonium salt of an inorganic acid, an alkali metal salt of an organic acid, or an ammonium salt of an organic acid.

Specific examples of the inorganic acid include
Hexafluoroantimonic acid, hexafluoroarsenic acid, hexafluorophosphoric acid, pentafluorohydroxoantimonic acid, tetrafluoroboric acid, trifluorotristrifluoromethyl phosphoric acid, trifluorotrispentafluoroethyl phosphoric acid, trifluorotrisheptafluoropropyl phosphoric acid,
Tetrakis (pentafluorophenyl) boric acid, tetrakis (trifluoromethylphenyl) boric acid, trifluoro (pentafluorophenyl) boric acid, tetrakis (difluorophenyl) boric acid, difluorobis (pentafluorophenyl) boric acid, etc. .

Specific examples of the alkali metal salt of the inorganic acid include lithium salt, sodium salt, potassium salt and the like of the inorganic acid. Specific examples of the inorganic acid ammonium salt include an ammonium salt containing an ammonium ion (NH ⁴⁺ ) or a quaternary ammonium salt of the inorganic acid. Examples of the quaternary ammonium salt include tetra-n-butylammonium salt.

Specific examples of the organic acid include
Methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid,
Benzenesulfonic acid, benzene-1,3-disulfonic acid, p-toluenesulfonic acid, anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-1,5-disulfonic acid, camphorsulfonic acid,
Bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, tris (trifluoromethanesulfonyl) methide, etc. be able to.

Specific examples of the alkali metal salt of the organic acid include lithium salt, sodium salt and potassium salt of the organic acid. Specific examples of the organic acid ammonium salt include ammonium salts containing ammonium ions (NH ⁴⁺ ) and quaternary ammonium salts of the organic acids. Examples of the quaternary ammonium salt include tetra-n-butylammonium salt.

  Among these salts, from the viewpoint of the acid strength and safety of the acid generated when the obtained triarylsulfonium salt is used as a photoacid generator or a photocationic polymerization initiator, sodium hexafluorophosphate, Potassium hexafluorophosphate, sodium trifluorotrispentafluoroethyl phosphate, potassium trifluorotrispentafluoroethyl phosphate, sodium trifluorotriseptafluoropropyl phosphate, potassium trifluorotriseptafluoropropyl phosphate, tetrakis (pentafluoro Phenyl) lithium borate, sodium tetrakis (pentafluorophenyl) borate, potassium tetrakis (pentafluorophenyl) borate, sodium trifluoromethanesulfonate, trifluoromethanesulfo Acid potassium, sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, sodium camphorsulfonate, potassium camphorsulfonate, bis (fluorosulfonyl) imide potassium, bis (Trifluoromethanesulfonyl) imide lithium, bis (trifluoromethanesulfonyl) imide potassium, bis (nonafluorobutanesulfonyl) imide potassium, bis (nonafluorobutanesulfonyl) imidoammonium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) ) Imidopotassium and tris (trifluoromethanesulfonyl) methide lithium are preferred.

  The use ratio of the alkali metal salt of inorganic acid, ammonium salt of inorganic acid, alkali metal salt of organic acid, or ammonium salt of organic acid is not particularly limited, but relative to 1 mol of diaryl sulfoxide (a) 0.8 to 2 mol is preferable, and 0.9 to 1.5 mol is more preferable. When the use ratio of the salt is 0.8 mol or more per 1 mol of (a), the yield can be further improved. Moreover, when the usage-amount of the said salt is 2 mol or less, it is more economical. Any of alkali metal salts of inorganic acids, ammonium salts of inorganic acids, alkali metal salts of organic acids, and ammonium salts of organic acids can be used as an aqueous solution. As a density | concentration when using as aqueous solution, it is preferable that it is 1-80 mass%, and it is more preferable that it is 3-50 mass%.

  The operation of reacting the reactant with an alkali metal salt of an inorganic acid, an ammonium salt of an inorganic acid, an alkali metal salt of an organic acid, or an ammonium salt of an organic acid is not particularly limited. What is necessary is just to mix the said salt. For example, a method of adding a predetermined amount of the salt to the reaction solution after the reaction, a method of adding the reaction solution after the reaction to a predetermined amount of the salt, a condensation after adding the reaction solution after the reaction to a predetermined amount of water A method of adding the salt after forming an aqueous solution of the reaction product, and adding the reaction solution after the reaction to a predetermined amount of water to form an aqueous solution of the condensation reaction product, and then adding the aqueous solution to the salt Methods and the like. During these reactions, if necessary, an acidic component present in the reaction system may be neutralized using a basic substance such as sodium hydroxide.

  In these operations, an organic solvent such as monochlorobenzene, ethyl acetate and dichloromethane may be present.

