JPS61100557A - Manufacture of triarylsulfonium salt - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing triarylsulfonium polyhalogen, metalloid or metalloid salts.

Prior to the present invention, various methods have been used to prepare triphenylsulfonium chloride of the formula: It can be decomposed into double decomposition. These alkali or alkaline earth metal halide salts are preferably represented by the following formula: % Formula % (2). where M is hydrogen or an alkali metal such as sodium, potassium or lithium, or an alkaline earth metal such as magnesium, paricum, zinc, etc. 6! and Y is a metal or metalloid, such as boron, phosphorus, antimony or arsenic, or a halogen group, such as fluorine (11), and n has a value of 4 to 6.

The process disclosed in Pltt, US Pat. No. 2,807,648, uses aluminum chloride to perform a direct 7 Li Deru-Crafts condensation of aromatic hydrocarbons. Cr1vello assigned to the applicant
An alternative method is disclosed in U.S. Pat. No. 4,574,066, which uses diphenyl sulfide and aluminum chloride in combination with chlorine.

Yet another method is disclosed in US Pat. No. 4,174,476 to Smith (8mlth), which uses a mixture of diaryl sulfide and diaryl sulfoxide in the presence of a strong acid. Although the methods described above have been useful for preparing triaryl sulfo;rum salts of formula (1), the yields from this reaction are often insufficient and the use of reactants such as diphenyl sulfoxide is often problematic. Therefore, it has been noticed that this method is uneconomical. moreover,
Some of the methods described above required isolation or separation of intermediates formed during the reaction before obtaining the desired final product. For example, the metathesis of a triarylsulfonium halide with an alkali metal or alkaline earth metal polyhalometal or metalloid salt of formula (2) has often required isolation of the triarylsulfonium halide beforehand.

The present invention provides a polyaryl sulfide, for example, a polyaryl sulfide having the following formula:
6-14) Aryl etc. RE is R group or RQR
” (-sR'-)b, R2, ν and R4 are divalent C(6-44)arylene groups or substituted C(6-14)arylene groups, and Q is 10-1-s( o) -1-8- or a combination thereof, and 2 is -0-1-8- or -C(R')
z-TE;J)S, BS is hydrogen or monovalent C(1-8)
t is an organic group, a is an integer equal to 0 or 1, and b is an integer equal to rho 3.] A temporary mixture of diaryl sulfide and diaryl sulfoxide is formed on the spot by partially oxidizing the compound contained in This was accomplished by discovering that this mixture could be converted in situ to the corresponding triarylsulfonate in the presence of a dehydrating agent and a strong protic acid.

Triarylsulfonium polyhalometal or metalloid salt can be produced in high yield by metathesis of triarylsulfonate as it is with polyhalometal or metalloid salt of formula (2) without isolation. .

DISCLOSURE OF THE INVENTION The present invention provides polyaryl sulfates of formula (3) or (4).
provides a method for forming triarylsulfonium polyhalogen or metalloid salts using phyto as a starting material, which method comprises (t) triarylsulfonate and an alkali metal or alkaline earth metal polyhalogen, or metathesis with a metalloid to produce a salt in the corresponding POIJ/% PIE or metalloid; recovering the salt, wherein the triarylsulfonate is a product obtained by partial oxidation of a polyarylsulfide raw material contacted with a strong acid under dehydrating conditions.

Examples of polyaryl sulfides included in formulas 3) and (4) are listed below.

OCH, CH3CH.

CHI CH3 r Gself11 Groups contained in R and R1 of formula (3) include, for example, phenyl, tolyl, quinryl, naphthyl, anthryl, chlorophenyl, methoxyphenyl, 9. R2, R
Groups included in 3 and R4 include, for example, phenylene, tolylene, xylylene, biphenylene, and the like.

