JPH0348654A - Compound of sulfonium compound - Google Patents

Abstract

PURPOSE:To readily obtain a sulfonium compound useful for a polymerization catalyst readily and in high yield by reacting a sulfide compound with a benzyl halide and, without isolating a middle reaction product, subjecting the reaction product to anion exchange reaction using a salt. CONSTITUTION:A sulfide compound shown by formula I (R1 is H, acetyl, methoxycarbonyl, ethoxycarbonyl, benzoyl, etc.; R2 is 1-4C alkyl or benzyl) is reacted with a benzyl halide in an organic solvent such as methanol at 25-35 deg.C to give a sulfonium halide shown by formula II (X is halogen). Then the compound is not isolated out of the reaction system and treated with a salt shown by the formula MY (M is alkali metal; Y is SbF6, PF6, BF4 or AsF6) to give the objective compound shown by formula III. The compound shown by formula III is effective as a polymerization catalyst for optically and/or thermally curable composition, especially a polymerizing and curing catalyst for epoxy resins and cationic polymerizable vinyl compounds such as styrene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a sulfonium compound represented by the following general formula.

(However, in the formula, R1 is hydrogen, an acetyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, a benzoyl group, a benzyloxycarbonyl group, or a phenoxycarbonyl group.

4-methoxybenzyloxycarbonyl group or 9-fluorenylmethoxycarbonyl group, R2 is an alkyl group having 1 to 4 carbon atoms or benzyl group, Y is SbF
6. PF (indicates either ASF or BF4.) More specifically, it is useful as a polymerization catalyst for photo and/or thermosetting compositions, particularly for the polymerization of cationically polymerizable vinyl compounds such as epoxy resins and styrene. The present invention relates to a method for producing a sulfonium compound that is effective as a curing catalyst.

[Prior Art] Conventionally, many methods for producing sulfonium compounds have been proposed. For example, in JP-A-55-125104, bis-[4-(diphenylsulfonio)phenylcosulfide bishalide MY (in the formula M
is an alkali metal.

Y is 5bFr, PF6. Indicates ASFG. A manufacturing method is disclosed in which the compound is mixed with a compound represented by the following formula and subjected to ion exchange. However, when MY is reacted in an aqueous solution according to this example, the target sulfonium compound is hydrated during the reaction or in the post-treatment stage because M S b F [, in particular, is very unstable in water. A decomposition reaction may occur, resulting in a low yield of sulfonium compounds or no sulfonium compounds at all. In addition, even if it is obtained, it cannot be obtained with high purity, so
Requires purification process.

In addition, the applicant has also submitted Japanese Patent Application No. 1-4231 and
No. 89517, polyfluoro(sub)metallic salts of benzyl 4-hydroxyphenylalkylsulfoniums are reacted with acid halides in the presence of a base to produce polyfluoro(sub)metallic salts of substituted oxyphenylbenzylalkylsulfoniums. The method is disclosed.

“Problems to be Solved by the Invention” The present invention is directed to isolating an intermediate product, a W-substituted oxyphenylpenzylalkylsulfonium halide compound, from an organic solvent during the production of the sulfonium compound. Instead, an alkali metal salt having a non-nucleophilic anion is added as a powder, and a 1 (3) ion exchange reaction is carried out to form polyfluoro-oxyphenylbenzylalkyl sulfonium in a relatively simple and high-yield manner. A method for producing a metal salt is provided.

[Means to solve the problem] 1! II. The present invention involves reacting a sulfide of the following general formula [Ill with a benzyl halide in an organic solvent to produce a sulfonium halide of the formula -a [Ill]; It consists of a method for producing a sulfonium compound represented by the general formula [II(]) by reacting the sulfonium halide compound represented by the formula [■] with a salt represented by MY without isolating the sulfonium halide compound outside the reaction system.

R, o-4 Prevention S R2 [1] (However, in the formula, R,, R2 and Y are the same as above, X is a halogen atom, and M is an alkali metal.) Function] In carrying out the present invention The substituted oxyphenylalkyl sulfide compound, which is a starting material, can be easily obtained by subjecting 4-hydroxyphenylalkyl sulfide to an esterification reaction with an acid halide or an acid anhydride.

Specific examples of this sulfide are 4-(acetoxy)phenylmethylsulfide, bonyloxy)phenylmethylsulfide, and 4-(benzoyloxy)phenylmethylsulfide.