  The reaction temperature is not particularly limited, but is preferably −10 to 100 ° C., and more preferably 0 to 80 ° C. When the reaction temperature is −10 ° C. or higher, the reaction rate can proceed faster. Moreover, when reaction temperature is 100 degrees C or less, it is more efficient from a viewpoint of energy efficiency.

  The triarylsulfonium salt thus obtained may be purified after completion of the reaction. Examples of the purification method include a method in which the precipitated solid is separated by filtration, or a method in which extraction is performed using an organic solvent such as monochlorobenzene, ethyl acetate, and dichloromethane, and then the organic solvent is distilled off.

Moreover, when it is desired to obtain the triarylsulfonium salt as a solution, it can be made into a solution by, for example, a method of adding a desired organic solvent to the concentrate and re-dissolving it.
Examples of such an organic solvent include propylene carbonate, γ-butyrolactone, propylene glycol-1-methyl ether-2-acetate, ethyl lactate, carbitol, carbitol acetate, and the like.

  The triarylsulfonium salt produced by the production method of the present invention has a very high purity and can be used as it is as a photoacid generator or a photocationic polymerization initiator. However, if necessary, monochlorobenzene, toluene, acetic acid can be used. It can be purified by a conventional method such as recrystallization with a solvent such as ethyl, acetone, methanol, ethanol, isopropanol, n-heptane, water or a mixture thereof, activated carbon treatment, or column purification.

The triarylsulfonium salt produced by the production method of the present invention has the formula (2):

(Wherein, R ¹ and R ² are the same as defined above, and R ³ has a monocyclic carbocyclic group which may have a substituent, independently of R ¹ and R ² , and has a substituent. A condensed polycyclic carbocyclic group which may optionally be substituted or a monocyclic heterocyclic group which may have a substituent, wherein X ⁻ represents an inorganic acid ion or an organic acid ion.

In the formula (2), the group represented by R ¹ and the group represented by R ² are the same as described above. (That is, it is the same as the group represented by R ¹ and the group represented by R ² of the diaryl sulfoxide (a) represented by the formula (1)).
In the formula (2), R ³ is a monovalent aryl group obtained by removing one hydrogen atom from the aromatic compound (b). In other words, the structural formula of the aromatic compound (b) can be described as “R ³ —H”.

Examples of R ³ include a phenyl group that may have a substituent, a naphthyl group that may have a substituent, and a thienyl group that may have a substituent. As the “substituent” of the phenyl group which may have a substituent, the naphthyl group which may have a substituent, and the thienyl group which may have a substituent, an alkyl group, an alkoxy group, an alkylthio group Hydroxy group, acetoxy group, halogen atom, phenoxy group, phenylthio group, thienyl group, thienyloxy group, thienylthio group and the like. 1-8 are preferable and, as for carbon number of an alkyl group here, 1-6 are more preferable. 1-6 are preferable and, as for carbon number of an alkoxy group here, 1-4 are more preferable.

Among them, the group R ³ in the case where the structural formula of each compound listed as a specific example of the aromatic compound (b) is described as “R ³ —H” can be preferably used.

