JP3063615B2 - Method for producing triarylsulfonium salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for generating an acid when absorbing and decomposing high energy rays such as far ultraviolet rays, excimer lasers, electron beams and X-rays to perform a condensation reaction, a decomposition reaction and a desorption reaction. Accordingly, the present invention relates to a method for producing a triarylsulfonium salt which is suitably used as a cationic photopolymerization or a component of a resist material.

[0002]

2. Description of the Related Art
As a general method for synthesizing an arylsulfonium salt, a method of condensing a diarylsulfoxide with an aromatic compound in the presence of an acid (S. Smiles and RLR)
ossignol, J. et al. Chem. Soc. , 745
(1908), F.C. Krollpfeoffer, an
d W. Hahn, Chem. Ber. , 86.10
49 (1953); H. Wiegand, W.C. E. FIG.
McEwen, J .; Org. Chem. , 33,267
1 (1968)) and the like. However, in these methods, since the condensation reaction is carried out under acidic conditions, it is difficult to introduce a substituent which is decomposed by an acid, that is, an acid labile group. When a nitrogen-containing substituent such as a group is introduced, an acid is trapped on the nitrogen, losing its electron donating property and deactivating it, so that nucleophilic attack on diaryl sulfoxide is less likely to occur, and the desired product is obtained. It becomes difficult. When a phenol derivative is used as a reagent, the active site of phenol is located at two positions, o-position and p-position.
Sulfonium salts having different substitution positions may be formed.

In addition to the above method, a solvent such as THF or diethyl ether of an aryl Grignard reagent is exchanged for an aliphatic-aromatic hydrocarbon solvent such as heptane-benzene, and then reacted with diphenyl sulfoxide or the like. Method (BS Wildi, SW Taylor and
H. A. Potratz, J .; Am. Chem. So
c. , 73.1965 (1951)), a method in which a solvent such as THF or diethyl ether of an aryl Grignard reagent is exchanged for an aliphatic-aromatic hydrocarbon solvent such as heptane-benzene, and then reacted with thionyl chloride (Research).
ch Disclosure 290,082 (198
8)) and the like, however, these methods require a complicated step of first distilling off the THF or diethyl ether solvent of the aryl Grignard reagent under reduced pressure and then diluting with a heptane-benzene solvent. is there. In addition, when the exchange of the solvent is insufficient, there are problems of yield and reproducibility such that the yield of the arylsulfonium salt is low or the arylsulfonium salt cannot be synthesized at all.

Further, a method of reacting a diaryl sulfoxide with a trialkylsilyl sulfonate under a low temperature condition and further reacting with an aryl Grignard reagent (R.
D. Miller, A .; F. Renaldo, and
H. Ito, J. et al. Org. Chem. , 53.5574
(1988)), but in this method,
Each reagent was added dropwise under low temperature conditions (-70 ° C),
And the temperature control is very complicated, and a cooling bath such as a dry ice-methanol bath and a water bath for aging the reaction are also required. Therefore, a low-temperature device or complicated replacement of the coolant is required, which is not an appropriate method in terms of industrial chemistry and cost. Furthermore, in this method, when a diaryl sulfoxide having an acid labile group is used as a raw material, the acid labile group is cleaved due to an acidic impurity of a trialkylsilyl sulfonate, and it is difficult to synthesize an aryl sulfonium salt. .

In addition, the present inventors have previously made a system in which a diaryl sulfoxide having an acid labile group is reacted with a trialkylsilyl sulfonate and then an aryl Grignard reagent is reacted with an organic base such as triethylamine or pyridine. To suppress the decomposition of the acid labile group and to synthesize a sulfonium salt having an acid labile group. However, in this method, the isolation yield of the raw material diaryl sulfoxide is low, so that the yield of the sulfonium salt may be inferior.In addition, since an organic base is used in the reaction system, there is a possibility that basic impurities may be mixed. Problem. Therefore, it is desired to produce the desired triarylsulfonium salt in high yield without using such an organic base. Further, in the conventional method, for example, after preparing a Grignard reagent in a separate reactor and adding it to the reaction system, it is difficult to perform all the reaction steps in one reactor, and improvement of this point is also demanded. .

The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a method for producing a triarylsulfonium salt, which can produce a triarylsulfonium salt easily and in a high yield.

