JP2803454B2 - Sulfonium complex or oxosulfonium complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel sulfonium complex or oxosulfonium complex which generates an active radical efficiently by giving light and / or heat energy. More specifically, it has a remarkably good effect as a polymerization initiator for a polymerizable substance, and requires high sensitivity by applying light energy from various light sources such as a mercury lamp or a laser and / or applying heat energy by heating or a thermal head. For forming various types of printing materials, hologram materials and various recording media using microcapsules, inks, adhesives, adhesives, adhesives, sealants, etc. It relates to a useful sulfonium complex or oxosulfonium complex.

[0002]

2. Description of the Related Art Hitherto, a large number of syntheses of various sulfonium complexes and oxosulfonium complexes have been reported, which are described in The Chemical Society of Japan, New Experimental Chemistry, Vol. 14, p. 1838 (Maruzen, 1978), Dai Famo,
Organic Sulfur Chemistry (Synthetic Reaction Edition), 237 pages (1982,
Doujin Kagaku), BMTrost and LSMelvin, Jr., “Su
lfer Ylides ", p. 6, (1975, Academic PRES
S) etc. In particular, diarylsulfonium complexes are described in The Chemical Society of Japan, Vol. 87, No. 5,
The diarylsulfonium complex is described in page 456 (1966), the diphenylsulfonium complex is described in The Chemical Society of Japan, Vol. 87, No. 10, p. 1969 (1966), and the Journal of Chemical Society (J. Chem. So
c.), (C), p. 682 (1970) report diaryl (aryloxy) sulfonium complexes. In addition, European Patent No. 35969 discloses some (diaryl) oxosulfonium complexes.

However, in all of the diarylsulfonium complexes and diaryloxosulfonium complexes reported in these documents and patents, the anion portion is a halogen atom, NO ₃ , BF ₄ , PF ₆ , SbF ₆ ,
An inorganic anion such as SbCl ₆ , AsF ₆ , ClO ₄ or HgI ₃ or an anion of an organic acid such as a sulfonic acid or a carboxylic acid such as trifluoromethyl sulfate, p-toluenesulfonate or benzoate, and the anion portion is an organic boron anion As the diarylsulfonium complex or diaryloxosulfonium complex consisting of
Only diaryl and triarylsulfonium borate complexes disclosed in JP-A-2-177760 are known, and neither a sulfonium complex nor an oxosulfonium complex represented by the following general formula (1) is known.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to propose a sulfonium complex and an oxosulfonium complex which generate an active radical efficiently by applying light and / or heat energy. For more information,
It has a remarkably good effect as a polymerization initiator for polymerizable substances, and various printing plates requiring high sensitivity by applying light energy from various light sources such as mercury lamps and lasers and / or heat energy from heating or a thermal head. Sulfonium useful for forming polymers and cured products with good physical properties, such as various recording media, printing inks, adhesives, adhesives, adhesives, and sealants that use materials, hologram materials, and microcapsules To provide a complex or an oxosulfonium complex.

A diarylsulfonium complex in which the anion portion comprises an organic boron anion is disclosed in JP-A-2-17776.
The diaryl and triarylsulfonium borate complexes disclosed in Japanese Patent Publication No. 0 are known, but all of these have low reduction potentials, so that they do not efficiently generate radicals and are not sensitive enough. . Therefore, development of a polymerization initiator that can solve these problems has been desired.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems in consideration of the above problems, and as a result, have reached the present invention. That is, the present invention is a sulfonium complex or an oxosulfonium complex represented by the general formula (1), which generates an active radical by applying light and / or thermal energy. General formula (1) (However, R ¹ and R ² each have an aryl group which may have a substituent, and R ³ has a phenacyl group which may have a substituent, a benzyl group which may have a substituent or a substituent. R ⁴ is an oxygen atom or a lone electron pair; R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group which may have a substituent, It is aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a group selected from optionally alicyclic group which may have a substituent, R ^5, R ⁶ , R ⁷ and R ⁸ do not simultaneously form an aryl group which may have a substituent.)

R ¹ and R ^{2 in} the general formula (1) are an aryl group which may have a substituent, for example, a phenyl group,
p-tolyl group, xylyl group, cumenyl group, naphthyl group,
Anthryl group, phenanthryl group, and the like, and the hydrogen atom of these groups may be further substituted with another substituent.Examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Halogen groups such as atoms,
Methoxy group, ethoxy group, alkoxy group such as tert-butoxy group, phenoxy group, aryloxy group such as p-tolyloxy group, methoxycarbonyl group, butoxycarbonyl group, acetoxy group, ester group such as benzoyloxy group, acetyl group, Acyl groups such as isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, and phenacyl group; alkylthio groups such as methylthio group and tert-butylthio group; arylthio groups such as phenylthio group and p-tolylthio group; methylamino group; cyclohexylamino group Such as alkylamino group, dimethylamino group,
Dialkylamino group such as diethylamino group, morpholino group, piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, te
alkyl groups such as rt-butyl group and dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, aryl groups such as phenanthryl group, etc., hydroxy group, carboxy group, formyl group , Mercapto, sulfo, mesyl, p-toluenesulfonyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, trimethylammonium, dimethylsulfo A niumyl group and a triphenylphenacylphosphonium group;

R ^{3 in the} general formula (1) is a phenacyl group which may have a substituent, a benzyl group which may have a substituent or an allyl group which may have a substituent. The phenacyl group which may have a substituent includes, for example, phenacyl group, p-chlorophenacyl group, p-bromophenacyl group, p-cyanophenacyl group, p-nitrophenacyl group, m-methoxy Examples of the benzyl group in which a phenacyl group or the like may also have a substituent include, for example, a benzyl group, a p-chlorobenzyl group,
Bromobenzyl group, p-cyanobenzyl group, m-nitrobenzyl group, p-nitrobenzyl group, anisyl group, etc.
Examples of the allyl group which may have a substituent include, for example,
Allyl group, cinnamyl group, 2-butenyl group, 3,3-dicyano-2-phenyl-2-propenyl group, 3,3-bis (methoxycarbonyl) -2-phenyl-2-propenyl group, and the like. May be further substituted with another substituent. Examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a methoxy group, a tert- Alkoxy groups such as butoxy groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, butoxycarbonyl groups,
Ester groups such as acetoxy group and benzoyloxy group, acyl groups such as acetyl group, acryloyl group and methoxalyl group; alkylthio groups such as methylthio group and tert-butylthio group; arylthio groups such as phenylthio group and p-tolylthio group; methylamino Group, alkylamino group such as cyclohexylamino group, dialkylamino group such as diethylamino group, morpholino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ter
In addition to alkyl groups such as t-butyl group and dodecyl group, aryl groups such as phenyl group and p-tolyl group, hydroxy group, carboxy group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, nitro group , Cyano group,
Examples include a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammonium group, a dimethylsulfonium group, and a triphenylphenacylphosphonium group.

