JPS6256465A - 4-vinyl-1-((2-phenythio)ethyl)benzene and alkyl substituted derivative thereof and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R is H or 1-4C alkyl; n is an integer 1-3). EXAMPLE:4-Vinyl-1-[(2-phenylthio)ethyl]benzene. USE:Useful as a polymerizable monomer. The polymer thereof is utilizable as a high polymer antioxidant, high polymer reaction agents, recording materials, etc. PREPARATION:p-Divinylbenzene is reacted with a thiophenol derivative in the presence of a radical reaction initiator, e.g. azobisisobutyronitrile, in a solvent, e.g. benzene or toluene, at 40-80 deg.C in nitrogen atmosphere to afford the aimed compound expressed by the formula. The reaction initiator is preferably used in an amount of 0.1-1.0mol% based on the p-divinylbenzene.

Description

Detailed Description of the Invention [Object of the Invention] The present invention provides a novel compound represented by the following structural formula, -f
An object of the present invention is to provide 4-vinyl-1-C(2-yenylthio)ethyl]benzene and alkyl-substituted derivatives and a method for producing the same.

Or it represents an alkyl group having 1 to 4 carbon atoms. n is an integer from 1 to 3. ) (Industrial Application Field) The compound of the present invention, 4-vinyl-1-C(2-phenylthio)ethyl]benzene, can be used as a styrene derivative, and its polymer can be used as a polymer antioxidant AIJ, a polymer reactant. It is expected to be used as an electronic recording material.

That is, the 4-vinyl-1-C(2-phenylthio)ethyl]benzene of the present invention is a useful substance as a radically polymerizable monomer, but it is a novel compound that has not been described in any known literature.

(Problems to be Solved by the Invention) Generally, sulfur-containing polymers have excellent heat resistance, electrical properties, and chemical resistance, and are expected to be applied as functional polymers.

On the other hand, by incorporating the unique reactivity of sulfur into polymers, it is possible to control reaction points through immobilization and express selectivity.
Polymer reactants that utilize steric effects and environmental effects, and polymer oxidative deterioration inhibitors that utilize the peroxide decomposition effect of sulfur have also been developed.

As a result of intensive efforts to develop polymers containing sulfur in the side chain, the present inventors have discovered a polymerizable sulfide-type styrene m-conductor, 4- Vinyl-1
It was discovered that -[: (2-phenylthio)ethyl]benzene can be obtained, leading to the present invention.

Alternatively, it represents a C1-C4 alkyl group. n is an integer from 1 to 3. ) [Structure of the Invention] (Means for Solving the Problem) The gist of the present invention represents a formula or a C1-C4 alkyl group. n is an integer from 1 to 3. ) and a method for producing the same.

That is, it is obtained by mixing P-divinylbenzene and thiophenol or a derivative thereof, and subjecting the mixture to azovisyain by a radical reaction using an initiator such as butyronitrile. The thiophenol derivative referred to herein refers to one having a thiophenol and a C1 to C4 alkyl group as a substituent.

For example, thiocresol, dimethylbenzenethiol,
Examples include ethylbenzenethiol and phthylbenzenethiol.

As the reaction initiator, in addition to azo compounds such as azobis-yne-butyronitrile and azohis-2-4-dimethylvaleronitrile, peroxides such as be/diyl peroxide and lauroyl peroxide are used, and the amount thereof depends on the raw material P- 0.01-10 mol% based on divinylbenzene, preferably 0.1-1.0
It is mole%.

Although the reaction may be carried out without a solvent, since P-divinylbenzene is a solid, it is more advantageous to use a solvent. As the solvent, aromatic hydrocarbons such as benzene and toluene are mainly used. All reactions are preferably carried out under a nitrogen atmosphere.

The molar ratio of P-divinylbenzene and thiophenol derivative is preferably around 1.0.

In this reaction, if the amount of thiophenol derivative is small, the yield will be small, and if the amount of thiophenol derivative is large, the diadduct R-φ-5-CH2-CH2+C
This is not preferable because H2-CH2-S-φ-R is produced as a by-product.

The completion of the reaction is determined by gas chromatography, and the reaction temperature is preferably 40°C to 80°C.9 When the reaction temperature was 55°C, the reaction time was 3 hours, and when the reaction temperature was 75°C, 1 hour was required. If the reaction temperature is too low, the reaction rate will be slow; if the reaction temperature is too high, side reactions will occur and the yield will decrease.