Specifically, as R ³ , phenyl group, alkylphenyl group, alkoxyphenyl group, alkylthiophenyl group, hydroxyphenyl group, acetoxyphenyl group, halogen-substituted phenyl group, phenoxyphenyl group, phenylthiophenyl group, naphthyl group, An alkylnaphthyl group, thienyl group, alkylthienyl group, alkylthiothienyl group, hydroxythienyl group, acetoxythienyl group, bitienyl group, phenylthienyl group, phenylthiothienyl group, or R ³ —H is a dithienyl ether or dithienyl sulfide Group (wherein the alkyl group of the alkylphenyl group, alkylthio group, alkylnaphthyl group, alkylthienyl group, or alkylthiothienyl group each independently has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms). The number of carbon atoms of the alkoxy group alkoxyphenyl group 1-6 is preferably, 1 to 4 is more preferred.). Examples of
More specifically, methylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, Isopropoxyphenyl group, n-butoxyphenyl group, isobutoxyphenyl group, sec-butoxyphenyl group, tert-butoxyphenyl group, methylthiophenyl group, ethylthiophenyl group, hydroxyphenyl group, acetoxyphenyl group, fluorophenyl group, chlorophenyl Group, bromophenyl group, biphenyl group, phenoxyphenyl group, phenylthiophenyl group, naphthyl group, methylnaphthyl group, methoxynaphthyl group, thienyl group, methylthienyl group, ethylthienyl group, n-propylthienyl Group, isopropylthienyl group, n-butylthienyl group, tert-butylthienyl group, methoxythienyl group, ethoxythienyl group, n-propoxythienyl group, isopropoxythienyl group, n-butoxythienyl group, isobutoxythienyl group, sec -Butoxythienyl group, tert-butoxythienyl group, methylthiothienyl group, ethylthiothienyl group, hydroxythienyl group, acetoxythienyl group, bitienyl group, phenylthienyl group, phenylthiothienyl group,
R ³ —H is dithienyl ether (preferably one in which the 2-positions of both thiophenes are linked by —O—) or dithienyl sulfide (preferably one in which the 2-positions of both thiophenes are linked by —S—)) Can be preferably exemplified,
More specifically,
2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group (ie, o-tolyl group, m-tolyl group, p-tolyl group), 2-ethylphenyl group, 3-ethylphenyl group, 4- Ethylphenyl group, 2-n-propylphenyl group, 3-n-propylphenyl group, 4-n-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-n- Butylphenyl group, 3-n-butylphenyl group, 4-n-butylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2 n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-n-propoxyphenyl group, 2-isopropoxyphenyl group, 3-isopropoxyphenyl group, 4-isopropoxyphenyl group, 2-n-butoxyphenyl group 3-n-butoxyphenyl group, 4-n-butoxyphenyl group, 2-isobutoxyphenyl group, 3-isobutoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 3-sec- Butoxyphenyl group, 4-sec-butoxyphenyl group, 2-tert-butoxyphenyl group, 3-tert-butoxyphenyl group, 4-tert-butoxyphenyl group, 2-methylthiophenyl group, 3-methylthiophenyl group, 4- Methylthiophenyl group, 2-ethylthiophenyl group, 3-ethylthiophene Group, 4-ethylthiophenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-acetoxyphenyl group, 3-acetoxyphenyl group, 4-acetoxyphenyl group, 2-fluorophenyl Group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-biphenyl Group, 3-biphenyl group, 4-biphenyl group, 2-phenoxyphenyl group, 3-phenoxyphenyl group, 4-phenoxyphenyl group, 2-phenylthiophenyl group, 3-phenylthiophenyl group, 4-phenylthiophenyl group ,
1-naphthyl group, 2-naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl- 1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, 2-methoxy-1-naphthyl group, 3-methoxy-1 -Naphthyl group, 4-methoxy-1-naphthyl group, 5-methoxy-1-naphthyl group, 6-methoxy-1-naphthyl group, 7-methoxy-1-naphthyl group, 8-methoxy-1-naphthyl group, 1 -Methoxy-2-naphthyl group, 3 Methoxy-2-naphthyl group, 4-methoxy-2-naphthyl group, 5-methoxy-2-naphthyl group, 6-methoxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group Group,
2-thienyl group, 3-thienyl group,
3-methylthienyl group, 4-methylthienyl group, 5-methylthienyl group (especially 3-methylthiophen-2-yl group, 4-methylthiophen-2-yl group, 5-methylthiophen-2-yl group),
3-ethylthienyl group, 4-ethylthienyl group, 5-ethylthienyl group (especially 3-ethylthiophen-2-yl group, 4-ethylthiophen-2-yl group, 5-ethylthiophen-2-yl group),
3-n-propylthienyl group, 4-n-propylthienyl group, 5-n-propylthienyl group (especially 3-n-propylthiophen-2-yl group, 4-n-propylthiophen-2-yl group, 5 -N-propylthiophen-2-yl group),
3-isopropylthienyl group, 4-isopropylthienyl group, 5-isopropylthienyl group (especially 3-isopropylthiophen-2-yl group, 4-isopropylthiophen-2-yl group, 5-isopropylthiophen-2-yl group),
3-n-butylthienyl group, 4-n-butylthienyl group, 5-n-butylthienyl group (especially 3-n-butylthiophen-2-yl group, 4-n-butylthiophen-2-yl group, 5 -N-butylthiophen-2-yl group),
3-tert-butylthienyl group, 4-tert-butylthienyl group, 5-tert-butylthienyl group (especially 3-tert-butylthiophen-2-yl group, 4-tert-butylthiophen-2-yl group, 5 -Tert-butylthiophen-2-yl group),
3-methoxythienyl group, 4-methoxythienyl group, 5-methoxythienyl group (especially 3-methoxythiophen-2-yl group, 4-methoxythiophen-2-yl group, 5-methoxythiophen-2-yl group),
3-ethoxythienyl group, 4-ethoxythienyl group, 5-ethoxythienyl group (especially 3-ethoxythiophen-2-yl group, 4-ethoxythiophen-2-yl group, 5-ethoxythiophen-2-yl group),
3-n-propoxythienyl group, 4-n-propoxythienyl group, 5-n-propoxythienyl group (especially 3-n-propoxythiophen-2-yl group, 4-n-propoxythiophen-2-yl group, 5 -N-propoxythiophen-2-yl group),
3-isopropoxythienyl group, 4-isopropoxythienyl group, 5-isopropoxythienyl group (especially 3-isopropoxythiophen-2-yl group, 4-isopropoxythiophen-2-yl group, 5-isopropoxythiophene- 2-yl group),
3-n-butoxythienyl group, 4-n-butoxythienyl group, 5-n-butoxythienyl group (especially 3-n-butoxythiophen-2-yl group, 4-n-butoxythiophen-2-yl group, 5 -N-butoxythiophen-2-yl group),
3-isobutoxythienyl group, 4-isobutoxythienyl group, 5-isobutoxythienyl group (especially 3-isobutoxythiophen-2-yl group, 4-isobutoxythiophen-2-yl group, 5-isobutoxythiophene- 2-yl group),
3-sec-butoxythienyl group, 4-sec-butoxythienyl group, 5-sec-butoxythienyl group (especially 3-sec-butoxythiophen-2-yl group, 4-sec-butoxythiophen-2-yl group, 5 -Sec-butoxythiophen-2-yl group),
3-tert-butoxythienyl group, 4-tert-butoxythienyl group, 5-tert-butoxythienyl group (especially 3-tert-butoxythiophen-2-yl group, 4-tert-butoxythiophen-2-yl group, 5 -Tert-butoxythiophen-2-yl group),
3-methylthiothienyl group, 4-methylthiothienyl group, 5-methylthiothienyl group (especially 3- (methylthio) thiophen-2-yl group, 4- (methylthio) thiophen-2-yl group, 5- (methylthio) thiophene- 2-yl group),
3-ethylthiothienyl group, 4-ethylthiothienyl group, 5-ethylthiothienyl group (especially 3- (ethylthio) thiophen-2-yl group, 4- (ethylthio) thiophen-2-yl group, 5- (ethylthio) ) Thiophen-2-yl group),
3-hydroxythienyl group, 4-hydroxythienyl group, 5-hydroxythienyl group (especially 3-hydroxythiophen-2-yl group, 4-hydroxythiophen-2-yl group, 5-hydroxythiophen-2-yl group),
3-acetoxythienyl group, 4-acetoxythienyl group, 5-acetoxythienyl group (especially 3-acetoxythiophen-2-yl group, 4-acetoxythiophen-2-yl group, 5-acetoxythiophen-2-yl group),
3-phenylthienyl group, 4-phenylthienyl group, 5-phenylthienyl group (especially 3-phenylthiophen-2-yl group, 4-phenylthiophen-2-yl group, 5-phenylthiophen-2-yl group),
3-phenylthiothienyl group, 4-phenylthiothienyl group, 5-phenylthiothienyl group (especially 3- (phenylthio) thiophen-2-yl group, 4- (phenylthio) thiophen-2-yl group, 5- (phenylthio) ) Thiophen-2-yl group), or
A group represented by the following structural formula;