Further, R ⁵ , R ⁶ , R ⁷ and R ⁸ of the general formula (1) may have an alkyl group which may have a substituent, an aryl group which may have a substituent, and An alkenyl group which may be substituted, an alkynyl group which may have a substituent, or a group selected from an alicyclic group which may have a substituent; examples of the alkyl group which may have such a substituent include: , Methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group,
Pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, etc., as the aryl group which may have a substituent, phenyl group, p-tolyl group, xylyl group, mesityl group, cumenyl group, etc. However, as the alkenyl group which may have a substituent, a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group and the like, and as an alkynyl group which may have a substituent, an ethynyl group, 1-
Hexinyl group, 1-propynyl group, etc., as the alicyclic group which may have a substituent, cyclohexyl group, cyclopentyl group, cyclohexenyl group, norbornyl group, bornyl group, menthyl group, pinanyl group, adamantyl group, etc. The hydrogen atom of these groups may be further substituted with another substituent. Examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, a halogen group such as an iodine atom, and a methoxy group. Groups, alkoxy groups such as tert-butoxy group, alkyl groups such as phenoxy group, methyl group, tert-butyl group and dodecyl group, aryl groups such as phenyl group and p-tolyl group, mesyl group, p-toluene Examples include a sulfonyl group and a trifluoromethyl group.

The substituent R ⁵ on the borate anion in the general formula (1) is an alkyl group which may have a substituent, and R ⁶ , R ⁷ and R ⁸ may have a substituent. When the structure is an aryl group, it is considered that the substituent R ⁵ on the borate anion, that is, the alkyl group which may have a substituent is preferentially and efficiently cleaved to generate a radical. When used, a significant increase in sensitivity is observed.

On the other hand, when all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are simultaneously an aryl group which may have a substituent, the borate anion is not efficiently cleaved and when used as a polymerization initiator, Such a structure is not preferable.

Accordingly, specific examples of the sulfonium complex and the oxosulfonium complex corresponding to the present invention include:
The cation moiety is diphenylphenacylsulfonium, bis (p-tert-butylphenyl) phenacylsulfonium, bis (p-chlorophenyl) phenacylsulfonium, diphenyl (p-chlorophenacyl) sulfonium, diphenyl (p-nitrophenacyl) sulfonium , Diphenyl (m-methoxyphenacyl) sulfonium, diphenyl (p-cyanophenacyl) sulfonium, diphenyl [(1-naphthyl) carbonylmethyl]
Sulfonium, diphenylbenzylsulfonium, bis (p-tert-butylphenyl) benzylsulfonium, bis (p-chlorophenyl) benzylsulfonium, diphenyl (p-chlorobenzyl) sulfonium,
Diphenyl (p-nitrobenzyl) sulfonium, diphenyl (p-cyanobenzyl) sulfonium, diphenyl [(1-naphthyl) methyl] sulfonium, diphenylallylsulfonium, bis (p-tert-butylphenyl) allylsulfonium, bis (p-chlorophenyl) ) Allylsulfonium, diphenyl (3,3-dicyano-2-phenyl-2-propenyl) sulfonium, diphenyl [3,3-bis (methoxycarbonyl) -2-
Phenyl-2-propenyl] sulfonium, diphenyl (3,3-dicyano-2-methyl-2-propenyl) sulfonium, diphenylphenacyloxosulfonium, bis (p-tert-butylphenyl) phenacyloxosulfonium, diphenyl (p- Chlorophenacyl) oxosulfonium, diphenyl (p-cyanophenacyl) oxosulfonium, diphenyl [(1-naphthyl) carbonylmethyl] oxosulfonium, diphenylbenzyloxosulfonium, bis (p-chlorophenyl) benzyloxosulfonium, diphenyl (p
-Cyanobenzyl) oxosulfonium, diphenylallyloxosulfonium, bis (p-tert-butylphenyl) allyloxosulfonium, diphenyl (3,3-dicyano-2-phenyl-2-propenyl)
Each sulfonium cation or oxosulfonium cation such as oxosulfonium and diphenyl [3,3-bis (methoxycarbonyl) -2-phenyl-2-propenyl] oxosulfonium;
Butyl triethyl borate, phenyl triethyl borate, tributyl benzyl borate, diethyl dibutyl borate, dibutyl diphenyl borate, methyl triphenyl borate, ethyl triphenyl borate, propyl triphenyl borate, isopropyl triphenyl borate, butyl triphenyl borate, sec-butyl triphenyl Borate, tert-butyl triphenyl borate, dodecyl triphenyl borate, benzyl triphenyl borate, vinyl triphenyl borate, ethynyl triphenyl borate, butyl trimesityl borate, butyl tris (p-methoxyphenyl) borate,
Butyl tris (p-fluorophenyl) borate, butyl tris (p-bromophenyl) borate, sec-butyl tris (p-methoxyphenyl) borate, sec
-Butyl tris (p-fluorophenyl) borate, t
Sulfonium complexes and oxosulfonium complexes composed of a combination with each borate anion such as tert-butyltris (p-bromophenyl) borate and butyltris [3,5-bis (trifluoromethyl) phenyl] borate. The invention is not limited to these examples.

The sulfonium complex or oxosulfonium complex of the general formula (1) of the present invention is obtained by converting the sulfonium complex or the oxosulfonium complex of the general formula (2) and the organic boron compound represented by the general formula (3) into a predetermined compound. It can be synthesized by reacting in an organic solvent or water, or a mixed solvent of water and an organic solvent.

General formula (2) (However, R ¹ and R ² each have an aryl group which may have a substituent, and R ³ has a phenacyl group which may have a substituent, a benzyl group which may have a substituent or a substituent. Allyl group, R ⁴ is an oxygen atom or a lone electron pair, X is a halogen atom, BF ₄ , PF ₆ , Sb
Inorganic anions such as F ₆ , SbCl ₆ , AsF ₆ and ClO ₄ , and anions of organic acids such as benzoate, methyl sulfate, trifluoromethyl sulfate, benzene sulfonate and p-toluene sulfonate are shown. )

General formula (3) (Where M is an alkali metal, ammonium or substituted ammonium, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group optionally having a substituent or an aryl group optionally having a substituent , an optionally substituted alkenyl group, an optionally substituted alkynyl group, a group selected from optionally alicyclic group which may have a substituent, R ^5,
All of R ⁶ , R ⁷ and R ⁸ do not simultaneously form an aryl group which may have a substituent. )

The sulfonium complex or oxosulfonium complex of the general formula (2), which is used as a starting material for synthesizing the sulfonium complex or the oxosulfonium complex of the general formula (1), can be obtained from the Chemical Society of Japan, New Experimental Chemistry, Chapter 14 roll,
1838 (Maruzen, 1978) and Daifushimo, Organic Sulfur Chemistry (Synthetic Reactions), 237 (1982, Doujin Kagaku), BMTrost and LSMelvin, Jr., “Sulfer Y
lides ", p. 6, (1975, Academic Press), and the journal of the Chemical Society of Japan, 87
Vol.5, 456 pages (1966), The Chemical Society of Japan,
Vol. 87, No. 10, p. 1969 (1966), Journal of Chemical Society (J. Chem. Soc.
), (C), p. 682 (1970), European Patent No. 35969, and the like, and a sulfonium complex and an oxosulfonium complex can be used.