In addition to using the polyarylsulfides of formulas (3) and (4) described above, polyarylenesulfide oligomers, such as (m is an integer having a value of 1-8), can be used, which are alkali sulfides. It can be prepared by condensing a metal such as sodium sulfide with a dino-aromatic compound such as p-dichlorobenzene or p-dibromobenzene. These polyarylene sulfide oligomers can be further arylated with aryldiazonium salts or diaryliodonium salts in the presence of a copper salt catalyst such as steel benzoate and a strong acid to form triarylsulfonium salts. Alternatively, these PoIJ
71J-renesulfide oligomers can also be partially oxidized and condensed to form polytriarylsulfonium salts.

Oxidizing agents that can be used in carrying out the present invention include, for example, CH3CO3H, HCOsHs CH3CHzCOsH
SCaHsC○3■, m-Ct-CH3CO3H,,H
2O2 iodosobenzene, iodosobenzene diacetate, potassium persulfate, sodium periodate, t-butyl hypochlorite, bromine, chloramine B and chlorobenzotriazole.

Dehydrating agents that can be used in the practice of this invention include, for example, acetic anhydride, angle pentoxide, polyphosphoric acid, maleic anhydride, phthalic anhydride, sulfur dioxide, trifluoroacetic anhydride, and concentrated sulfuric acid-AE6.

As used herein, the term "strong acid" refers to sulfuric acid, perchloric acid, nitric acid, fluoroboric acid, hydrofluoric acid and benzenesulfonic acid.

The polyhalometal or metalloid salt of formula 12) contains NaAsF.
6, KPF, , NaS bF@, NaBF4, KSbC
41, NaFeC4, LizBic14, Na5nCt
@ and HAsF6. Other compounds that can be used to metathesize triarylsulfonate salts obtained by the practice of this invention include, for example, KCtOn, NaCO2C
There are F5, KSO3CF, and KSOsC@H.

In practicing the present invention, the diaryl sulfide is partially oxidized using the conventional oxidizing agents described above. For good results, approximately (L
It has been found that it is good to use 2 to 0.7 moles of oxidizing agent. An organic solvent can be used to accelerate the reaction if desired. Examples of organic solvents that can be used include, for example, chloroform, methylene chloride, carbon tetrachloride, acetic acid, benzene and chlorobenzene.

Partial oxidation of diaryl sulfide is performed at a temperature of 0 to 90°C.
Satisfactory results can be obtained within this range.

Sufficient dehydrating agent and strong acid can be used to effect the conversion of the resulting mixture of diaryl sulfide and diaryl sulfoxide. When using concentrated sulfuric acid,
It can act both as a strong acid and as a dehydrating agent. Temperatures that can be used to carry out partial oxidation of diaryl sulfide as well as dehydration and protonation are e.g.
The temperature is 100°C, preferably 0°C to 60°C.

The conversion of the Schiff 1J-rulsulfide into a mixture of diarylsulfide and diarylsulfoxide can be carried out within 1 to 10 hours under the operating conditions described above, and after the conversion is complete, the corresponding triarylsulfonate salt of the resulting component Dehydration and protonation can be carried out.

After this, the metathesis reaction is carried out by adding a solution of the polyhalo metalloid or metal salt to the reaction mixture, or by pouring the reaction mixture directly into a cooled borino tip or aqueous solution of the metalloid salt depending on the specific conditions. It can be carried out.

Recovery of the desired triarylsulfonium salt or metalloid salt can then be performed using standard recovery methods, such as recrystallization, filtration, etc.

Examples of the invention will now be given by way of illustration and not by way of limitation. All parts are parts by weight.

Example 1 9.3t (α05 mol) of diphenyl sulfide,
12.5TI! 4.759 (Q, 025 mol) of 40% peracetic acid was slowly added to the mixture of 100% acetic anhydride and 50% methylene chloride, with stirring, cooled to 0°C. When the mixture was stirred, a slight ripening reaction was observed. After the addition was complete, 1.5- concentrated sulfuric acid was added. Concentrated sulfuric acid was slowly added while keeping the temperature below 10°C. The color of the reaction mixture was initially pale purple and then gradually faded upon standing. After 1 hour at room temperature, 5,72 liters of potassium hexafluoroarsenate dissolved in about 50 liters of distilled water was added to the mixture. The mixture was stirred vigorously for 1.5 hours, then the methylene chloride layer was separated using a separatory funnel. The methylene chloride was then removed using a rotary evaporator, leaving a yellow oil. Treatment of the yellow oil with ether gave a white crystalline product. Recrystallization from methanol gave a product with a melting point of 86-88°C. Based on the method of preparation, the product was hasiphenyl-4-thiophenoxyphenolsulfonium hexafluoroarsenate. Product identity was confirmed by NMR spectrum.