[0007]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted various studies in order to achieve the above object, and as a result, have found that an excess amount of the aryl Grignard reagent represented by the following general formula (1) is obtained. By reacting with thionyl chloride and then with a triorganosilyl sulfonate or triorganosilyl halide represented by the following general formula (2):
Producing a triarylsulfonium salt represented by the following general formula (3) in high yield without using an organic base;
In this case, it has been found that the entire reaction can be carried out in the reactor used for the preparation of the above-mentioned aryl Grignard reagent, and the reaction device and the reaction operation are simplified.

[0008]

Embedded image (Wherein, R ^{1 to} R ⁵ represent a hydrogen atom or a monovalent organic group, which may be the same or different. R ⁶ represents the same or different monovalent hydrocarbon group, and X represents Represents a bromine atom or a chlorine atom, and Y represents a substituted or unsubstituted alkylsulfonate or arylsulfonate or a halogen atom.)

That is, in the production of a triarylsulfonium salt, the decomposition of an acid labile group can be suppressed without using an organic base by using the above-mentioned aryl Grignard reagent which is a strong alkali as a raw material. In the synthesis process, for example, bis (p-tert-butoxyphenyl)
In order to eliminate the need for isolation of a sulfoxide compound such as sulfoxide or a complicated change of a cooling bath at the time of dropping of triorganosilyl sulfonate, all the reactions can be carried out in a reactor prepared with a Grignard reagent, The inventors have found that the operation in the process becomes very simple, and have accomplished the present invention.

Accordingly, the present invention is to react the aryl Grignard reagent represented by the above general formula (1) with thionyl chloride,
Then, a triorganosilylsulfonate or a triorganosilyl halide represented by the above general formula (2) is reacted to produce a triarylsulfonium salt represented by the above general formula (3). A manufacturing method is provided.

Hereinafter, the present invention will be described in more detail. The aryl Grignard reagent used in the present invention is represented by the following general formula (1).

[0012]

Embedded image

Here, R ^{1 to} R ⁵ are a hydrogen atom or a monovalent organic group, and may be the same or different. In this case, examples of the monovalent organic group include a monovalent hydrocarbon group having 1 to 14 carbon atoms, particularly 1 to 10 carbon atoms (eg, an alkyl group and an aryl group), and an alkoxy group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms. ,
An acetal group or a ketal group having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms in the alkyl group, particularly 1 to 4 carbon atoms;
A dialkylaminoalkyl group represented by ² N-R'- (R is an alkyl group having 1 to 6, particularly 1 to 4 carbon atoms, R 'is an alkylene group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms); 1
To 8, especially 1 to 6 alkylthio groups, 6 to 14 carbon atoms,
Particularly, there may be mentioned 6 to 10 arylthio groups. Also,
X represents a bromine atom or a chlorine atom.

The alkyl group for R ^{1 to} R ⁵ may be linear, branched or cyclic, but may be a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hexyl group, cyclohexyl group and the like, among which methyl group,
Ethyl, isopropyl and tert-butyl groups are more preferably used. As the alkoxy group, linear,
Although it may be branched or cyclic, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a hexyloxy group, a cyclohexyloxy group, and the like, Among them, methoxy group, ethoxy group, isopropoxy group, te
An rt-butoxy group is more preferably used. Examples of the acetal group or ketal group include a tetrahydropyranyloxy group, a tetrahydrofuranyloxy group, a 1-ethoxyethyloxy group, a 1-propoxyethoxy group, and the like, among which a tetrahydropyranyloxy group and a 1-ethoxyethyloxy group are exemplified. It is preferably used. Examples of the dialkylamino group include an N, N-dimethylamino group, an N, N-diethylamino group, an N, N-dibutylamino group,
An N-dimethylaminoethyl group, an N, N-dibutylaminobutyl group and the like are used, and among them, an N, N-dimethylamino group is more preferably used. Further, an aryl group, an aryloxy group, an arylthio group and the like are also preferably used,
A substituent other than the above substituents may be used as long as the substituent can be stably present as the Grignard reagent.

The substitution position may be any of the o, m and p positions. However, it is difficult to obtain an arylsulfonium salt having a substituent having a large steric hindrance at the o position.
And p-positions are preferred.

The above-mentioned aryl Grignard reagent is prepared by a conventional method using an aryl compound represented by the following formula and magnesium.
It can be prepared in an organic solvent such as HF solvent.

[0017]

Embedded image (In the formula, R ^{1 to} R ⁵ and X have the same meanings as described above.)

Next, the triorganosilyl sulfonate or triorganosilyl halide used in the present invention is represented by the following general formula (2). (R ⁶ ) ₃ SiY (2)

Here, R ⁶ is a linear, branched or cyclic monovalent hydrocarbon group, which may be the same or different. In this case, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 6, particularly 1 to 4 carbon atoms, preferably an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms, and preferably 7 to 10 carbon atoms. And particularly, 7 to 8 aralkyl groups and the like. Among them, an alkyl group is preferable.