Further, as for the organic boron compound represented by the general formula (3), which is another starting material for synthesizing the sulfonium complex or the oxosulfonium complex represented by the general formula (1), Liebig's analene (Liebig's
Ann.), 563, 110, (1949), Journal of Organic Chemistry (J. Org.
Chem.), Vol. 29, p. 1971 (1964), Journal of Chemical Society Parkin 2
(J. Chem. Soc., Perkin 2), p. 1225 (1978)
And the like can be used.

In this case, it is preferable to use different solvents depending on the solubility of the raw materials in the solvent, the properties of the target sulfonium complex or oxosulfonium complex, and the like.

For example, when the raw materials are all water-soluble, specifically, when the anion part of the raw material sulfonium complex or oxosulfonium complex is chlorine or bromine and the cation part of the raw material boron compound is an alkali metal, the reaction solvent When water is used, the target sulfonium complex or oxosulfonium complex is almost insoluble in water, and thus the crystals formed in the reaction system are filtered, washed with water, and dried to obtain the target sulfonium complex or oxosulfonium complex. be able to. Also, at this time, if an organic solvent poorly miscible with water, such as dichloromethane, chloroform, ethyl acetate, benzene, ether, etc., is allowed to coexist in the reaction system, the desired sulfonium complex or oxosulfonium complex can be formed. At the same time, it can be extracted into the organic layer. This method is particularly suitable for the synthesis of an oily sulfonium complex or oxosulfonium complex which is unstable or hardly crystallized in water. However, in this case, it is necessary that the organic solvent used dissolves the formed sulfonium complex or oxosulfonium complex. On the other hand, when any of the raw materials has poor solubility in water, specifically, the anion portion of the sulfonium complex or oxosulfonium complex of the raw material is BF ₄ , PF ₆ , S
When bF ₆ , AsF ₆ , ClO ₄ , methyl sulfate, trifluoromethyl sulfate, benzene sulfonate, p-toluene sulfonate, or the like, or when the cation moiety of the raw material organic boron compound is quaternary ammonium, the reaction solvent is based on the raw material. It is preferable to use a highly soluble organic solvent or a mixed solvent of water and an organic solvent. At this time, an organic solvent that is mutually mixed with water, for example, lower alcohol, acetonitrile, acetone, tetrahydrofuran,
When dimethylformamide, dimethylsulfoxide, or the like is used, after completion of the reaction, the desired sulfonium complex or oxosulfonium complex can be easily formed by adding an excessive amount of a solvent such as water, which hardly dissolves the desired sulfonium complex or oxosulfonium complex. It can be obtained in crystalline or oily form. The sulfonium complex or oxosulfonium complex thus obtained can be used as it is for normal purposes, but it can be recrystallized from an organic solvent to obtain a higher purity product.

The reaction temperature is higher than the melting point of the reaction solvent,
The reaction may be performed at any temperature below the temperature at which the raw material or the generated sulfonium complex or oxosulfonium complex decomposes.However, this reaction does not involve the passage of a large amount of heat during the reaction. Since the reaction proceeds promptly, the reaction is preferably performed at around room temperature from the viewpoint of economy and safety.

The FD-MS spectrum of the sulfonium complex or oxosulfonium complex represented by the general formula (1) of the present invention shows a fragment peak derived from a sulfonium cation or an oxosulfonium cation, respectively. Alternatively, the composition of the elements constituting the oxosulfonium complex can be determined, and thus the identification can be performed.

[0022]

The sulfonium complex or oxosulfonium complex represented by the general formula (1) of the present invention may have a phenacyl group or a substituent which may have a substituent on the sulfonium cation or the oxosulfonium cation. It is considered that by introducing a good benzyl group or an allyl group which may have a substituent, free radicals are efficiently generated by excitation and decomposition by application of light and / or thermal energy. At the same time, an improvement in crystallinity and solubility in organic solvents is obtained, whereby good stability is obtained.

[0023]

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

Example 1 Synthesis of diphenylphenacylsulfonium butyltriphenylborate Diphenylphenacylsulfonium perchlorate
A solution of 5.03 g of lithium butyltriphenylborate in 50 ml of acetonitrile was added to a solution of 65 g in 100 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
Was added. The dichloromethane layer was washed with water, dried and concentrated.
3.67 g of diphenylphenacylsulfoniumbutyltriphenylborate as white crystals was obtained. Melting point: 121 to 124 ° C. (gradual decomposition from about 110 ° C.) The IR spectrum is shown in FIG. FD-MS m / z 305 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₄₂ H ₄₁ BOS theoretical value C; 83.43%, H; 6.83% measured value C: 83.52%, H; 6.91%

Example 2 Synthesis of bis (p-tert-butylphenyl) phenacylsulfonium (sec-butyl) triphenylborate 5.00 g of bis (p-tert-butylphenyl) phenacylsulfonium hexafluorophosphate in 100 ml of acetonitrile A solution in which 2.61 g of lithium sec-butyltriphenylborate was dissolved in 50 ml of acetonitrile was added to the dissolved solution, and the solution was added at room temperature for 30 minutes.
For a minute. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-tert-butylphenyl) phenacylsulfonium (sec-butyl) triphenylborate 4.32 was obtained.
g was obtained. FD-MS m / z 417 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₅₀ H ₅₇ BOS Theoretical value C: 83.77%, H: 8.01% Measurement value C: 83.63%, H: 8.13%

Example 3 Synthesis of bis (p-tolyl) (p-nitrophenacyl) sulfonium-tert-butyltris (p-methoxyphenyl) borate Bis (p-tolyl) (p-nitrophenacyl) sulfonium hexafluorophosphate A solution in which 4.43 g of tetramethylammonium-tert-butyltris (p-methoxyphenyl) borate was dissolved in 50 ml of acetone was added to a solution of 5.00 g in 100 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. afterwards,
200 ml of water was added, and the precipitated yellow oily component was separated off.
100 ml of dichloromethane were added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.27 g of bis (p-tolyl) (p-nitrophenacyl) sulfonium-tert-butyltris (p-methoxyphenyl) borate. FD-MS m / z 378 ( (M-B (C 4 H 9) (C
₆ H ₄ OCH ₃ ) ₃ ) ⁺ ) Elemental analysis C ₄₇ H ₅₀ BNO ₆ S Theoretical C; 73.53%, H; 6.56%, N;
82% found C; 73.42%, H; 6.64%, N;
78%

Example 4 Synthesis of bis (p-chlorophenyl) (p-methoxyphenacyl) sulfoniummethyltris (p-fluorophenyl) borate Bis (p-chlorophenyl) (p-methoxyphenacyl) sulfonium hexafluorophosphate 00
g in 100 ml of acetonitrile, a solution in which 2.80 g of lithium methyl tris (p-fluorophenyl) borate was dissolved in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of methanol was added to separate the precipitated crystals, and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 3.31 g of bis (p-chlorophenyl) (p-methoxyphenacyl) sulfonium methyltris (p-fluorophenyl) borate. FD-MS m / z 403 ( (M-B (CH 3) (C 6
H ₄ F) ₃ ) ⁺ ) Elemental analysis C ₄₀ H ₃₂ BCl ₂ F ₃ O ₂ S Theoretical value C: 67.15%, H: 4.51% Measurement value C: 67.09%, H: 4.72 %