,

Or

Can be illustrated more preferably.

In the formula (2), the inorganic acid ion represented by X ⁻ is an inorganic acid ion of an alkali metal salt or an ammonium salt of an inorganic acid subjected to the reaction. Specifically, hexafluoroantimonate ion, hexafluoroarsenate ion, hexafluorophosphate ion, pentafluorohydroxoantimonate ion, tetrafluoroborate ion, trifluorotristrifluoromethyl phosphate ion, trifluorotrispenta Fluoroethyl phosphate ion, trifluorotriseptafluoropropyl phosphate ion, tetrakis (pentafluorophenyl) borate ion, tetrakis (trifluoromethylphenyl) borate ion, trifluoro (pentafluorophenyl) borate ion, tetrakis ( Examples thereof include difluorophenyl) borate ion and difluorobis (pentafluorophenyl) borate ion.

In the formula (1), the organic acid ion represented by X ⁻ is an organic acid ion of an alkali metal salt or ammonium salt of an organic acid subjected to the reaction. Specifically, methane sulfonate ion, ethane sulfonate ion, propane sulfonate ion, butane sulfonate ion, octane sulfonate ion, trifluoromethane sulfonate ion, perfluorobutane sulfonate ion, perfluorohexane sulfonate ion, Benzenesulfonic acid ion, benzene-1,3-disulfonic acid ion, p-toluenesulfonic acid ion, anthraquinone-1-sulfonic acid ion, anthraquinone-2-sulfonic acid ion, anthraquinone-1,5-disulfonic acid ion, camphorsulfone Acid ion, bis (fluorosulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, cyclo-hexafluoropropane-1,3 Bis (sulfonyl) imide ion, tris (trifluoromethanesulfonyl) Mechidoion like.