Y represents a substituted or unsubstituted alkylsulfonate or arylsulfonate or a halogen atom, for example, methanesulfonate, trifluoromethanesulfonate, nonafluorobutanesulfonate, benzenesulfonate, p-toluenesulfonate, 2,4
-Dimethylbenzenesulfonate, 4-tert-butylbenzenesulfonate, pentafluorobenzenesulfonate, 4-fluorobenzenesulfonate, 2,
It is preferable to use a sulfonate such as 2,2-trifluoroethanesulfonate and a halogen atom such as a chlorine atom, a bromine atom and an iodine atom. As such triorganosilyl sulfonates or triorganosilyl halides using a sulfonate or a halogen atom, specifically, trimethylsilyl chloride, tert-butyldimethylsilyl chloride, triethylsilyl bromide, tert-
Butyldimethylsilyl bromide, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl-p-
Toluenesulfonate, trimethylsilyl-4-ter
t-butylbenzenesulfonate, trimethylsilylnonafluorobutanesulfonate, trimethylsilylbenzenesulfonate, tert-butyldimethylsilyl-
p-toluenesulfonate, dimethyl-iso-propylsilyltrifluoromethanesulfonate, trimethylsilyl-2,2,2-trifluoroethanesulfonate, trimethylsilylpentafluorobenzenesulfonate, dimethylphenylsilyltrifluoromethanesulfonate, triethylsilyl-4-fluorobenzenesulfonate, etc. Among them, trimethylsilyl chloride, tert-butyldimethylsilyl chloride, trimethylsilyltrifluoromethanesulfonate, trimethylsilyl-p-toluenesulfonate, tert-butyldimethylsilyltrifluoromethanesulfonate and the like are particularly preferably used.

The method for producing a triarylsulfonium salt according to the present invention is characterized in that the aryl Grignard reagent is used as a solution in an organic solvent such as a THF solvent used for the preparation, or after further diluted with an organic solvent such as THF. A solution of thionyl or thionyl chloride in THF is added dropwise to obtain a diaryl sulfoxide, and the triorganosilyl sulfonate or triorganosilyl halide is isolated without isolating the diaryl sulfoxide, that is, with the aryl Grignard reagent remaining in the reaction system. It is preferable to synthesize a triarylsulfonium salt represented by the following general formula (3) by dropping.

[0022]

Embedded image (However, in the formula, R ^{1 to} R ⁵ and Y have the same meaning as described above.)

In the reaction of the above-mentioned aryl Grignard reagent with thionyl chloride, thionyl chloride is used in an amount of preferably 0.1 to 0.4 mol, particularly 0.2 to 0.1 mol per mol of the aryl Grignard reagent.
Preferably it is 0.3 mol. Thionyl chloride is 0.
When the amount is less than 1 mol, the amount of arylsulfoxide formed is reduced. When the amount of thionyl chloride is more than 0.4 mol, the amount of the aryl Grignard reagent remaining after the reaction with thionyl chloride is reduced, and as a result, the amount of formed triarylsulfonium salt is reduced. Is reduced.

The reaction temperature is preferably -70 to 70 ° C, particularly preferably 0 to 10 ° C. If the reaction temperature is too low, the aryl Grignard reagent solidifies, and a large amount of diluting solvent is required to prevent the solidification. If the reaction temperature is too high, the substituent may be decomposed depending on the type of the substituent. Further, thionyl chloride can be added dropwise as it is or after being diluted with an organic solvent such as THF. However, in order to avoid a rapid rise in temperature due to the reaction, it is preferable to add the thionyl chloride dropwise. The aging of the reaction after the dropwise addition of thionyl chloride is not more than 2 hours, especially 0.5 to 1 hour.
It is preferable to carry out for a time.

When the triorganosilyl sulfonate or triorganosilyl halide is added dropwise after aging of the above reaction, 0.1 to 1 mol of triorganosilyl sulfonate or triorganosilyl halide is added to 1 mol of the aryl Grignard reagent. In particular, it is preferable to drop at a rate of 0.5 to 1 mol. When the amount of triorganosilyl sulfonate or triorganosilyl halide is less than 0.1 mol, the amount of arylsulfonium salt formed is small, and when the amount of triorganosilyl sulfonate or triorganosilyl halide is more than 1 mol, triarylsulfonium having an acid labile group During the synthesis of the salt, the decomposition of the acid labile group may proceed due to acidic impurities in the triorganosilyl sulfonate or triorganosilyl halide.
Further, the temperature range is desirably -10 to 20C for the same reason as in the case of the reaction of thionyl chloride.