Example 5 Synthesis of phenyl (1-naphthyl) (1-naphthyl-carbonylmethyl) sulfonium (2-tert-butylethenyl) tris (p-bromophenyl) borate Phenyl (1-naphthyl) (1-naphthyl-carbonyl) Methyl) sulfonium hexafluoroantimonate (6.41 g) dissolved in acetonitrile (100 ml) was added with (2-tert-butylethenyl) tris (p-
A solution prepared by dissolving 5.58 g of lithium (bromophenyl) borate in 50 ml of acetonitrile was added, and the solution was added at room temperature for 30 minutes.
For a minute. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 4.27 g of phenyl (1-naphthyl) (1-naphthyl-carbonylmethyl) sulfonium (2-tert-butylethenyl) tris (p-bromophenyl) borate. FD-MS m / z 405 ( (M-B (C 6 H 11) (C
₆ H ₄ Br) ₃ ) ⁺ ) Elemental analysis C ₅₂ H ₄₄ BBr ₃ OS Theoretical value C: 64.55%, H: 4.58% Measurement value C: 64.39%, H: 4.69%

Example 6 Diphenyl-p-fluorophenacylsulfonium (2
Synthesis of -tert-butylethenyl) trimesityl borate In a solution of 5.00 g of diphenyl-p-fluorophenacylsulfonium perchlorate in 100 ml of acetonitrile, 5.59 g of sodium (2-tert-butylethenyl) trimesitylborate was added to acetone 50.
The solution dissolved in ml was added and stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and diphenyl-p
3.11 g of -fluorophenacylsulfonium (2-tert-butylethenyl) trimesityl borate was obtained. FD-MS m / z 323 ( (M-B (C 6 H 9) (C
₆ H ₂ (CH ₃ ) ₃ ) ₃ ) ⁺ ) Elemental analysis C ₅₃ H ₅₈ BFOS theoretical value C: 82.36%, H: 7.56% measured value C: 82.19%, H: 7.42%

Example 7 Phenyl (9-anthryl) (p-chlorophenacyl)
Synthesis of sulfonium (tert-butyl) triethyl borate phenyl (9-anthryl) (p-chlorophenacyl)
To a solution of 5.00 g of sulfonium hexafluoroarsenate dissolved in 100 ml of acetonitrile was added ter
A solution prepared by dissolving 1.29 g of lithium t-butyltriethylborate in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.43 g of phenyl (9-anthryl) (p-chlorophenacyl) sulfonium (tert-butyl) triethyl borate. FD-MS m / z 439 ( (M-B (tert-C 4 H 9)
_{(C 2 H 5) 3)} +) Elemental analysis C ₃₈ H ₄₄ BClOS theory C; 76.70%, H; 7.45 % measured value C; 76.58%, H; 7.29 %

Example 8 Synthesis of diphenyl (p-bromophenacyl) sulfonium phenyl tributyl borate 5.00 g of diphenyl (p-bromophenacyl) sulfonium tetrafluoroborate was added to acetonitrile 100
A solution in which 2.82 g of lithium phenyltributylborate was dissolved in 50 ml of acetonitrile was added to the solution dissolved in 50 ml, and the mixture was stirred at room temperature for 30 minutes. Then water 2
To the mixture, 00 ml was added, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and diphenyl (p-bromophenacyl) sulfonium phenyl tributyl borate 2.23 was obtained.
g was obtained. FD-MS m / z 383 ( (M-B (C 6 H 5) (C
₄ H ₉ ) ₃ ) ⁺ ) Elemental analysis C ₃₈ H ₄₈ BBrOS Theoretical value C: 70.92%, H: 7.52% Measurement value C: 71.05%, H: 7.39%

Example 9 Synthesis of diphenyl (p-cyanophenacyl) sulfonium allyltriethyl borate 5.00 g of diphenyl (p-cyanophenacyl) sulfonium tetrafluoroborate was added to acetonitrile 100
A solution in which 1.75 g of lithium allyltriethylborate was dissolved in 50 ml of acetonitrile was added to the solution dissolved in 50 ml, and the mixture was stirred at room temperature for 30 minutes. After that, water 20
0 ml was added, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and 3.41 g of diphenyl (p-cyanophenacyl) sulfonium allyltriethyl borate was obtained.
I got FD-MS m / z 330 ((MB (CH ₂ CHC
H ₂ ) (C ₂ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₃₀ H ₃₆ BNOS Theoretical C; 76.75%, H; 7.73%, N;
98% found C; 76.82%, H; 7.82%, N;
89%

Example 10 Synthesis of diphenyl (p-methylphenacyl) sulfoniumbenzyltriethyl borate Diphenyl (p-methylphenacyl) sulfonium (p
A solution of 2.07 g of lithium benzyltriethylborate in 50 ml of acetonitrile was added to a solution of 5.00 g of (toluenesulfonate) in 100 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.12 g of diphenyl (p-methylphenacyl) sulfoniumbenzyltriethylborate. FD-MS m / z 319 ((MB (CH ₂ C ₆ H
₅ ) (C ₂ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₃₄ H ₄₁ BOS theoretical value C: 80.30%, H: 8.13% measured value C: 80.27%, H: 8.05%

Example 11 Synthesis of diphenylphenacyloxosulfonium butyltriphenylborate In a solution of 6.72 g of diphenylphenacyloxosulfonium perchlorate in 100 ml of acetonitrile, 5.00 g of lithium butyltriphenylborate was added.
Was dissolved in 50 ml of tetrahydrofuran, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 3.87 g of diphenylphenacyloxosulfoniumbutyltriphenylborate. FD-MS m / z 321 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₄₂ H ₄₁ BO ₂ S Theoretical value C: 81.28%, H: 6.66% Measurement value C: 81.32%, H: 6.72%

Example 12 Synthesis of bis (p-tert-butylphenyl) phenacyloxosulfonium (sec-butyl) triphenylborate 5.00 g of bis (p-tert-butylphenyl) phenacyloxosulfonium hexafluorophosphate
Was dissolved in 100 ml of acetonitrile.
A solution in which 2.54 g of lithium c-butyltriphenylborate was dissolved in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
Was added. The dichloromethane layer was washed with water, dried and concentrated.
4.43 g of bis (p-tert-butylphenyl) phenacyloxosulfonium (sec-butyl) triphenylborate was obtained. FD-MS m / z 435 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₅₀ H ₅₇ BO ₂ S Theoretical value C: 81.94%, H: 7.84% Measurement value C: 82.02%, H: 7.94%