  Among these, from the viewpoint of the acid strength and safety of the acid generated when the obtained triarylsulfonium salt is used as a photoacid generator or a photocationic polymerization initiator, hexafluorophosphate ions, trifluorotris Pentafluoroethyl phosphate ion, trifluorotrisheptafluoropropyl phosphate ion, tetrakis (pentafluorophenyl) borate ion, trifluoromethanesulfonate ion, perfluorobutanesulfonate ion, p-toluenesulfonate ion, camphorsulfonate Ion, bis (fluorosulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, cyclo-hexafluoropropane-1,3-bis (sulfonyl) ion Doion and tris (trifluoromethanesulfonyl) Mechidoion are preferred.

Specific examples of the triarylsulfonium salt that can be produced by the production method of the present invention include:
Diphenyl (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl (4-methoxyphenyl) sulfonium perfluorobutanesulfonate, diphenyl (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, diphenyl (4-methoxyphenyl) sulfonium tetrakis ( Pentafluorophenyl) borate, (4-methoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) imide,
Diphenyl (4-ethoxyphenyl) sulfonium hexafluorophosphate, diphenyl (4-ethoxyphenyl) sulfonium perfluorobutanesulfonate, diphenyl (4-ethoxyphenyl) sulfonium trifluoromethanesulfonate, diphenyl (4-ethoxyphenyl) sulfonium tetrakis ( Pentafluorophenyl) borate, (4-ethoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) imide,
Bis (4-methylphenyl) (4-ethoxyphenyl) sulfonium hexafluorophosphate, bis (4-methylphenyl) (4-ethoxyphenyl) sulfonium perfluorobutanesulfonate, bis (4-methylphenyl) (4-ethoxy) Phenyl) sulfonium trifluoromethanesulfonate, bis (4-methylphenyl) (4-ethoxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate, bis (4-methylphenyl) (4-ethoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) Imide,
Bis (4-methylphenyl) (4-butoxyphenyl) sulfonium hexafluorophosphate, bis (4-methylphenyl) (4-butoxyphenyl) sulfonium perfluorobutanesulfonate, bis (4-methylphenyl) (4-butoxy) Phenyl) sulfonium trifluoromethanesulfonate, bis (4-methylphenyl) (4-butoxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate, bis (4-methylphenyl) (4-butoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) Imide,
Bis (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium hexafluorophosphate, bis (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium perfluorobutanesulfonate, bis (4-methoxyphenyl) (4 -Phenylthiophenyl) sulfonium trifluoromethanesulfonate, bis (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium tetrakispentafluorophenylborate, bis (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium bis (trifluoro) Lomethanesulfonyl) imide,
Bis (4-methoxyphenyl) [5- (thiophen-2-ylthio) -thiophen-2-yl] sulfonium fluorophosphate, bis (4-methoxyphenyl) [5- (thiophen-2-ylthio) -thiophen-2 -Yl] sulfonium perfluorobutanesulfonate, bis (4-methoxyphenyl) [5- (thiophen-2-ylthio) -thiophen-2-yl] sulfonium trifluoromethanesulfonate, bis (4-methoxyphenyl) [5- (Thiophen-2-ylthio) -thiophen-2-yl] sulfonium tetrakis (pentafluorophenyl) borate, bis (4-methoxyphenyl) [5- (thiophen-2-ylthio) -thiophen-2-yl] sulfonium bis ( Trifluoromethanesulfonyl) imide,
Bis (4-methylphenyl) (4-phenoxyphenyl) sulfonium hexafluorophosphate, bis (4-methylphenyl) (4-phenoxyphenyl) sulfonium perfluorobutanesulfonate, bis (4-methylphenyl) (4-phenoxy) Phenyl) sulfonium trifluoromethanesulfonate, bis (4-methylphenyl) (4-phenoxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate, bis (4-methylphenyl) (4-phenoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) Imide,
Bis (4-methoxyphenyl) [5- (thiophen-2-ylthio) -thiophen-2-yl] tetrakispentafluorophenylborate,
Diphenyl (4-methoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) imide,
Etc. are preferable.

  Although not particularly limited, in the present invention, the yield of the triarylsulfonium salt represented by the formula (2) obtained with respect to the diaryl sulfoxide represented by the formula (1) as a raw material is preferably 80% or more. 85% or more is more preferable, 90% or more is more preferable, and 95% or more is more preferable.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples at all.