The production method of the present invention comprises changing the type of the substituent of the above triarylsulfonium salt,
Various functions as a photoacid generator can be effectively introduced into the triarylsulfonium salt.

That is, according to the method for producing a triarylsulfonium salt of the present invention, for example, tertiary acid labile group
tris (4-tert-butoxyphenyl) sulfonium salt having a t-butoxy group;
tris (3,4-di-t) having two ert-butoxy groups
Functional substituents such as ert-butoxyphenyl) sulfonium salt and tris (4-dimethylaminophenyl) sulfonium salt having a dialkylamino group as a basic component can be introduced into the sulfonium salt. And, for example, a sulfonium salt having a tert-butoxy group which is an acid labile group, a phenol derivative having alkali solubility is generated by decomposition of the acid labile group by the action of an acid generated by irradiation with high energy rays, Since the solubility in an alkaline aqueous solution is different before and after irradiation, it can be suitably used as a component of a chemically amplified positive resist material having a large dissolution contrast and a high resolution suitable for fine processing technology. In addition, sulfonium salts having an amino group as a basic component have no problems such as volatilization of a basic substance, poor compatibility, uneven dispersion, and the like, which occur when a simple basic substance is added. The effect of the group appears with good reproducibility, and it is suitable as a component of a chemically amplified positive resist material. These sulfonium salts can exert great power especially in deep ultraviolet lithography.

[0028]

According to the method for producing a triarylsulfonium salt of the present invention, a triarylsulfonium salt having a functional substituent such as a tert-butoxy group or a dimethylamino group can be prepared by a very simple method and It can be synthesized in high yield.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 Tris trifluoromethanesulfonate (4-tert-
Butoxyphenyl ) sulfonium Synthetic metal magnesium 60.7 g (2.5 mol), 4-te
A Grignard reagent was prepared by a conventional method using 461 g (2.5 mol) of rt-butoxyphenyl chloride and 700 g of THF. The Grignard solution was allowed to cool, and further cooled in an ice water bath, and then 59.5 g (0.5 mol) of thionyl chloride was used.
Was added dropwise at a temperature not exceeding 30 ° C., and the reaction was aged for about 30 minutes. Next, trimethylsilyl trifluoromethanesulfonate 27
7.8 g (1.25 mol) were added dropwise at a temperature not exceeding 20 ° C. Further, the reaction was aged for 1 hour, and then left at room temperature overnight. After the reaction solution was cooled again in an ice water bath,
1800 g of 6.7% aqueous ammonium chloride solution (NH ₄ C
l 300 g + H ₂ O 1500 g) is added at a temperature not exceeding 30 ° C., and after liquid separation, chloroform 1000 is added to the organic layer.
g, and washed three times with 1000 g of water. Thereafter, the solvent was distilled off under reduced pressure with a rotary evaporator,
The resulting oily residue was recrystallized to give 141 g (yield 4 g).
5%), 99% pure tris (4-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate was isolated.

Comparative Example 1 Tris (4-tert-trifluoromethanesulfonate )
Synthesis of butoxyphenyl) sulfonium 24.3 g (1 mol) of magnesium, 203.2 g (1.1 mol) of 4-tert-butoxyphenyl chloride,
A Grignard reagent prepared by a conventional method using 280 g of THF was diluted with 500 g of THF, and cooled to −60 ° C. or lower in a dry ice methanol bath. Then thionyl chloride 4
A solution obtained by diluting 7.5 g (0.4 mol) with 70 g of THF was added dropwise at a temperature not exceeding 0 ° C. over 1 hour. After aging for 1 hour in an ice bath, 36 g of water was added to decompose excess Grignard reagent. 400 g of a saturated aqueous solution of ammonium chloride and 300 g of water were further added to 1000 g of methylene chloride to carry out liquid separation, and the organic solvent layer was washed with 700 g of pure water.
I went there. The organic solvent layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained oil was recrystallized to isolate bis (4-tert-butoxyphenyl) sulfoxide in a yield of 60%.

A solution prepared by dissolving 30.0 g (0.087 mol) of bis (4-tert-butoxyphenyl) sulfoxide and 13.4 g (0.17 mol) of pyridine in 200 g of THF was added with (trimethylsilyl) trifluoromethanesulfonate 37. 0.8 g (0.17 mol) at 0 ° C
The mixture was stirred and added dropwise while controlling the temperature so as not to exceed. Then, the reaction temperature was set to 0 to 5 ° C., and the mixture was stirred for 10 minutes.