Example 13 Synthesis of bis (p-chlorophenyl) (p-methoxyphenacyl) oxosulfonium methyltris (p-fluorophenyl) borate Bis (p-chlorophenyl) (p-methoxyphenacyl) oxosulfonium hexafluorophosphate To a solution of 5.00 g in 100 ml of acetonitrile was added a solution of 2.62 g of lithium methyl tris (p-fluorophenyl) borate in 50 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. Then water 2
To the mixture, 00 ml was added, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-chlorophenyl) (p
3.26 g of -methoxyphenacyl) oxosulfonium methyltris (p-fluorophenyl) borate were obtained. FD-MS m / z 419 ( (M-B (CH 3) (C 6
H ₄ F) ₃ ) ⁺ ) Elemental analysis C ₄₀ H ₃₂ BCl ₂ F ₃ O ₃ S Theoretical value C: 65.68%, H: 4.41% Measured value C: 65.78%, H: 4.52 %

Example 14 Synthesis of diphenyl (p-bromophenacyl) oxosulfonium phenyl tributyl borate 2.82 g of lithium phenyl tributyl borate was added to a solution of 5.00 g of diphenyl (p-bromophenacyl) oxosulfonium tetrafluoroborate in 100 ml of acetonitrile. Was dissolved in 50 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.23 g of diphenyl (p-bromophenacyl) oxosulfonium phenyl tributyl borate. FD-MS m / z 400 ( (M-B (C 6 H 5) (C
₄ H ₉ ) ₃ ) ⁺ ) Elemental analysis C ₃₈ H ₄₈ BBrO ₂ S Theoretical C: 70.92%, H: 7.52% Measured C: 71.05%, H: 7.39%

Example 15 Synthesis of diphenylbenzylsulfonium butyltriphenylborate 4.05 g of lithium butyltriphenylborate was added to a solution of 5.00 g of diphenylbenzylsulfonium tetrafluoroborate in 100 ml of acetonitrile.
Was dissolved in 50 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
ml was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.95 g of diphenylbenzylsulfoniumbutyltriphenylborate. FD-MS m / z 277 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₄₁ H ₄₁ BS Theoretical value C: 85.40%, H: 7.17% Measurement value C: 85.32%, H: 7.04%

Example 16 Diphenyl (p-cyanobenzyl) sulfonium (se
Synthesis of c-butyl) triphenyl borate 5.00 g of diphenyl (p-cyanobenzyl) sulfonium hexafluorophosphate in acetonitrile 10
To a solution dissolved in 0 ml, 3.30 g of lithium sec-butyltriphenylborate was added to 50 ml of acetonitrile.
Was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.82 g of diphenyl (p-cyanobenzyl) sulfonium (sec-butyl) triphenylborate. FD-MS m / z 302 ( (M-B (C 4 H 9) (C
₆ H ₅₎ 3) ⁺⁾ Elemental analysis C ₄₂ H ₄₀ BNS theory C; 83.85%, H; 6.70 %, N; 2.
33% found C; 83.95%, H; 6.64%, N;
28%

Example 17 Synthesis of bis (p-tert-butylphenyl) (p-chlorobensyl) sulfonium methyltris (p-methoxyphenyl) borate Bis (p-tert-butylphenyl) (p-chlorobensyl) sulfonium hexafluorophosphate 5.
Then, 3.70 g of tetramethylammonium methyltris (p-methoxyphenyl) borate was added to a solution prepared by dissolving 100 g of acetonitrile in 100 ml of acetonitrile.
A solution dissolved in 0 ml was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of methanol was added to separate the precipitated crystals, and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-ter
2.31 g of (t-butylphenyl) (p-chlorobenzyl) sulfonium methyltris (p-methoxyphenyl) borate were obtained. FD-MS m / z 423 ( (M-B (CH 3) ((C 6
H ₄ OCH ₃ ) ₃ ) ⁺ ) Elemental analysis C ₄₉ H ₅₆ BCIO ₃ S Theoretical value C: 76.30%, H: 7.32% Measurement value C: 76.21%, H: 7.18%

Example 18 Synthesis of bis (p-chlorophenyl) (p-bromobensyl) sulfonium (2-phenylethenyl) tris (p-fluorophenyl) borate Bis (p-chlorophenyl) (p-bromobensyl) sulfonium hexafluorophosphate A solution of 3.50 g of lithium (2-phenylethenyl) tris (p-fluorophenyl) borate in 50 ml of acetonitrile was added to a solution of 5.00 g in 100 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. . afterwards,
200 ml of water was added, and the precipitated yellow oily component was separated off.
100 ml of dichloromethane were added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-chlorophenyl) was removed.
(P-bromobensyl) sulfonium (2-phenylethenyl) tris (p-fluorophenyl) borate
85 g were obtained. FD-MS m / z 423 ((MB (CHCHC ₆
H ₅ ) (C ₆ H ₄ F) ₃ ) ⁺ ) Elemental analysis C ₄₅ H ₃₃ BBrCl ₂ F 3 S Theoretical C: 65.56%, H: 4.04% Measured C: 65.42%, H; 3.99%

Example 19 Synthesis of phenyl (1-naphthyl) (1-naphthylmethyl) sulfoniumallyltris (p-bromophenyl) borate 5.00 g of phenyl (1-naphthyl) (1-naphthylmethyl) sulfonium hexafluoroantimonate Was dissolved in 100 ml of acetone, a solution of 4.30 g of lithium allyltris (p-bromophenyl) borate dissolved in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
Was added. The dichloromethane layer was washed with water, dried and concentrated.
There was obtained 2.52 g of phenyl (1-naphthyl) (1-naphthylmethyl) sulfonium allyltris (p-bromophenyl) borate. FD-MS m / z 377 ((MB (CH ₂ CHC
H ₂ ) (C ₆ H ₄ Br) ₃ ) ⁺ ) Elemental analysis C ₄₈ H ₃₈ BBr ₃ S Theoretical value C: 64.24%, H: 4.27% Measurement value C: 64.36%, H; 4 .22%

Example 20 Synthesis of phenyl (p-phenylthiophenyl) (p-nitrobenzyl) sulfoniumbenzyltriphenylborate 5.00 g of phenyl (p-phenylthiophenyl) (p-nitrobenzyl) sulfonium perchlorate in 100 ml of acetonitrile Was added to a solution of 3.21 g of lithium benzyltriphenylborate in 50 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and phenyl (p
2.42 g of -phenylthiophenyl) (p-nitrobenzyl) sulfoniumbenzyltriphenylborate were obtained. FD-MS m / z 430 ((MB (CH ₂ C ₆ H
_{5) ((C 6 H 5} ) 3) +) Elemental analysis C ₅₀ H ₄₂ BNO ₂ S ₂ theory C; 78.62%, H; 5.54 %, N; 1.
83% found C; 78.54%, H; 5.41%, N;
86%

Example 21 Diphenyl (p-methylbenzyl) sulfonium (te
Synthesis of rt-butyl) triethyl borate 5.00 g of diphenyl (p-methylbenzyl) sulfonium hexafluoroarsenate in acetonitrile 10
To a solution dissolved in 0 ml, 1.69 g of lithium tert-butyltriethylborate was added in 50 ml of acetonitrile.
Was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 1.28 g of diphenyl (p-methylbenzyl) sulfonium (tert-butyl) triethyl borate. FD-MS m / z 291 ((MB (CH ₂ C ₆ H
₄ CH ₃ ) ((C ₂ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₃₀ H ₄₃ BS Theoretical value C: 80.69%, H: 9.71% Measurement value C: 80.42%, H; 62%