4-(Benzyloxycarbonyloxy)phenylmethyl sulfide, 4-(phenoxycarbonyloxy)phenylmethyl sulfide, 4-(4-methoxybenzyloxycarbonyloxy)phenylmethyl sulfide, 4-(9-fluorenylmethoxycarbonyl) Oxy)
Phenylmethyl sulfide, 4-(tert-butoxycarbonyloxy)phenylmethyl sulfide, ethyl-4-acetogycyphenyl sulfide, ethyl-4
-(methoxycarbonyloxy)phenyl sulfide,
Examples include 4-(tert-butoxycarbonyloxy)phenylpropyl sulfide.

Specific examples of benzyl halides reacted with the sulfides include benzyl chloride and benzyl bromide. These are used in a molar ratio of 1.0 to 3.0 to the sulfides. Preferably the molar ratio is 1.0 to 1.2. As the organic solvent, one or more alcoholic mixed solvents selected from methanol, ethanol, propatool, etc. are particularly preferred, and the reaction temperature is 40°C or lower, preferably 25°C.
React at a temperature range of ~35°C. Reaction time is 3-7
2 hours, preferably 24 to 48 hours.

The produced substituted or unsubstituted oxyphenylbenzylalkylsulfonium halide compound is continuously converted into an alkali metal salt having a non-nucleophilic anion, such as KSbF6, without being isolated or purified from the reaction solvent. NaSbF6.
NaBF4゜L i BF4. NaPFr,,
KP FG, NaAs FG.

The polyfluoro(sub)metal salt of substituted or unsubstituted oxyphenylbenzylalkylsulfonium is obtained by anion exchange with K A s F G or the like at room temperature.

The amount of alkali metal salt to be used may be in excess of 0.8 to 2% relative to the sulfonium halide compound in order to complete the reaction with the sulfonium halide compound.
．． 0 molar ratio is preferred, more preferably 0.9 to 1.1
It is a molar ratio.

After the reaction, the organic solvent is concentrated and distilled off under reduced pressure, and the residue is extracted with ethyl acetate, dried, and concentrated. The residue is crystallized by a conventional method to isolate a substituted or unsubstituted oxyphenylalkyl sulfonium halide compound as an intermediate product,
The sulfonium compound targeted by the present invention can be easily obtained in high yield without purification.

Specific examples include 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate,
4-acetoxyphenylbenzylmethylsulfonium hexafluoroarsenate.

11-acetoxyphenylbenzylmethylsulfonium tetrafluoroborate, 4-ace1-xyphenylbenzylmethylsulfonium hexafluorophosphate-1, benzyl-4-(benzyloxycarbonyloxy)phenylmethylsulfonium hexafluoroantimonate, benzyl -4-(benzoyloxyphenyl)methylsulfonium hexafluoroantimonate.

Benzylmethyl-4-(phenoxycarbonyloxy)
Phenylsulfonium hexafluoroantimonate, benzyl-4-(methoxycarbonyloxyzafluoroantimonate, benzyl-4-(4meth)~
Hexafluoroantimonate, benzyl-4-(9-fluorenylmethoxycarbonyloxy)phenylmethylsulfonium Hexafluoroantimonate, benzylethyl-4-(ethoxycarbonyloxy) phenylmethylsulfonium
Hexafluoroantimonate, benzyl-4-(tert-butoxycarbonyloxy)phenylmethylsulfonium Hexafluoroantimonate, benzylethyl-4-(benzyloxycarbonyloxy)phenylsulfonium
Examples include hexafluoroantimonate.

EXAMPLES Examples of the present invention will now be given by way of illustration and not limitation.

Example 1 100 g of 4-acetoxyphenylmethyl sulfide was dissolved in 150 g of methanol, and 69 g of benzyl chloride was added to the solution.
．． 5 g was added, heated to 35° C., and stirred for 24 hours.

Next, while stirring the generated methanol layer containing 4-acetoxyphenylbenzylmethylsulfonium chloride, 150.6 g of potassium hexafluoroantimonate was added as a powder, and the mixture was further stirred at room temperature for 1 hour.

The reaction solution is concentrated under reduced pressure, and the residue is extracted with ethyl acetate, washed with water, dried, and concentrated under reduced pressure. A white crystalline substance was obtained from the residue. The product was 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate. The product was confirmed by NMR spectroscopy. The yield is 20
5.2 g, yield 73.5%, melting point 115.0-117°C.

Example 2 50 g of 4-(methoxysulfonyloxy)phenylmethyl sulfide was dissolved in 75 g of methanol, 32 g of benzyl chloride was added thereto, and the mixture was heated to 35°C and stirred for 24 hours. While stirring the methanol layer containing 4-(methoxycarbonyloxy)phenylmethylsulfonium chloride, 69.3 g of potassium hexafluoroantimonate was added as a powder, and the mixture was further stirred at room temperature for 1 hour.