The obtained reaction solution was mixed with 4.2 g (0.17 mol) of metallic magnesium, 50 g of THF and 4-te
34.3 g of rt-butoxyphenyl chloride (0.1
(9 mol) was added dropwise while controlling the reaction temperature so as not to exceed 0 ° C.

Next, the reaction temperature was adjusted to 0 to 5 ° C., and the mixture was further stirred for 60 minutes to complete the reaction.

After water was added dropwise to the obtained reaction solution to decompose excess Grignard reagent, filtration was performed to remove the generated inorganic salts. Methylene chloride 60 is added to the obtained filtrate.
0 g, saturated aqueous ammonium chloride solution 300 g, water 400
and then washed twice with 400 g of water. The obtained organic layer was distilled off under reduced pressure to obtain an oily substance. The oil was recrystallized to obtain tris (4-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate having a yield of 50% and a purity of 99%. The yield of this two-step synthesis is 60% for the first step and 50% for the second step.
Therefore, the yield was finally 30%.

Example 2 Tris (3,4-di-t-trifluoromethanesulfonate )
Synthesis of tert-butoxyphenyl ) sulfonium 3,4-di-tert-butoxyphenyl chloride 5
1.3 g (0.2 mol) and 4.9 g of metallic magnesium
(0.2 mol), and a Grignard reagent was prepared by a conventional method using 100 g of THF. The Grignard solution was allowed to cool, and further cooled in an ice water bath, and then 5.8 g of thionyl chloride (0.
(049 mol) in 10 g of THF was added dropwise at a temperature not exceeding 30 ° C., and the reaction was aged for about 30 minutes. Next, 26.7 g (0.12 mol) of trimethylsilyltrifluoromethanesulfonate was added dropwise at a temperature not exceeding 20 ° C. Further, the reaction was aged for 1 hour, and then left at room temperature overnight. After the reaction solution was cooled again in an ice water bath, 200 g of a 16.7% aqueous ammonium chloride solution was added to 30 g of the reaction solution.
After adding at a temperature not exceeding ℃, and separating the solution, 100 g of chloroform was added to the organic layer, and the mixture was washed three times with 100 g of water.
Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain an oily substance. The oil was recrystallized to yield 1
3.2 g (yield 32%) of 99% pure tris (3,4-di-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate was isolated.

Comparative Example 2 Tris (3,4-di-t-trifluoromethanesulfonate )
Synthesis of tert-butoxyphenyl ) sulfonium A Grignard reagent was prepared by a conventional method using 3,4-di-tert-butoxyphenyl chloride, metallic magnesium and THF, and further reacted with thionyl chloride to obtain bis (3,4- Di-tert-butoxyphenyl) sulfoxide was obtained in a yield of 64%. Next, this bis (3,4-di-tert-butoxyphenyl) sulfoxide 58.9.
g (0.12 mol) was dissolved in 120 g of THF and cooled in an ice-water bath. To this 12.1 g of triethylamine
(0.12 mol), and 68.3 g (0.31 mol) of trimethylsilyl triflate was further added dropwise while controlling so as not to exceed 10 ° C. In this solution,
61.6 g (0.24 mol) of 1,2-di-tert-butoxy-4-chlorobenzene, metallic magnesium 5.8
g (0.24 mol) and 100 g of THF were added dropwise while controlling a Grignard reagent prepared by a conventional method so as not to exceed 10 ° C. Further, the reaction temperature is set to 0 to 10 ° C.
The reaction was aged for 30 minutes. After the reaction was stopped and separated by adding 700 g of a 20% aqueous ammonium chloride solution to the reaction solution, 300 g of chloroform was added to the organic layer. After the organic layer was washed twice with 300 g of water, the solvent was distilled off under reduced pressure to obtain an oil. This oil was subjected to column chromatography (silica gel: eluent, chloroform-methanol) to give tris (3,4-di-tert-trifluoromethanesulfonic acid) with a yield of 20% and a purity of 99%.
(t-butoxyphenyl) sulfonium was obtained. The final yield of this two-step synthesis was 13%.