Example 1
<Preparation of diphenyl (4-ethoxyphenyl) sulfonium hexafluorophosphate>
In a 100 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, diphenylsulfoxide 20.2 g (0.10 mol), ethoxybenzene 13.4 g (0.11 mol), methanesulfonic acid 28.8 g (0.30 mol) and 0.13 g (0.001 mol) of aluminum chloride were added, and 50.6 g (0.50 mol) of concentrated sulfuric acid was added dropwise over 2 hours while maintaining the internal temperature at 5 to 15 ° C. . After completion of the dropwise addition, the reaction solution of the condensation reaction product was obtained by stirring for 3 hours while maintaining the same temperature. The reaction rate of diphenyl sulfoxide was 99%.

  A 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 19.3 g (0.105 mol) of potassium hexafluorophosphate, 100 g of water and 100 g of monochlorobenzene, and the internal temperature was 25-40. The whole amount of the reaction solution was added dropwise over 30 minutes while maintaining the temperature. Furthermore, after stirring at 30-40 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Next, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 43.9 g of a pale yellow concentrate. The yield of diphenyl (4-ethoxyphenyl) sulfonium hexafluorophosphate with respect to diphenyl sulfoxide was 97.0%, and the purity by HPLC analysis was 98.3%.

Example 2
<Preparation of diphenyl (4-methoxyphenyl) sulfonium hexafluorophosphate>
In a 100 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, diphenylsulfoxide 20.2 g (0.10 mol), anisole 11.9 g (0.11 mol), methanesulfonic acid 28.8 g ( 0.30 mol) and 0.08 g (0.0006 mol) of aluminum chloride were charged, and 30.3 g (0.30 mol) of concentrated sulfuric acid was added dropwise over 2 hours while maintaining the internal temperature at 5 to 15 ° C. After completion of the dropwise addition, the reaction solution of the condensation reaction product was obtained by stirring for 4 hours while maintaining the same temperature. The reaction rate of diphenyl sulfoxide was 99.7%.

  A 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 19.3 g (0.105 mol) of potassium hexafluorophosphate, 100 g of water and 100 g of monochlorobenzene, and the internal temperature was 25 to 35. The whole amount of the reaction solution was added dropwise over 30 minutes while maintaining the temperature. Furthermore, after stirring at 30-35 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Subsequently, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 43.0 g of a pale yellow concentrate. The yield of diphenyl (4-methoxyphenyl) sulfonium hexafluorophosphate with respect to diphenyl sulfoxide was 98.1%, and the purity by HPLC analysis was 99.3%.

Example 3
<Preparation of bis (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium tetrakispentafluorophenyl borate>
A 100 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 5.2 g (0.02 mol) of bis (4-methoxyphenyl) sulfoxide, 3.9 g (0.02 mol) of diphenyl sulfide, While charging 5.8 g (0.06 mol) of methanesulfonic acid and 0.03 g (0.0002 mol) of aluminum chloride and maintaining the internal temperature at 5 to 15 ° C., 6.1 g (0.06 mol) of concentrated sulfuric acid was added. The solution was added dropwise over 1 hour. After completion of dropping, the mixture was stirred for 2 hours while maintaining the same temperature, and further stirred at 20 to 25 ° C. for 1 hour to obtain a reaction solution of the condensation reaction product. The reaction rate of bis (4-methoxyphenyl) sulfoxide was 99.5%.

  In a 300 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 18.8 g (0.02 mol) of tetrakis (pentafluorophenyl) lithium borate (73 wt% -diethyl ether complex), 100 g of water and Monochlorobenzene (50 g) was charged, and the entire amount of the reaction solution was added dropwise over 30 minutes while maintaining the internal temperature at 30 to 50 ° C. Furthermore, after stirring at 40-50 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Next, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 21.1 g of a pale yellow concentrate. The yield of bis (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium tetrakispentafluorophenylborate relative to bis (4-methoxyphenyl) sulfoxide was 95.0%, and the purity by HPLC analysis was 99.1%. there were.

Example 4
<Preparation of diphenyl (4-methoxyphenyl) sulfonium hexafluorophosphate>
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 20.2 g (0.10 mol) of diphenyl sulfoxide, 11.9 g (0.11 mol) of anisole, and 30.0 g (0. 50 mol) and 0.13 g (0.001 mol) of aluminum chloride were charged, and 60.7 g (0.60 mol) of concentrated sulfuric acid was added dropwise over 1 hour while maintaining the internal temperature at 5 to 15 ° C. After completion of the dropping, the mixture was stirred for 2 hours while maintaining the same temperature, and further stirred at 20 to 25 ° C. for 3 hours to obtain a reaction solution of the condensation reaction product. The reaction rate of diphenyl sulfoxide was 99.3%.