The yield of the recrystallized product was 52 f, or a yield of 25%.

A solution containing 3% by weight of the above photoinitiator was evaluated with the photoinitiator of 4-vinylcyclohexene dioxide. The resulting solution was cast as a 3 mil film on a glass plate and G11i:l! ! Exposure was carried out using a H, 3'l 7 Nakasho mercury arc lamp. A tack-free film was obtained within 1 second.

Example 2 The procedure of Example 1 was repeated. However, in this example, 46 tons of potassium hexafluorophosphate was used instead of potassium hexafluoroarsenate. Melting point 91-93 after recrystallization from methanol
Diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate having a temperature of 5.691.
This sulfonium hexafluorophosphate salt was also evaluated as a 3 mil film on glass as a 3X solution of the photoinitiator in 4-vinylcyclohexene dioxide (dissolved).
It showed a tack-free time of 1 second.

Example 3 To a mixture of 9.3 t (11.05 mol) nocyphenylsulfide, 12 rpl acetic anhydride, 50 ml methylene chloride and 1.5-0 concentrated sulfuric acid, with stirring, 0
A 4.75F (11025 mole) 4OX peracetic acid solution was added dropwise at <0>C. With continued stirring, the temperature of the mixture was maintained below 10° C. for 1 hour. A solution of 5.71 of potassium hexafluoroarsenate in 50 d of water was then added and the reaction mixture was treated as described in Example 1. After recrystallization from methanol at 7'C, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroarsenate was obtained in a yield of &65F (yield 47.5%).

Example 4 A mixture of 9,5 F (5 moles of CLO) diphenyl sulfide and 6.75 F (1025 moles) of potassium persulfate was stirred and 25-ml of chilled concentrated sulfuric acid was added dropwise while the temperature was kept at 0. The temperature was kept at ~5°C. The solution appeared deep purple and slowly turned green. The mixture was stirred at room temperature for 1 hour. The mixture was then poured into 100° C. ice water containing 5,72 hexafluoride and potassium acid. A white precipitate was obtained.

Based on the method of preparation, the product was diphenyl-4-thiophenoxyphenylsulfonium hexafluoroarsenate. Compound identification is further determined by melting point and N
M.P.

Confirmed by spectrum. The product yield was FL8t, which was 63% of theory. A 3% solution of hexafluoroarsenate sulfonium salt was evaluated as a photoinitiator for 4-vinylcyclohexene dioxide and 3% solution on glass was evaluated.
When exposed as a mill film to a C)E LaT 7 lamp, a tack-free time of 1 second was obtained.

Example 5 9,39 (0.05 mol) of diphenyl sulfide,
12.5 rye of acetic anhydride and 4.75 ? ((
A mixture of 40% peracetic acid (L025 mol) was kept at 0°C;
To this was added 1.5-chlorinated sulfuric acid. 1 of the obtained mixture
Stir for an hour and then pour the mixture into a solution of 5.72 parts potassium arsenate hexate in 100 parts water. The product obtained was a pale yellow oil, which was recrystallized from methanol. Based on the manufacturing method, the product is diphenyl-4
-thiophenoxyphenylsulfonium hexafluoroarsenate. This was obtained in a yield of 3a, a%. It was evaluated as shown in Example 4 and was found to be an effective photoinitiator.

Example 6 The procedure of Example 5 was repeated. However, in this example, 65 g of sodium hexafluoride antimonate was used in place of 5.79 potassium hexafluoroarsenate. Diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate was obtained in a yield of 59%. A 3% solution of this hexafluoroantimonate salt as a photoinitiator for 4-vinylcyclohexene dioxide was evaluated according to the procedure of Example 40 and a tack-free time of about Q, 5 seconds was obtained.