Example 3 Tris (4-dimethylatrifluoromethanesulfonate)
Synthesis of minophenyl) sulfonium 100 g of 4-bromo-N, N-dimethylaniline (0.
5 mol), 12.1 g (0.5 mol) of metallic magnesium
A Grignard reagent was prepared by a conventional method using and 250 g of THF. After cooling the Grignard solution and further cooling in an ice water bath, a solution obtained by diluting 14.3 g (0.12 mol) of thionyl chloride with 20 g of THF was added dropwise at a temperature not exceeding 30 ° C., and the reaction was matured. Performed for 30 minutes. Next, 66.7 g of trimethylsilyl trifluoromethanesulfonate
(0.3 mol) was added dropwise at a temperature not exceeding 20 ° C. Further, the reaction was aged for 1 hour and then left at room temperature overnight. After the reaction solution was cooled again in an ice water bath, 14.6%
820 g of an aqueous ammonium chloride solution was added at a temperature not exceeding 30 ° C., and after liquid separation, 200 g of chloroform was added to the organic layer, followed by washing three times with 200 g of water. Thereafter, the solvent was distilled off under reduced pressure by a rotary evaporator, and the obtained oily residue was recrystallized to give a yield of 36.5 g (56%).
Tris trifluoromethanesulfonic acid having a purity of 99% (4
-Dimethylaminophenyl) sulfonium was isolated.

Comparative Example 3 Tris (4-dimethylatrifluoromethanesulfonate)
Synthesis of minophenyl) sulfonium Bis (4-dimethylaminophenyl) sulfoxide is prepared by preparing a Grignard reagent by a conventional method using 4-dimethylaminophenyl bromide, metallic magnesium and THF, and reacting the Grignard reagent with thionyl chloride. Was obtained in a yield of 33%. 7.0 g (0.024 mol) of this bis (4-dimethylaminophenyl) sulfoxide
Was dissolved in 100 g of methylene chloride and cooled to −70 ° C. using a dry ice methanol bath, and then 6.0 g (0.027 mol) of trimethylsilyl triflate was dissolved.
Was stirred and dropped at a temperature not exceeding -60 ° C.

Then, the reaction temperature was adjusted to 0 to 5 ° C. by replacing the dry ice methanol bath with an ice water bath, followed by stirring for 10 minutes.

The resulting reaction solution was cooled again to -70 ° C. using a dry ice methanol bath, and then 9.9 g (0.049 mol) of 4-bromo-N, N-dimethylaniline and 1.19 g of metallic magnesium were added. A Grignard reagent prepared by an ordinary method using 2 g (0.049 mol) and 20 g of THF was stirred and added dropwise at a reaction temperature not exceeding -60 ° C.

Then, the reaction was replaced with an ice-water bath again, and the reaction temperature was set to 0.
The mixture was stirred at 分 間 5 ° C. for 60 minutes to complete the reaction.

After 300 g of a 15% aqueous ammonium chloride solution was added to the reaction solution to carry out liquid separation, the organic solvent layer was washed twice with 150 g of water. The solvent was distilled off from the obtained organic layer under reduced pressure using a rotary evaporator to obtain an oily substance. The obtained oil was subjected to silica gel column chromatography to obtain tris (4-dimethylaminophenyl) sulfonium trifluoromethanesulfonate with a yield of 40% and a purity of 99%. The final yield of this two-step synthesis was 13% since the first step was 33% and the second step was 40%.

Example 4 Tris p-toluenesulfonate (4-tert-butoxy)
Synthesis of (cyclophenyl) sulfonium In Example 1, trimethylsilyl-p-toluenesulfonate (boiling point 113 to 117 ° C) obtained by a conventional method using p-toluenesulfonic acid and trimethylsilyl chloride instead of 277.8 g of trimethylsilyltrifluoromethanesulfonate. /0.5-0.6mmHg)
A sulfonium salt having p-toluenesulfonic acid as a counter anion was synthesized in the same manner as in Example 1 except that 305 g (1.25 mol) of p-toluenesulfone having a yield of 45% and a purity of 99% was used. Tris acid (4-tert
-Butoxyphenyl) sulfonium was obtained.

Comparative Example 4 Tris p-toluenesulfonic acid (4-tert-butoxy)
Synthesis of Cyphenyl) sulfonium Bis (4-tert) obtained in a yield of 60% as in Comparative Example 1.
-Butoxyphenyl) sulfoxide 10.0 g (0.0
29 mol), and a solution of 5.8 g (0.058 mol) of triethylamine dissolved in 115 g of THF was added with 14.2 g (0.2%) of (trimethylsilyl) p-toluenesulfonate.
(058 mol) was stirred and added dropwise while controlling the temperature so as not to exceed 0 ° C. Then, the reaction temperature was adjusted to 0 to 5 ° C., and the mixture was stirred for 30 minutes.