Example 22 Synthesis of diphenyl (p-methoxybenzyl) sulfonium phenyl tributyl borate 5.00 g of diphenyl (p-methoxybenzyl) sulfonium tetrafluoroborate was added to acetonitrile 100
A solution prepared by dissolving 3.26 g of lithium phenyltributylborate in 50 ml of acetonitrile was added to the solution dissolved in 50 ml, and the mixture was stirred at room temperature for 30 minutes. Then water 2
To the mixture, 00 ml was added, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and diphenyl (p-methoxybenzyl) sulfonium phenyl tributyl borate 1.99 was obtained.
g was obtained. FD-MS m / z 307 ( (M-B (C 6 H 5) ((C
₄ H ₉ ) ₃ ) ⁺ ) Elemental analysis C ₃₈ H ₅₁ BOS Theoretical value C: 80.54%, H: 9.07% Measurement value C: 80.53%, H: 9.12%

Example 23 Synthesis of diphenyl (p-phenylthiobenzyl) sulfoniumbenzyltriethyl borate A solution prepared by dissolving 5.00 g of diphenyl (p-phenylthiobenzyl) sulfonium hexafluorophosphate in 100 ml of acetonitrile was charged with lithium benzyltriethylborate. A solution obtained by dissolving 0.85 g in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.04 g of diphenyl (p-phenylthiobenzyl) sulfoniumbenzyltriethylborate. FD-MS m / z 385 ((MB (CH ₂ C ₆ H
_{5) ((C 2 H 5} ) 3) +) Elemental analysis C ₃₈ H ₄₃ BS ₂ theory C; 79.42%, H; 7.54 % measured value C; 79.31%, H; 7.39 %

Example 24 Synthesis of diphenylbenzyloxosulfoniumbutyltriphenylborate In a solution of 5.00 g of diphenylbenzyloxosulfonium tetrafluoroborate in 100 ml of acetonitrile, 4.00 g of lithium butyltriphenylborate was added to 50 m of tetrahydrofuran.
The solution dissolved in 1 was added and stirred at room temperature for 30 minutes.
Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and diphenylbenzyloxosulfoniumbutyltriphenylborate was obtained at 2.7.
8 g were obtained. FD-MS m / z 293 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₄₁ H ₄₁ BOS theoretical value C; 83.09%, H; 6.97% measured value C; 83.15%, H; 7.01%

Example 25 Synthesis of diphenyl (p-cyanobenzyl) oxosulfonium (sec-butyl) triphenylborate 5.00 g of diphenyl (p-cyanobenzyl) oxosulfonium hexafluorophosphate was added to dioxane 1
A solution in which 3.25 g of lithium sec-butyltriphenylborate was dissolved in 50 ml of dioxane was added to the solution dissolved in 00 ml, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of methanol was added to separate the precipitated crystals, and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.41 g of diphenyl (p-cyanobenzyl) oxosulfonium (sec-butyl) triphenylborate. FD-MS m / z 318 ( (M-B (C 4 H 9) (C
₆ H _{5) 3)} ⁺⁾ Elemental analysis C ₄₂ H ₄₀ BNOS theory C; 81.67%, H; 6.53 %, N; 2.
27% found C; 81.49%, H; 6.47%, N;
29%

Example 26 Bis (p-chlorophenyl) (p-bromobenzyl) oxosulfonium (2-phenylethenyl) tris (p
Synthesis of-(fluorophenyl) borate bis (p-chlorophenyl) (p-bromobensyl) oxosulfonium hexafluorophosphate 5.00
g in a solution of 100 ml of acetonitrile,
3.48 g of lithium (2-phenylethenyl) tris (p-fluorophenyl) borate was added to 50 m of acetonitrile.
The solution dissolved in 1 was added and stirred at room temperature for 30 minutes.
Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried, and concentrated to obtain 1.95 g of bis (p-chlorophenyl) (p-bromobenzyl) oxosulfonium (2-phenylethenyl) tris (p-fluorophenyl) borate. FD-MS m / z 439 ((MB (CHCHC ₆
H ₅ ) (C ₆ H ₄ F) ₃ ) ⁺ ) Elemental analysis C ₄₅ H ₃₃ BBrCl ₂ F ₃ OS theoretical C: 64.31%, H; 3.96% measured C: 64.12%, H ; 3.92%

Example 27 Synthesis of diphenyl (p-methoxybenzyl) oxosulfonium phenyltributyl borate A solution prepared by dissolving 5.00 g of diphenyl (p-methoxybenzyl) oxosulfonium tetrafluoroborate in 100 ml of acetonitrile was charged with lithium phenyltributylborate. A solution obtained by dissolving .14 g in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 2.25 g of diphenyl (p-methoxybenzyl) oxosulfoniumphenyltributylborate. FD-MS m / z 323 ( (M-B (C 6 H 5) ((C
₄ H ₉ ) ₃ ) ⁺ ) Elemental analysis C ₃₈ H ₅₁ BO ₂ S Theoretical value C: 78.33%, H: 8.82% Measurement value C: 78.12%, H: 8.92%

Example 28 Synthesis of diphenylallyl sulfonium butyl triphenyl borate A solution prepared by dissolving 5.00 g of diphenyl allyl sulfonium tetrafluoroborate in 100 ml of acetonitrile and 4.70 g of lithium butyl triphenyl borate in 50 ml of acetonitrile Was added and stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
1 was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 3.87 g of diphenylallylsulfoniumbutyltriphenylborate. FD-MS m / z 227 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₃₇ H ₃₉ BS Theoretical C; 84.39%, H; 7.47% Measured C: 84.42%, H; 7.34%

Example 29 Synthesis of diphenyl (3,3-dicyano-2-phenyl-2-propenyl) sulfonium (sec-butyl) triphenylborate Diphenyl (3,3-dicyano-2-phenyl-2-propenyl) sulfonium Tetrafluoroborate 5.0
0 g in a solution of 100 ml of acetonitrile,
3.35 g of lithium sec-butyltriphenylborate
Was dissolved in 50 ml of acetonitrile, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
ml was added. The dichloromethane layer was washed with water, dried, concentrated, and treated with diphenyl (3,3-dicyano-2-phenyl-2).
2.87 g of -propenyl) sulfonium (sec-butyl) triphenylborate were obtained. FD-MS m / z 353 ( (M-B (C 4 H 9) (C
₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₄₅ H ₄₁ BN ₂ S theoretical C: 82.81%, H: 6.33%, N;
29% measured value C: 82.72%, H: 6.27%, N: 4.
34%