Example 7 4.75P (α0
25 mol) of 40% peracetic acid solution was added dropwise. The addition of peracetic acid was done at a rate sufficient to maintain the reaction mixture at about 15°C. An orange reaction mixture was obtained and became homogeneous. After stirring at room temperature for O,S hours, the reaction mixture was stirred for 10
It was cooled to <0>C and 15-acetic acid was added. 5 to the resulting solution
- of concentrated sulfuric acid was added dropwise. As the sulfuric acid was added, a deep purple color appeared, gradually fading, and when half of the sulfuric acid had been added, it turned yellow. After the addition was complete, the reaction mixture was kept stirring for 2 hours. The solution was then poured into 300 trlt of cold water and a solution of 5 t of KPF dissolved in 50 t of water was added. The resulting solution was stirred for 1 hour.

Separate methylene chloride from the aqueous layer by a separatory funnel;
The solvent was evaporated using a rotary evaporator. An oil was obtained which was purified by chromatography on neutral alumina using methylene chloride as eluent.

The product was washed with cyclohexane. A solidified glassy product was obtained in 50% yield and had a wide melting point from around 62°C.

Based on the manufacturing method and elemental analysis, the product had the following formula:

W value ((4@HrISsPFs): %C959,
02;%H, 5゜69;%P, 4.23゜Actual value:%
C, 5a69;%H,x94:%P, 4.05゜4
- A mixture of vinyl fucurohexe/dioxide and 3% by weight of the above photoinitiator was applied to an aluminum substrate. Exposure of the coated substrate to ultraviolet light using a 1 (3T7) lamp 4 inches apart was found to yield a tack-free film within 1 second.

Example 8 The above procedure was repeated, but in this example, after the 1,4-dithiophenoxybenzene oxidation step, 5-acetic acid and 10
- concentrated sulfuric acid was used. The resulting mixture was then divided into two equal portions. One portion was metathesized with sodium hexafluoroantimonate. A yellowish-white solid with a melting point of 82° C. was obtained in a yield of 75.8%. Based on the manufacturing method, the product had the following formula:

Calculated value:%C,52,49:%H1528;%8,1
5.55゜actual value 2%C, 52,19; punishment, 559;
%8, 15.77° Potassium hexafluoroarsenate was added to the remaining half of the above mixture. The solution was triturated in n-hexane,
The resulting oil was washed several more times with separate portions of n-hexane.

A yellowish-white glassy product was obtained which was dried under reduced pressure to give the product in a yield of 7'5.8%. Based on the manufacturing method, the product was a photoinitiator with the formula:

Calculated value: %C, 55, 64; Hagi, 548: %S, 1&
49° Actual value: %c, 54.61: Silk, 570;
%S, 14.47゜Example? 1a42F (0.1 mol) dibenzothiophene, 30
9.5 f (105 moles) of 35% peracetic acid was added to a mixture of - of acetic acid and fod of methylene chloride with stirring. During the addition, a mild exotherm was observed and the temperature rose to 30°C. After addition of peracetic acid, the reaction mixture was stirred at room temperature for 1 hour.

Next, add 5otI! to this mixture! 1 of acetic anhydride was added, and 10-1 of concentrated sulfuric acid was added. The reaction mixture was cooled during the addition, keeping the temperature below 15°C. Additional 5-methylene chloride was added to alleviate caking in the flask, and the mixture was stirred for 1 hour and then poured into approximately 500 ml of water containing 105 moles of potassium hexafluorophosphate. A brown precipitate was obtained which was collected by filtration and washed once with water and then with ethyl ether. The resulting product was dried under reduced pressure at 60° C. for about 12 hours. 19.7f, i.e. yield 8
2% product was obtained. Based on the manufacturing method, the product had the following formula:

A 3% solution of the photoinitiator was prepared by dissolving the salt in 4-vinylfuclohexe/dioxide.