To the obtained reaction solution, 1.4 g (0.058 mol) of metallic magnesium, 16 g of THF and 4-t
ert-butoxyphenyl chloride 11.8 g (0.
(064 mol) was added dropwise while controlling the reaction temperature so as not to exceed 0 ° C. Next, the reaction was stirred for an additional 60 minutes so that the reaction temperature was 0 to 5 ° C., and the reaction was terminated.

After the excess Grignard reagent was decomposed by adding water dropwise to the obtained reaction solution, filtration was performed to remove the generated inorganic salts. Methylene chloride 60 is added to the obtained filtrate.
0 g, saturated aqueous ammonium chloride solution 200 g, water 200
g, and then washed three times with 500 g of water. The obtained organic layer was distilled off under reduced pressure to obtain an oily substance. The obtained oil was recrystallized to obtain tris (4-tert-butoxyphenyl) sulfonium p-toluenesulfonate having a yield of 28% and a purity of 99%. Since the isolation yield of the raw material sulfoxide was 60%, the final yield was 17%.

Example 5 Tris (4-dimethylaminophenyl ) p-toluenesulfonate
Synthesis of phenyl) sulfonium 100 g of 4-bromo-N, N-dimethylaniline (0.
5 mol), 12.1 g (0.5 mol) of metallic magnesium
And a 500-g portion of THF to prepare a Grignard reagent by a conventional method. After cooling the Grignard solution, it was cooled in an ice water bath. 14.3 g (0.12 mol) of thionyl chloride was added to THF
The solution diluted with 20 g was added dropwise at a temperature not exceeding 30 ° C. The reaction was aged for about 30 minutes. Next, 73.3 g of trimethylsilyl-p-toluenesulfonate (0.3
Mol) was added dropwise at a temperature not exceeding 20 ° C. Further, the reaction was aged for 1 hour, and then left at room temperature overnight. The reaction solution was cooled again in an ice-water bath, 1500 g of an aqueous 14.6% ammonium chloride solution was added at a temperature not exceeding 30 ° C. After liquid separation, 400 g of chloroform was added to the organic layer, and 200 g of water was added.
And washed three times. The solvent was distilled off under reduced pressure using a rotary evaporator, and the obtained oily residue was recrystallized to give a yield of 3
9.9 g (yield 59%) of tris (4-dimethylaminophenyl) sulfonium p-toluenesulfonate having a purity of 99% were isolated.

[Comparative Example 5] Tris (4-dimethylaminophen ) p-toluenesulfonate
Synthesis of phenyl ) sulfonium A Grignard reagent was prepared from 4-dimethylaminophenyl bromide and metallic magnesium in a THF solvent by a conventional method.
By reacting with thionyl chloride, bis (4-dimethylaminophenyl) sulfoxide was obtained in a yield of 33%.

The above bis (4-dimethylaminophenyl)
A solution of 7.0 g (0.024 mol) of sulfoxide dissolved in 200 g of methylene chloride was cooled to -70 ° C using a dry ice methanol bath, and then trimethylsilyl-
6.6 g (0.027 mol) of p-toluenesulfonate
Was stirred and dropped at a temperature not exceeding -60 ° C.

Next, the reaction temperature was set to 0 to 5 ° C. by replacing the dry ice methanol bath with an ice water bath, followed by stirring for 10 minutes.

After the obtained reaction solution was cooled again to -70 ° C using a dry ice methanol bath, 4-bromo-
10 g (0.05 mol) of N, N-dimethylaniline, 1.2 g (0.05 mol) of metallic magnesium and THF20
The Grignard reagent prepared by a conventional method using g was stirred and added dropwise at a temperature at which the reaction temperature did not exceed -60 ° C.

Next, the reaction temperature was changed to 0 by replacing the ice water bath again.
The mixture was stirred at 分 間 5 ° C. for 60 minutes to complete the reaction.

After 500 g of a 15% aqueous ammonium chloride solution was added to the reaction solution to carry out liquid separation, the organic solvent layer was separated with water 2
Water washing was performed twice using 00 g. The solvent was distilled off from the obtained organic layer under reduced pressure using a rotary evaporator to obtain an oily substance. The resulting oil was subjected to silica gel column chromatography to give a yield of 6.1 g (45%).
99% pure tris (4-dimethylaminophenyl) sulfonium p-toluenesulfonate was obtained.

The yield of this two-step synthesis was 15% since the first step was 33% and the second step was 45%.