  A 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 19.3 g (0.105 mol) of potassium hexafluorophosphate, 100 g of water and 100 g of monochlorobenzene, and the internal temperature was 25 to 35. The whole amount of the reaction solution was added dropwise over 30 minutes while maintaining the temperature. Furthermore, after stirring at 30-35 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Next, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 42.5 g of a pale yellow concentrate. The yield of diphenyl (4-methoxyphenyl) sulfonium hexafluorophosphate with respect to diphenyl sulfoxide was 97.0%, and the purity by HPLC analysis was 99.1%.

Example 5
<Preparation of bis (4-methylphenyl) (4-butoxyphenyl) sulfonium hexafluorophosphate>
In a 100 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 23.0 g (0.10 mol) of bis (4-methylphenyl) sulfoxide, 16.5 g (0.11 mol) of butoxybenzene, Charge 28.8 g (0.30 mol) of methanesulfonic acid and 0.08 g (0.0006 mol) of aluminum chloride and maintain 30.3 g (0.30 mol) of concentrated sulfuric acid while maintaining the internal temperature at 5 to 15 ° C. It was dripped over 2 hours. After completion of the dropwise addition, the reaction solution of the condensation reaction product was obtained by stirring for 4 hours while maintaining the same temperature. The reaction rate of bis (4-methylphenyl) sulfoxide was 98.5%.

  A 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 19.3 g (0.105 mol) of potassium hexafluorophosphate, 100 g of water and 100 g of monochlorobenzene, and the internal temperature was 25 to 35. The whole amount of the reaction solution was added dropwise over 30 minutes while maintaining the temperature. Furthermore, after stirring at 30-35 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Subsequently, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 49.1 g of a pale yellow concentrate. The yield of bis (4-methylphenyl) (4-butoxyphenyl) sulfonium hexafluorophosphate relative to bis (4-methylphenyl) sulfoxide was 96.6%, and the purity by HPLC analysis was 97.5%. .

Example 6
<Preparation of bis (4-methylphenyl) (4-ethoxyphenyl) sulfonium hexafluorophosphate>
In a 100 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 23.0 g (0.10 mol) of bis (4-methylphenyl) sulfoxide, 13.4 g (0.11 mol) of ethoxybenzene, Charge 28.8 g (0.30 mol) of methanesulfonic acid and 0.08 g (0.0006 mol) of aluminum chloride and maintain 30.3 g (0.30 mol) of concentrated sulfuric acid while maintaining the internal temperature at 5 to 15 ° C. It was dripped over 2 hours. After completion of the dropwise addition, the reaction solution of the condensation reaction product was obtained by stirring for 4 hours while maintaining the same temperature. The reaction rate of bis (4-methylphenyl) sulfoxide was 99.2%.

  A 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 19.3 g (0.105 mol) of potassium hexafluorophosphate, 100 g of water and 100 g of monochlorobenzene, and the internal temperature was 25 to 35. The whole amount of the reaction solution was added dropwise over 30 minutes while maintaining the temperature. Furthermore, after stirring at 30-35 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Next, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 46.1 g of a pale yellow concentrate. The yield of bis (4-methylphenyl) (4-ethoxyphenyl) sulfonium hexafluorophosphate relative to bis (4-methylphenyl) sulfoxide was 96.0%, and the purity by HPLC analysis was 98.7%. .

Example 7
<Preparation of bis (4-methoxyphenyl) [5- (thiophen-2-ylthio) -thiophen-2-yl] tetrakispentafluorophenylborate>
A 100 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 5.2 g (0.02 mol) of bis (4-methoxyphenyl) sulfoxide and 4.0 g of 2,2′-dithienyl sulfide ( 0.02 mol), 9.6 g of acetic acid (0.16 mol) and 0.03 g of aluminum chloride (0.0002 mol) were charged, and 13.7 g of concentrated sulfuric acid was added while maintaining the internal temperature at 5 to 15 ° C. 14 mol) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred for 4 hours while maintaining the same temperature, and further stirred at 20 to 25 ° C. for 2 hours to obtain a reaction solution of the condensation reaction product. The reaction rate of bis (4-methoxyphenyl) sulfoxide was 96.5%.

  In a 300 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 18.8 g (0.02 mol) of tetrakis (pentafluorophenyl) lithium borate (73 wt% -diethyl ether complex), 100 g of water and Monochlorobenzene (50 g) was charged, and the entire amount of the reaction solution was added dropwise over 30 minutes while maintaining the internal temperature at 30 to 50 ° C. Furthermore, after stirring at 40-50 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Next, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 21.6 g of a pale yellow concentrate. The yield of bis (4-methoxyphenyl) [5- (thiophen-2-ylthio) -thiophen-2-yl] tetrakispentafluorophenylborate relative to bis (4-methoxyphenyl) sulfoxide is 96.2%, HPLC The analytical purity was 96.1%.