The resulting mixture was coated as a 1 mil film on a glass plate and exposed using a GE H3'I'7 Nakasho mercury arc lamp. A tack-free cured film was obtained within 2-3 seconds.

Example 10 □

In a solution of 3 AOr (α3 mol) of thiophenol dissolved in 120 r/dimethylacetamide,
19.69 (154 moles) of potassium hydroxide powder was added. The temperature of the reaction mixture rose spontaneously to 50°C. After the exotherm subsided, the reaction mixture was heated to 165°C and
It was heated in a bowl that collected 20 - hours of water. 44.89 (Q, 15 moles) of 4.41-dibromobiphenyl was then added to the cooled solution. After addition,
The solution was heated to reflux for 6 hours. After the mixture has cooled, approx.
0 logo water was added to obtain a slightly brown precipitate, which was suctioned, filtered, washed with water, and heated at 60°C under reduced pressure for about 12 min.
Dry for an hour. Product yield was electrostatic.

Depending on the method of preparation, the product was a sub-longitudinal disulfide.

1 asr (105 mol) of the above bisulfide, 20 ml
of glacial acetic acid and 40 methylene chloride; 4.
75 t (1025 mol) of 40% peracetic acid were added dropwise. The addition of peracetic acid was controlled to maintain the temperature at 10-15°C. After the reaction was completed, the reaction mixture was stirred at 25° C. for 1.5 hours. The reaction mixture was then cooled to 10 DEG C. again, and 15 portions of acetic anhydride were added, followed by 5 portions of concentrated sulfuric acid. The temperature was kept at 10-15° C. during the addition and then stirred at room temperature for 2 hours. The reaction mixture was heated to 300 trrl.
of water, and a suspension of 52 potassium hexafluorophosphate in 100 methylene chloride was added. The mixture was stirred for 12 hours, then thorium chloride was added to saturate the aqueous layer. Retaining the methylene chloride layer, the solvent was removed and the remaining solid was washed with ethyl ether. The obtained product was purified by recrystallization from acetonitrile. Based on the method of preparation, the product was an arylsulfonium salt having the formula:

Fg - A 3% solution of the above sulfonium salt in 4-vinylcyclohexene dioxide was coated as a 1 mil film on a glass plate and exposed with a GE Hs Ty medium pressure mercury arc lamp at a distance of 6 inches.

A tack-free film was obtained after an exposure time of 5 seconds.

Example 11 21'L 1 ? (105 mol) Nosy 4.4' -
19. to a mixture of phenoxydiphenyl sulfide, 40 vol of acetic acid and 20 mg of methylene chloride.
Of ([L10 mol) of 40% peracetic acid was added. The addition of peroxygen beak was kept at a rate such that the reaction temperature did not exceed 10-15°C. After the addition was complete, the reaction mixture was stirred for 1 hour and then poured into 300ft of water. The methylene chloride layer was separated ii':t L and the solvent was removed using a rotary evaporator. A yellow oil was obtained, which was purified by recrystallization from acetonitrile ethyl ether. Based on the method of preparation and packaging, the product was a tris sulfoxide having the formula:

Calculated value:%C,ls4.0:%H,4,0:%0.
I C1,66° Actual value: %C,64,13; X'
H, A99: %n, IQ, 39°15? (1008
mol) of the above tris sulfoxide, 10-acetic anhydride and 5? of diphenyl sulfide, 5fII
t of concentrated sulfuric acid was added. Addition of sulfuric acid is carried out at a temperature of 10-1
The temperature was kept at a rate that did not exceed 5°C. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours and then poured into 500 fri water containing 40 F potassium hexafluorophosphate and 20 F/methylene chloride. Separate the methylene chloride layer;
The solvent was evaporated. The resulting white solid was washed with ethyl ether, filtered and dried under reduced pressure at 60°C. The product was obtained by recrystallization from acetonitrile/ethyl ether. Based on the method of preparation and IR spectrum, this product is an arylsulfonium hexafluoride with the formula: (4
It was an acid salt.

The above bissulfonium g@t was dissolved in 4-vinylcyclohexene dioxide to make a 3% solution.