[Examples 6 to 9] Instead of trimethylsilyl-p-toluenesulfonate used in Example 5, trimethylsilyl-p-fluorobenzenesulfonate, trimethylsilyl-2,2,2-trifluoroethanesulfonate, trimethylsilylnonafluorobutane The synthesis was carried out in the same manner as in Example 5 except that sulfonate and trimethylsilylpentafluorobenzenesulfonate were used, and the desired products were obtained in the following yields and purities, respectively. Example 6 Tris (4-dimethylaminophenyl) sulfonium p-fluorobenzenesulfonate (99% purity, 55% yield)
%) Example 7 Tris 2,2,2-trifluoroethanesulfonic acid (4
-Dimethylaminophenyl) sulfonium (purity 99
%, Yield 48%) Example 8 Tris (4-dimethylaminophenyl) sulfonium nonafluorobutanesulfonate (purity 99%, yield 58)
%) Example 9 Tris (4-dimethylaminophenyl) sulfonium pentafluorobenzenesulfonate (purity: 99%, yield: 5%)
0%)

[Comparative Examples 6 to 9] Instead of trimethylsilyl-p-toluenesulfonate used in Comparative Example 5, trimethylsilyl-p-fluorobenzenesulfonate, trimethylsilyl-2,2,2-trifluoroethanesulfonate, trimethylsilylnonafluorobutane The synthesis was carried out in the same manner as in Comparative Example 5 except that sulfonate and trimethylsilylpentafluorobenzenesulfonate were used, and the desired products were obtained in the following yields and purities, respectively. Comparative Example 6 Tris (4-dimethylaminophenyl) sulfonium p-fluorobenzenesulfonate (98% purity, 38 yield)
%) The yield of this two-step synthesis was 13% since the first step was 33% and the second step was 38%. Comparative Example 7 Tris 2,2,2-trifluoroethanesulfonic acid (4
-Dimethylaminophenyl) sulfonium (purity 99
%, Yield 37%) The yield of this two-step synthesis method was 12% because the first step was 33% and the second step was 37%. Comparative Example 8 Tris (4-dimethylaminophenyl) sulfonium nonafluorobutanesulfonate (99% purity, 45% yield)
%) The yield of this two-step synthesis was 15% since the first step was 33% and the second step was 45%. Comparative Example 9 Tris (4-dimethylaminophenyl) sulfonium pentafluorobenzenesulfonate (purity 99%, yield 4
1%) The yield of this two-step synthesis was 13% since the first step was 33% and the second step was 28%. Table 1 shows the yields in the production methods of the above Examples and Comparative Examples.

[0058]

[Table 1]

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Shimada sequentially 28-1 Nishifukushima, Oku-ku, Nakakushiro-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd. Synthetic Technology Research Laboratories (72) Inventor Toshinobu Ishihara Nishigata 28-1 Nishi-Fukushima Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (56) References JP-A-2-1469 (JP, A) JP-A-53-44533 (JP, A) JP-A-61-212554 (JP) , A) Research Disclosure, No. 290 p. 414 (1988) Journal of Organic Chemistry, Vol. 53 No. 23 p. 5571-5573 (1988) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 381/12 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R ^{1 to} R ⁵ represent a hydrogen atom or a monovalent organic group, which may be the same or different from each other, and X represents a bromine atom or a chlorine atom). With thionyl chloride, and then the following general formula (2) (R ⁶ ) ₃ SiY (2) (wherein R ⁶ is the same or different monovalent hydrocarbon group, and Y is substituted or unsubstituted) A substituted alkylsulfonate, an arylsulfonate or a halogen atom) represented by the following general formula (3): (Wherein, R ^{1 to} R ⁵ and Y have the same meanings as described above). 2. The method according to claim 1, wherein R ^{1 to} R ⁵ in the general formula (1) are a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an acetal group, a ketal group, an aryloxy group, a dialkylamino group, a dialkylaminoalkyl group, The method for producing a triarylsulfonium salt according to claim 1, which is an alkylthio group or an arylthio group. 3. After reacting 0.1 to 0.4 mol of thionyl chloride with respect to 1 mol of the aryl Grignard reagent of the general formula (1), 1 mol of the aryl Grignard reagent of the general formula (2) 3. The process for producing a triarylsulfonium salt according to claim 1, wherein 0.1 to 1 mol of the triorganosilylsulfonate or triorganosilyl halide is reacted. 4. The triorganosilyl sulfonate of the general formula (2) without adding a reaction product after adding thionyl chloride to the reactor in which the aryl Grignard reagent of the general formula (1) is prepared. 4. The method for producing a triarylsulfonium salt according to claim 1, wherein a triorganosilyl halide is added.