DE3104744A1 - METHOD FOR PRODUCING COMPLEX TRIARYL SULPHONIUM SALTS - Google Patents

Description

Process for the preparation of complex triarylsulfonium salts

Before the filing date of the present invention, how as shown in U.S. Patent 4,173,476, various complex triphenylsulfonium salts by heating a mixture of diphenyl sulfide, diphenyl sulfoxide and phosphorus pentoxide manufactured. Another method according to German patent application P 30 35 807.7 * is based on the use of a Diaryl thioether and a diaryl iodonium salt in the presence of a copper (II) catalyst. Another method is based on the use of aluminum chloride as described in US Pat. No. 2,807,648. Although the aforementioned procedures for thioaryloxytriarylsulfonium salts can be used, exceeds the yield that can be obtained with these methods receives, rarely 50%. It is therefore desirable to have a process for the preparation of thioaryloxytriarylsulfonium salts with to create significantly improved yields.

The present invention therefore provides a process for the preparation of triarylsulfonium salts of the general formula I.

* (own file 8479-RD-11717)

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R — SR ¹ S ⁺ ΜΧ ~ (I)

ι η

created in which one

(1) the self-condensation of diaryl sulfide of the general formula

R-S-R

causes in the presence of elemental halogen and a Lewis acid,

(2) the obtained diaryl sulfide self-condensation reaction product of (1) at temperatures of up to 100 ° C with a metal salt of the general formula II

YMX _n (II)

implements, and

(3) the triarylsulfonium salt of the general formula I wins,

being in the formulas

R is a monovalent, aromatic, organic radical with 6

up to 13 carbon atoms,
-ι

R is a divalent, aromatic, organic radical with 6 up to 13 carbon atoms /

Y is an alkali metal or alkaline earth metal ion, M is a metal or metalloid,
X is a halogen radical

means and the index
η has a value from 4 to 6, inclusive.

The radicals encompassed by R in the general formula I can be identical or different and are, for example, phenyl, ToIy1, XyIyI, Naphthyl, Anthryl, etc. From R the general The radicals included in formula I are, for example, phenylene, tolylene,

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Xylylene, naphthylene, etc. The aforementioned radicals R and R can also be replaced by 1 to 4 C ^ ₁ ". -Alkyl or -alkoxy radicals,

ν l - ο )

such as methyl, methoxy, ethyl, propyl, butoxy, etc., halogen radicals, for example chlorine, bromine or fluorine, etc., as well as nitro, carbonyl and carboxy, may be substituted. Some

of the radicals comprised by MX are, for example, PF ,, η b

BF

, SbF ₅ OH

and SbCl,

Some of the triarylsulfonium salts of the general formula I are compounds of the formulas below;

CH.

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31Q4744

SbF,

Br

■ S AsF,

Br

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310A744

NO ₂

Suitable metal salts of the general formula II are, for example, sodium or potassium tetrafluoroborate, NaPFg, NaAsFg, KSbFg, KAsFg, Ca (PFg) ₃ , Mg (AsFg) ₃ , HPFg, HAsFg, HSbFg, Ba (AsFg) ₂ , Pb (PFg) ₃ , Zn (AsFg) ₃ , etc.

In practicing the present invention, a diaryl sulfide such as diphenyl sulfide, dinaphthyl sulfide, etc., is reacted with an elemental halogen and Lewis acid to produce a triarylsulfonium halide complex. Although the order of addition of the reactants is not critical, it is preferred to introduce the halogen in the presence of the Lewis acid catalyst. Accordingly, a mixture of the diaryl sulfide and the Lewis acid can be prepared initially. Suitable Lewis acid catalysts that can be used include, for example, aluminum chloride (AlCl ₃ ), SnCl., BF ₃ , BCl ₃ , PF ₅ , SbF ₅ , AsF ₅ , etc. It can range from about 0.5 to 2, 0 moles of elemental halogen, for example chlorine, bromine, etc., per mole of diaryl sulfide and 10 to 90 percent by weight of the Lewis acid catalyst, based on the mixture of diaryl sulfide, elemental halogen and Lewis acid catalyst, can be used. Temperatures can range from between

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-10 ° to 10O ⁰ C, and are preferably applied from 0 ° to 25 ° C, along with a movement of the mixture, such as stirring.

After the triarylsulfonium halide is formed as a result of the complete introduction of halogen into the mixture the mixture obtained can be poured into ice water to destroy the Lewis acid complex. The triarylsulfonium halide can then be obtained from the mixture by conventional procedures and further with an alkali metal or alkaline earth metal, or a polyhalometalloid for causing a reaction with the triarylsulfonium halide be made to react. If desired, the polyhalometalloid can be added directly to the mixture without Isolation of the triarylsulfonium halide can be added.

The mixture obtained can be heated to a temperature of 0 to 100 ^° C. and stirred for 0.1 to 24 hours. The triarylsulfonium polyhalide metalloid salt obtained can be separated off by customary procedures, such as decanting, filtering, etc., and then first washed with water and dried in a vacuum oven at temperatures of about 40 ° to 120 ° C.

The following examples serve to explain the practical implementation of the process according to the invention in more detail. however, these are not intended to limit the invention. All parts are parts by weight.

example 1

Elemental chlorine was slowly passed in gaseous form into a container containing 37.2 parts of diphenyl sulfide and 13.34 parts Contained aluminum chloride. After passing in 9.5 parts of chlorine

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the mixture was poured into approximately 500 parts of ice water. A white, semisolid was obtained in about 95% yield Material. The white, semi-solid material was 4-thiophenoxyphenyl-S-diphenylsulfonium chloride from the manufacturing process.