A 1 mil film of this solution was UV cured as described in Example 10. The film becomes tack-free after an exposure time of 1 second.
The present invention allows for the use of a very wide variety of polyaryl sulfides, oxidizing agents, acids, and dehydrating agents. This is as shown in the explanation preceding 111.

In addition, the present invention also provides the following arylsulfonium salts.

FJ R'q(-n'q-)cn'-5-n'R7゜small iI Here, R6 is a C(6-14) aryl group or a substituted C(
6-+4) aryl group, and bi is divalent C(6-44
) arylene group or a substituted C(6-14) arylene group, Q is 10-1-s(o)-1-8- or a combination thereof, and M is a transition metal or metalloid.
R2 is a bivalent arylene selected from B% R
8 is a trivalent C(6-14) arylene group or a substituted C(
6-+4) arylene group, 2 is 10-, -8- or -c(W)z-, R5 is hydrogen or monovalent C
(1-8) group, a is an integer equal to 0 or 1, and C is an integer equal to 1-3.

In addition to the above-mentioned arylsulfonium salts, sulfonium salts of the following formula: (wherein R6, R7 and Q are as defined above 9) are also included in the present invention.

-one

Claims (1)

[Claims] 1. In forming a triarylsulfonium polyhalometal or metalloid salt using a polyarylsulfide as a starting material, (A) a triarylsulfonate and an alkali metal or alkaline earth metal polyhalometal; or metathesis with a metalloid salt to produce the corresponding polyhalometal or metalloid salt; (B) recovering the triarylsulfonium polyhalometal or metalloid salt obtained from the mixture of step (A); A process for producing a triarylsulfonium polyhalometal or metalloid salt, wherein the triarylsulfonate is a product obtained by partial oxidation of a polyarylsulfide raw material brought into contact with a strong acid under dehydrating conditions. 2. In forming a triarylsulfonium polyhalometal or metalloid salt using a diarylsulfide as a starting material, (A) partial oxidation of the diarylsulfide is carried out to in situ produce substantially equimolar amounts of the diarylsulfide and the corresponding (B) converting the reactants obtained in step (A) to the corresponding triarylsulfonate salts using a strong acid under dehydrating conditions; (C) step (B); triarylsulfonate of the formula: [In the formula, M is hydrogen, an alkali metal or an alkaline earth metal, Y is a metal or metalloid, X is a halogen group, and n is a value of 4 to 6 (D) recovering the triarylsulfonium polyhalometal or metalloid salt obtained from the mixture of step (C). Method of manufacturing salt. 5. The method according to claim 2, wherein the diaryl sulfide is diphenyl sulfide. 4. The method according to claim 2, wherein the oxidizing agent is peracetic acid. 5. The method according to claim 2, wherein the strong acid is sulfuric acid. 6. The method according to claim 2, wherein the dehydrating agent is acetic anhydride. 7. The method according to claim 2, wherein the oxidizing agent is potassium persulfate. 8. The method according to claim 1, wherein the polyaryl sulfide is 1,4-dithiophenoxybenzene. 9. The method according to claim 1, wherein the polyaryl sulfide is dibenzothiophene. 10. An arylsulfonium salt selected from the following formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R^6 is a C_(_6_-_1_4_) aryl group or a substituted C_(_6_-_1_4) aryl group, and R ^7 is a divalent C_(_6_-_1_4_)arylene group or a substituted C_(_6_-_1_4_)arylene group, Q is -O-, =SO, -S- or a combination thereof, and M is a transition metal or semimetal, R^2
is a divalent arylene group selected from R^7 groups, and R
^8 is a trivalent C_(_6_-_1_4) arylene group or a substituted C_(_6_-_1_4) arylene group, Z is -O-, -S- or -C(R^5)_2-, and R ^5 is hydrogen or monovalent C_(_1_-_8_)
group, a is an integer equal to 0 or 1, and c is 1-3
is an integer equal to . 11. Compound of the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 12. Compound of the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 13. Compound of the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 14. Compound of the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 15. Compound of the following formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