Example 30 Bis (p-chlorophenyl) (3,3-dicyano-2-
Synthesis of methyl-2-propenyl) sulfonium methyltris (p-methoxyphenyl) borate bis (p-chlorophenyl) (3,3-dicyano-2-
To a solution of 5.00 g of methyl-2-propenyl) sulfonium hexafluorophosphate dissolved in 100 ml of acetonitrile was added a solution of 4.17 g of tetramethylammonium methyltris (p-methoxyphenyl) borate dissolved in 50 ml of acetonitrile. For 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
Was added. The dichloromethane layer was washed with water, dried and concentrated.
Bis (p-chlorophenyl) (3,3-dicyano-2-
2.85 g of methyl-2-propenyl) sulfonium methyltris (p-methoxyphenyl) borate were obtained. FD-MS m / z 359 ( (M-B (CH 3) (C 6
H ₄ OCH ₃ ) ₃ ) ⁺ ) Elemental analysis C ₄₀ H ₃₇ BCl ₂ N ₂ O ₃ S Theoretical C; 67.90%, H; 5.27%, N;
96% found C; 68.02%, H; 5.34%, N;
02%

Example 31 Synthesis of bis (p-tert-butylphenyl) [3,3-bis (methoxycarbonyl) -2-phenyl-2-propenyl] sulfoniumvinyltris (p-fluorophenyl) borate tert-butylphenyl) [3,3-bis (methoxycarbonyl) -2-phenyl-2-propenyl] sulfonium perchlorate in a solution of 5.00 g in 100 ml of acetonitrile was charged with lithium vinyl tris (p-fluorophenyl) borate. A solution of 0.17 g in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
1 was added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-tert-butylphenyl) [3,3-
2.85 g of [bis (methoxycarbonyl) -2-phenyl-2-propenyl] sulfonium vinyltris (p-fluorophenyl) borate were obtained. FD-MS m / z 531 ((MB (CHCH ₂ ) (
C ₆ H ₄ F) ₃ ) ⁺ ) Elemental analysis C ₅₃ H ₅₄ BF ₃ O ₄ S Theoretical C: 74.47%, H: 6.37% Measured C: 74.56%, H; 6.29 %

Example 32 Bis (p-fluorophenyl) (3,3-dicyano-2
Synthesis of -p-tolyl-2-propenyl) sulfoniumphenyltributylborate bis (p-fluorophenyl) (3,3-dicyano-2
5.00 g of -p-tolyl-2-propenyl) sulfonium (p-toluenesulfonate) was added to acetonitrile 10
A solution in which 2.38 g of lithium phenyltributylborate was dissolved in 50 ml of acetonitrile was added to the solution dissolved in 0 ml, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-fluorophenyl)
(3,3-dicyano-2-p-tolyl-2-propenyl) sulfonium phenyl tributyl borate 2.09
g was obtained. FD-MS m / z 403 ( (M-B (C 6 H 5) (C
₄ H ₉ ) ₃ ) ⁺ ) Elemental analysis C ₄₂ H ₄₆ BF ₂ N ₂ S Theoretical value C; 76.12%, H; 7.45%, N;
23% found C; 76.23%, H; 7.39%, N;
32%

Example 33 Phenyl (1-naphthyl) [3,3-dicyano-2-
Synthesis of (p-chlorophenyl) -2-propenyl] sulfonium allyltriethyl borate phenyl (1-naphthyl) [3,3-dicyano-2-
(P-Chlorophenyl) -2-propenyl] sulfonium hexafluoroastatenate in a solution of 5.00 g of acetonitrile in 100 ml of acetonitrile was added with a solution of 1.16 g of lithium allyltriethylborate in 50 ml of acetonitrile. For a minute. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and phenyl (1-naphthyl) [3,3-dicyano-2- (p-chlorophenyl) was used.
-2-propenyl] sulfonium allyltriethyl borate 1.53 g was obtained. FD-MS m / z 437 ((MB (CH ₂ CHC
H ₂ ) (C ₂ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₃₆ H ₃₈ BClN ₂ S Theoretical C; 74.93%, H; 6.64%, N;
86% found C; 75.02%, H; 6.54%, N;
92%

Example 34 Synthesis of diphenylallyloxosulfonium butyltriphenylborate In a solution of 5.00 g of diphenylallyloxosulfonium tetrafluoroborate in 100 ml of acetonitrile, 4.7 lithium butyltriphenylborate was added.
A solution of 0 g in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated to obtain 3.87 g of diphenylallyloxosulfoniumbutyltriphenylborate. FD-MS m / z 243 ( (M-B (n- C 4 H 9) (
C ₆ H ₅ ) ₃ ) ⁺ ) Elemental analysis C ₃₇ H ₃₉ BOS Theoretical value C: 81.91%, H: 7.25% Measurement value C: 82.01%, H: 7.32%

Example 35 Synthesis of Diphenyl (3,3-dicyano-2-phenyl-2-propenyl) oxosulfonium (sec-butyl) triphenylborate Diphenyl (3,3-dicyano-2-phenyl-2-phenyl) A solution of 5.00 g of (propenyl) oxosulfonium tetrafluoroborate in 100 ml of acetonitrile was charged with lithium sec-butyltriphenylborate.
A solution in which 35 g was dissolved in 50 ml of acetonitrile was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and diphenyl (3,3-dicyano-2-phenyl-2-propenyl) oxosulfonium (sec-
2.87 g of (butyl) triphenylborate were obtained. FD-MS m / z 369 ( (M-B (C 4 H 9) (C
₆ H _{5) 3)} ⁺⁾ Elemental analysis C ₄₅ H ₄₁ BN ₂ OS theory C; 80.83%, H; 6.18 %, N; 4.
19% found C; 80.75%, H; 6.24%, N;
25%

Example 36 Synthesis of bis (p-tert-butylphenyl) [3,3-bis (methoxycarbonyl) -2-phenyl-2-propenyl] oxosulfonium vinyltris (p-fluorophenyl) borate -Tert-butylphenyl) [3,3-bis (methoxycarbonyl) -2-phenyl-2-propenyl] oxosulfonium perchlorate in a solution of 5.00 g in 100 ml of acetonitrile was added with vinyl tris (p-fluorophenyl) borate. Lithium 4.17
g was dissolved in 50 ml of acetonitrile,
The mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated off.
0 ml was added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-tert-butylphenyl) [3,3
-Bis (methoxycarbonyl) -2-phenyl-2-propenyl] oxosulfonium vinyltris (p-fluorophenyl) borate 2.85 g was obtained. FD-MS m / z 547 ((MB (CHCH ₂ ) (
C ₆ H ₄ F) ₃ ) ⁺ ) Elemental analysis C ₅₃ H ₅₄ BF ₃ O ₅ S Theoretical C: 73.10%, H: 6.25% Measured C: 73.21%, H: 6.29 %