To the aforementioned triphenylsulfonium chloride was added 22.8 parts of potassium hexafluoroarsenate in 300 parts of hot water admitted. The mixture was warmed to a temperature of about 60 ° C. and stirred for 1 hour. By decanting an orange-colored oil was separated off, which was washed first with water and then with anhydrous ethyl ether became. Finally the product was dried in a vacuum oven at 60 ° C for a period of about 8 hours. According to its manufacturing process, the product had its

Formula:

of its ultraviolet and 13 C-NMR spectra the following

Based on the diphenyl sulfide used as the starting material, the yield of the above sulfonium salt was 80% obtain.

A 3% solution of the above salt in 4-vinylcyclohexene dioxide had a tack-free time of less than 1 second when viewed after application to a glass substrate in the form of a 50.8 ym (2 mil) thick layer using a GE iOTT medium pressure mercury arc lamp, which is in a

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- 10 -

Was mounted 15.24 cm (6 inches) from the solution, irradiated.

Example 2

To a stirred mixture of 50 parts of diphenyl sulfide and about 300 parts of glacial acetic acid, 90 parts of bromine were slowly added. The temperature of the reaction mixture rose to 30 ^° C. and a yellow precipitate formed. After all of the bromine had been added, the reaction mixture was heated to 50 ° to 60 ° C. and held at that temperature for 2.5 hours. The mixture was then allowed to cool and a product was isolated by filtration which was dried in vacuo. A product yield of 82.4% was achieved. By its method of manufacture, the product was 4,4'-dibromo-diphenyl sulfide.

Chlorine gas was slowly passed into a stirred mixture of 75.7 parts of the above 4,4'-dibromodiphenyl sulfide dissolved in 435 parts of benzene. After 33 parts of chlorine gas had been introduced, an orange-colored crystalline product was obtained. A solid was isolated by filtration and washed with cold benzene and hexane. A yield of 89% of 4,4 ¹ -dibromodiphenylchlorosulfonium chloride was achieved.

27.9 parts of the above 4,4'-dibromo-diphenylchlorosulfonium chloride were added in small portions over 10 minutes with stirring to a mixture of 40 parts anhydrous Aluminum chloride in about 110 parts diphenyl sulfide admitted. During the addition the reaction mixture turned dark brown and then purple in color. The solution became more Stirred for 3 hours at room temperature and then poured into 150 parts of ice water. A yellow oil was obtained which

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was isolated by decantation. After washing twice with ethyl ether, the oil with 100 parts of water and 15 Parts of potassium hexafluoroarsenate mixed. The mixture was stirred vigorously for 1 hour and the resulting product, the was a yellow oil, was removed by decantation and washed once again with ethyl ether. According to its manufacturing process the product was a salt of the following formula:

AsF,

Br

A 3% solution of the above salt in 4-vinylcyclohexene dioxide had a cure time of 3 to 5 seconds when viewed using a GE H3T7 lamp as in Example 1 described, irradiated.

Although the foregoing examples focus on only a few of the very numerous variables of the present invention It should be noted that the invention encompasses a much broader process for the preparation of triarylsulfonium salts of the general formula I based on the reaction of a diaryl sulfide and a Lewis acid catalyst, turned off is.

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Claims (7)

31047U Dr. rer. near Horst Schüler PATENTANWALT 6000 Frankfurt / Main 1, Feb. 10, 1981 Kaiserstraße 41 Dr. Sch / Um / Hk, Telefon (0611) 235555 Telex: 04-10759 mapat d Postscheck-Account: 282420-602 Frankfurt-M. '' Bank account: 225/0389 Deutsche Bank AG, Frankfurt / M. 8591-RD-11944 GENERAL ELECTRIC COMPANY 1, River Road Schenectady, N.Y., U.S.A. claims 1.J Process for the preparation of a complex triarylsulfonium salt the general formula R.
¹ S ⁺ / 7 \ R-S-R ¹ -S ⁺ MX characterized in that one (1) the self-condensation of diaryl sulfide of the general formula R-s-R causes in the presence of elemental halogen and a Lewis acid, (2) the resulting diaryl sulfide self-condensation reaction product of (1) at temperatures of up to 10O ⁰ C with a metal salt of the general formula YMX _n
implements, and (3) the triarylsulfonium salt is obtained from the mixture of (2), being in the formulas R is a monovalent, aromatic, organic radical with 6 130047/0556 J..!. ·: ..:.: ;; -; · ■; Ί 31Q4744 up to 13 carbon atoms,
ι
R is a divalent, aromatic, organic radical with 6 up to 13 carbon atoms, Y is an alkali metal or alkaline earth metal ion, M is a metal or metalloid,
X is a halogen radical
means, and the index η has a value from 4 to 6, inclusive. 2. The method according to claim 1, characterized in that that the diaryl sulfide is diphenyl sulfide. 3. The method according to claim 1, characterized in that that the elemental halogen is chlorine. 4. The method according to claim 1, characterized in that that the Lewis acid is aluminum chloride. 5. The method according to claim 1, characterized in that that the metal salt is potassium hexafluoroarsenate. 6. The method according to claim 1, characterized in that that the metal salt is potassium hexafluoroantimonate. 7. The method according to claim 1, characterized in that that the metal salt is potassium hexafluorophosphate 130047/0556