Example 8
<Preparation of diphenyl (4-methoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) imide>
In a 100 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, diphenylsulfoxide 20.2 g (0.10 mol), anisole 11.9 g (0.11 mol), methanesulfonic acid 28.8 g ( 0.30 mol) and 0.10 g (0.0006 mol) of iron (III) chloride (anhydrous) were charged, and 30.3 g (0.30 mol) of concentrated sulfuric acid was added while maintaining the internal temperature at 5 to 15 ° C. It was added dropwise over time. After completion of the dropwise addition, the reaction solution of the condensation reaction product was obtained by stirring for 4 hours while maintaining the same temperature. The reaction rate of diphenyl sulfoxide was 99.6%.

  A 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 30.1 g (0.105 mol) of bis (trifluoromethanesulfonyl) imide lithium, 100 g of water and 100 g of monochlorobenzene, and the internal temperature was adjusted. While maintaining the temperature at 25 to 35 ° C., the entire amount of the reaction solution was added dropwise over 30 minutes. Furthermore, after stirring at 30-35 degreeC for 30 minutes, the monochlorobenzene layer was fractionated. Subsequently, the obtained monochlorobenzene layer was washed with 50 g of water, and then monochlorobenzene was distilled off to obtain 56.3 g of a pale yellow concentrate. The yield of diphenyl (4-methoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) imide with respect to diphenyl sulfoxide was 98.2%, and the purity by HPLC analysis was 99.3%.

Comparative Example 1 (corresponding to Example 1; no AlCl ₃ )
The reaction was carried out in the same manner as in Example 1 except that aluminum chloride was not used, but the reaction rate of diphenyl sulfoxide was only 10%. Thereafter, stirring was further continued at 20 to 25 ° C. for 3 hours. The reaction rate of diphenyl sulfoxide was 20%, and the production yield of diphenyl (4-ethoxyphenyl) sulfonium hexafluorophosphate, which is the target sulfonium salt, was 10%.

Comparative Example 2 (corresponding to Example 2: no methanesulfonic acid and concentrated sulfuric acid)
A 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 11.9 g (0.11 mol) of anisole, 100 g of monochlorobenzene and 26.7 g (0.20 mol) of aluminum chloride. While maintaining the temperature at 20 to 30 ° C., 20.2 g (0.10 mol) of diphenyl sulfoxide was added in portions over 1 hour. After completion of the addition, the mixture was stirred for 5 hours while maintaining the same temperature, but the reaction did not proceed at all.

  From the above results, according to the production method of the present invention, for example, a triarylsulfonium salt useful as a photoacid generator or a photocationic polymerization initiator can be easily produced in high yield and high purity. all right.

Claims (5)

Formula (1):

(Wherein R ¹ and R ² are each independently a monocyclic carbocyclic group which may have a substituent, a condensed polycyclic carbocyclic group which may have a substituent, or a substituent. A diaryl sulfoxide (a) represented by the following formula (1) and an aromatic compound (b): a Lewis acid (c), a sulfonic acid and / or a carboxylic acid (d ), As well as in the presence of sulfuric acid,
Reaction with an alkali metal salt of an inorganic acid, an ammonium salt of an inorganic acid, an alkali metal salt of an organic acid, or an ammonium salt of an organic acid, formula (2)
Formula (2):

(In the formula, R ¹ and R ² are the same as defined above, and R ³ independently has a monocyclic carbocyclic group, which may have a substituent, independently of R ¹ and R ^2. A condensed polycyclic carbocyclic group which may optionally be substituted or a monocyclic heterocyclic group which may have a substituent, wherein X ⁻ represents an inorganic acid ion or an organic acid ion. A method for producing a salt.   The aromatic compound (b) is at least one selected from the group consisting of arylalkyl ethers, polyaryl ethers, arylalkyl sulfides, polyaryl sulfides, and optionally substituted thiophenes. A process for producing the described triarylsulfonium salt.   The triaryl according to claim 1 or 2, wherein the Lewis acid (c) is at least one selected from the group consisting of aluminum chloride, aluminum bromide, iron chloride, iron bromide, zinc chloride, and zinc bromide. A method for producing a sulfonium salt.   The triaryl according to any one of claims 1 to 3, wherein the sulfonic acid and / or carboxylic acid (d) is at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, acetic acid, and propionic acid. A method for producing a sulfonium salt. The triarylsulfonium salt according to any one of claims 1 to 4, wherein the use ratio of the Lewis acid (c) is 0.0001 to 0.1 mol with respect to 1 mol of the diaryl sulfoxide (a). Method.