Example 37 Bis (p-fluorophenyl) [3,3-dicyano-2
Synthesis of -p-tolyl-2-propenyl] sulfonium phenyl tributyl borate bis (p-fluorophenyl) [3,3-dicyano-2
-P-tolyl-2-propenyl] sulfonium (p-toluenesulfonate) in 5.00 g of acetonitrile 10
A solution in which 2.38 g of lithium phenyltributylborate was dissolved in 50 ml of acetonitrile was added to the solution dissolved in 0 ml, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 200 ml of water was added thereto, and the precipitated yellow oily component was separated and 100 ml of dichloromethane was added. The dichloromethane layer was washed with water, dried and concentrated, and bis (p-fluorophenyl)
[3,3-dicyano-2-p-tolyl-2-propenyl] sulfonium phenyl tributyl borate 2.09
g was obtained. FD-MS m / z 419 ( (M-B (C 6 H 5) (C
₄ H ₉ ) ₃ ) ⁺ ) Elemental analysis C ₄₂ H ₄₆ BF ₂ N ₂ OS Theory C: 74.32%, H: 7.28%, N;
13% measured C; 74.25%, H; 7.34%, N;
22%

Reference Examples 1 to 6 and Comparative Examples 1 and 2 50 parts of pentaerythritol triacrylate as a compound having a radically polymerizable ethylenically unsaturated bond and 1 part of diphenylphenacylsulfonium butyl triphenylborate as a sulfonium complex of the present invention A mixture of about 5 microns on a glass plate,
Further, a sample in which a polyethylene terephthalate film having a thickness of about 25 μm was adhered thereon was prepared.
When the sample was held in an oven at 150 ° C. for 10 minutes, the sample cured and clearly gave a polymerized product. Instead of diphenylphenacylsulfoniumbutyltriphenylborate, diphenylbenzylsulfoniumbutyltriphenylborate, diphenylallylsulfoniumbutyltriphenylborate, diphenylphenacyloxosulfoniumbutyltriphenylborate, diphenylbenzyloxosulfoniumbutyltriphenylborate, diphenylallyloxo When using sulfonium butyl triphenyl borate, both samples cured and clearly gave polymerization products,
No polymerization product was observed under the same conditions in a sample containing known diphenylphenacylsulfonium tetrafluoroborate or diphenylphenacyloxosulfonium hexafluorophosphate instead of diphenylphenacylsulfoniumbutyltriphenylborate.

Reference Examples 7 to 12 and Comparative Examples 3 and 4 50 parts of pentaerythritol triacrylate as a compound having an ethylenically unsaturated bond capable of radical polymerization and 1 part of dimethylphenacylsulfonium butyl triphenyl borate as a polymerization initiator were diluted. The mixture is dissolved in 100 parts of dioxane as a solvent, and the mixture
After drying in a hot air oven at 70 ° C. for 2 minutes, a 10% aqueous solution of polyvinyl alcohol was applied thereon to a thickness of about 5 μm, and this was again heated with hot air at 70 ° C. A sample was prepared which was dried in an oven for 2 minutes. When this sample was irradiated with a 500 mW high pressure mercury lamp for 30 seconds, it hardened and clearly gave a polymerization product. Instead of diphenylphenacylsulfonium butyltriphenylborate,
When diphenylbenzylsulfonium butyl triphenyl borate, diphenyl allyl sulfonium butyl triphenyl borate, diphenyl phenacyl oxo sulfonium butyl triphenyl borate, diphenyl benzyl oxo sulfonium butyl triphenyl borate, when using diphenyl allyl oxo sulfonium butyl triphenyl borate, any The sample cured to give apparently polymerized products, but the sample containing the known diphenylphenacylsulfonium tetrafluoroborate and diphenylphenacyloxosulfonium hexafluorophosphate instead of diphenylphenacylsulfonium butyltriphenylborate did not. Under the conditions, no polymerization product was observed.

Reference Examples 13 to 18 and Comparative Examples 5 to 7 360 parts of methyl ethyl ketone as a diluting solvent, 20 parts of polymethyl methacrylate as a binder, 20 parts of pentaerythritol triacrylate as a compound having a radically polymerizable ethylenically unsaturated bond, as sensitive adhesive 3,3'-carbonyl bis (7-diethylamino coumarin) sulfonium complexes or oxosulfonium complex 1.2 × 10 ^-5 of the present invention shown in table 1 below as a polymerization initiator to a solution 2g consisting of 1 part Mol was added to obtain a photosensitive solution. This photosensitive solution is applied on a glass plate to a thickness of about 2 μm using a spin coater, and a 10% aqueous polyvinyl alcohol solution is applied thereon as an oxygen barrier layer to a thickness of about 5 μm using a spin coater. did. An argon ion laser beam (48 mm in beam diameter 1.5 mm) is applied to this photosensitive plate.
8 nm) for different exposure times, then developed with water and toluene, and the exposure energy that gives a cured spot diameter equivalent to the laser beam diameter is shown in Table 1 as sensitivity. As comparative examples, Table 1 also shows the sensitivities when known diphenylphenacylsulfonium tetrafluoroborate, diphenylphenacyloxosulfonium hexafluorophosphate and triphenylsulfoniumbutyltriphenylborate were used as polymerization initiators. As is clear from the results in Table 1, when the sulfonium complex or the oxosulfonium complex of the present invention was used as a polymerization initiator, known diphenylphenacylsulfonium tetrafluoroborate, diphenylphenacyloxosulfonium hexafluorophosphate and triphenylphenacyl oxosulfonium hexafluorophosphate were used. It can be seen that the sensitivity was improved in each case as compared with the case where phenylsulfoniumbutyltriphenylborate was used as the polymerization initiator.

[0064]

[Table 1]

[0065]

The sulfonium complex and the oxosulfonium complex represented by the general formula (1) according to the present invention are a phenacyl group which may have a substituent or a substituent as a substituent on the sulfonium cation or the oxosulfonium cation. By introducing a benzyl group which may have a substituent or an allyl group which may have a substituent, free radicals are efficiently generated by applying light and / or thermal energy.

Accordingly, it has a remarkably good effect as a polymerization initiator for a polymerizable substance, and requires high sensitivity by applying light energy from various light sources such as a mercury lamp or laser and / or applying heat energy by heating or a thermal head. Various printing plate materials, various recording media and inks, adhesives, adhesives using hologram materials and microcapsules,
It is useful for forming polymers and cured products having good physical properties such as adhesives and sealants.

[0067]

[Brief description of the drawings]

FIG. 1 shows an IR spectrum (in a KBr tablet) of the sulfonium complex synthesized in Example 1.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-121269 (JP, A) JP-A-64-29419 (JP, A) JP-A-2-157760 (JP, A) JP-A-5-157760 213861 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 5/02 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A sulfonium complex or an oxosulfonium complex represented by the general formula (1), which generates an active radical upon application of light and / or heat energy. General formula (1) (However, R ¹ and R ² each have an aryl group which may have a substituent, and R ³ has a phenacyl group which may have a substituent, a benzyl group which may have a substituent or a substituent. R ⁴ is an oxygen atom or a lone electron pair; R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group which may have a substituent, It is aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a group selected from optionally alicyclic group which may have a substituent, R ^5, R ⁶ , R ⁷ and R ⁸ do not simultaneously form an aryl group which may have a substituent.) 2. In the general formula (1), R ⁵ is an alkyl group which may have a substituent, and R ⁶ , R ⁷ and R ⁸ are aryl groups which may have a substituent. The sulfonium complex or oxosulfonium complex according to claim 1, wherein