The reaction solution was concentrated under reduced pressure, and the same procedure as in Example 1 was performed to obtain a white crystalline substance. The product was benzyl-4-(methoxycarbonyloxy)phenylmethylsulfonium hexafluoroantimonate. The product was confirmed by NMR spectrum.

Yield: 203.6g, yield 75.4%, melting point: 72.0~
The temperature was 75.0°C.

Example 3 10'Og of 4-(phenoxylsulfonyloxy)phenylmethylsulfide was dissolved in 150g of methanol, and 48.7g of benzyl chloride was added thereto, heated to 35°C, and stirred for 24 hours. Next, while stirring the generated methanol layer containing benzylmethyl-4-(phenoxycarbonyloxy)phenylsulfonium chloride, 105.5 g of potassium hexafluoroantimonate was added as a powder, and the mixture was stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure, and the same procedure as in Example 1 was performed to obtain white crystals. The product was benzylmethyl-4-(phenoxycarbonyloxy)phenylsulfonium hexafluoroantimonate. The product was confirmed by NMR spectrum. Yield: 192.5g, yield 85.3%, melting point 94
．． The temperature was 0 to 96.0°C.

Example 4 4-(benzoyloxy)phenylmethyl sulfide 7
0 g was dissolved in 105 g of methanol, 35.5 g of benzyl chloride was added thereto, and the mixture was heated to 35° C. and stirred for 24 hours. Next, while stirring the generated methanol solution containing benzylmethyl-4-(benzoyloxy)phenylsulfonium chloride at room temperature, 77 g of potassium hexafluoroantimonate was added as a powder, and the mixture was stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure, and the same operation as in Example 1 was performed to obtain a white crystalline substance.

The product was benzylmethyl-4-(benzoyloxy)phenylsulfonium hexafluoroantimonate. The product was confirmed by NMR spectrum. Yield: 131.5g, yield: 82.2%.

The melting point was 113.0-115.0°C.

Example 5 100 g of 4-(benzyloxycarbonyloxy)phenylmethyl sulfide was dissolved in 150 g of methanol, 45.6 g of benzyl chloride was added thereto, and the mixture was heated to 35° C. and stirred for 24 hours. Next, the benzyl-4-(
While stirring the methanol solution containing benzyloxycarbonyloxy)phenylmethylsulfonium chloride, 98.9 g of potassium hexafluorandimonate was added as a powder, and the mixture was stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure, and the same operation as in Example 1 was performed to obtain a white crystalline substance. The product was benzyl-4-(benzyloxycarbonyloxy)phenylmethylsulfonium hexafluoroantimone-1. The product was confirmed by NMR spectrum. The yield was 194.9 parts, yield 90.
0%, melting point 119-120°C.

Example 6 The procedure of Example 5 was repeated. However, in this example, 66.2 g of potassium hexafluorophosphate was used instead of potassium hexafluorandimonate. Yield: 160.4 g of benzyl-4-(benzyloxycarbonyloxy)phenylmethylsulfonium hexafluorophosphate;
Obtained in a yield of 87.3%, with a melting point of 114.0-116.
It was 0'C.

Comparative Example The same procedure as in Example 4 was repeated except for adding an aqueous solution of potassium hexafluoroantimonate to prepare benzylmethyl-4.
-(benzoyloxy)phenylsulfonium hexafluorophosphate was synthesized, but hydrolysis occurred during the reaction or post-treatment, and the desired sulfonium compound could not be obtained.

[Effects of the Invention] According to the production method of the present invention, substituted or unsubstituted oxyphenyl can be produced continuously and effectively in high yield with relatively simple operations and without isolating intermediate products from organic solvents. Polyfluoro(sub)metallic compounds of benzylalkylsulfonium can be produced.

Claims (3)

[Claims] (1) A sulfide compound of the following general formula [I] and benzyl halide are reacted in an organic solvent to produce a sulfonium halide compound of the general formula [II], and then a sulfonium halide compound of the general formula [II] is produced. without isolating it outside the reaction system, by allowing the salt represented by MY to act,
General formula [III
] A method for producing a sulfonium compound represented by: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (However, R_1 in the formula is hydrogen or an acetyl group. , methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, benzoyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-methoxybenzyloxycarbonyl group, 9-fluorenylmethoxycarbonyl group, R_2 is Alkyl group or benzyl group having 1 to 4 carbon atoms, X is a halogen atom, M is an alkali metal, Y is SbF_6, PF_6, AsF_6, BF
_4. ) (2) The manufacturing method according to claim 1, wherein the organic solvent is one or more alcoholic solvents selected from methanol, ethanol, and propanol. (3) The manufacturing method according to claim 1, wherein the reaction temperature for producing the sulfonium halide compound of general formula [II] is 25 to 35°C.