(Function) Example of reaction between P-vinylbenzene and thiophenol
Trans, Faraday So
c,), 30 18 (1934), R, Brow
n etal ;Journal Opchemical Society 4 (J, Chem, Soc, -L old 1.331
By analogy with 5), the reaction between P-divinylbenzene and thiophenol derivative of the present invention is based on Markownikof's
produces products that do not obey the law of f. This means that 'H
-It is in good agreement with the results of NMR analysis, suggesting the structure CH2=CI (-CFCFI2- CH2-S) [Example 1] Four flasks equipped with a stirrer, thermometer, and reflux condenser P-divinylbenzene9.13 P-tobenzene32-
Add the solution. After adding AIBN35.5 cape and purging with nitrogen, thiophenol 7- is added using a syringe. 75℃ on oil bath
The mixture was heated and stirred under a nitrogen atmosphere at -1. After 70 minutes, gas chromatography analysis showed that the yield was 90% or more.

P-tert-butylcatechol was added to the reaction mixture, the reaction mixture was cooled, and its drained water was added.

The aqueous layer is extracted six times with a benzene/ether (3:2) mixed solvent, mixed with the previously separated organic layer, and hydroxylated.) IJ
Washed with a cold aqueous solution of um, then 1 liter of water. After drying this with anhydrous magnesium sulfate, anhydrous iron chloride (III
) was added and the extraction solvent was removed. Then, fractional distillation was carried out under reduced pressure to obtain a fraction with a boiling point of 129-131''C10.04% Hg.

1. Elemental analysis CBS Theoretical value (%) 80.0 6.7 13.3 Actual value (9c
) 80.1 6.6 1131 nD
1.6206 3, 'HNMR (in CDCj!3) I value 7.0
3 (m, 9H) 6.48 (mjH) 5.48
(m, IH) 5.01 (m, IH) 2. ．． 88(
m, 4) 1) 4, IRcn-1 3050v = CH2,vC-H(rn).

1800 7CH=CI(2(W) 1630 νc=c(W), 1585 IC-
C(S)1510 JC-C(S), 1480
JCH2(S)1440 JCH2-5(S),
995 #=CI(m)740 a-@D (
S), 895, y-k (=Σ>Cm) From the above, the structure of this fraction is 4-viny#-1-CC2
-queerthio)ethyl]benzene.

[Example 2] 7.8 N of P-divinylbenzene and P-
A solution consisting of thiocresol 7.3y, AIBNO 1091 and benzene 45TfLt is added.

Heat at 75° C. for 2 hours in an oil bath under a nitrogen atmosphere. By applying the same post-treatment as in Example 1, bT) 13
A fraction of 10.06 Hg was obtained at 3°C.

1. Elemental analysis CI5 Theoretical value (%) 80.3 7.13 12.6 Actual value (%) 80.0 7.2 12.5Z, 'HN
MR (in CD (J3) δ value 7.00 (m, 8H
) 6.52 (m, IH) 5.52 (m, IH
) 5.03 (m, IH) 190 (m, 4H)
2.23 (S, 3H) From this, it was confirmed that the structure of this fraction was 4-vinyl-1-[2-(P-1 tylphenylthio)ethyl]benzene.

〔Effect of the invention〕

According to the present invention, the novel polymerizable sulfur-containing monomer 4-vinyl-1-C(2-phenylthio)ethyl]benzene and its alkyl-substituted derivatives can be easily obtained, and the polymer is used as a polymeric antioxidant.

It is expected to be applied to polymer reactants, recording materials, etc.

Applicant: Yuji Masuda, Representative of Steel Chemical Industry Co., Ltd. (Voluntary amendment written by Yuji Masuda) October 26, 1985 1 Indication of the case 1985 Patent Application No. 196650 2 Name of the invention 4-vinyl-1 [(2-phenyldio) ) Ethyl]benzene and its alkyl-substituted derivatives and their manufacturing method 3. Relationship with the case of the person making the amendment Patent applicant (δ0794-37-2151) 4. Subject of the amendment Description 5. Contents of the amendment (1) Description Page 5, line 5, "Azobis-iso-butyro" is corrected to "Azobisisobutyro".

(2) "P-vinylbengene" on page 6, line 11 of the specification is corrected to "vinylbenpine."

(3) "Translations of the Faraday Society" on page 6, lines 12-13 of the specification shall be amended to "Transactions of the Faraday Society."

(4) Correct "Journal of the Chemical Society" in lines 13 and 14 of box 6 to "Journal of the Chemical Society."

Claims (5)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R represents hydrogen or an alkyl group of C_1 to C_4. n is an integer of 1 to 3.) 4-vinyl-
1-[(2-phenylthio)ethyl]benzene and its alkyl derivatives. (2) Patent claims in which R is hydrogen A compound described in range (1). (3) General formula characterized by reacting P-divinylbenzene and a thiophenol derivative in the presence of a radical reaction initiator ▲There are mathematical formulas, chemical formulas, tables, etc. Represented by ▼ (the meanings of the symbols are the same as above) 4-vinyl-1-[
A method for producing (2-phenylthio)ethyl]benzenes. (4) The method according to claim (3), wherein the thiophenol derivative is thiophenol. (5) The method according to claim (3), wherein the radical reaction initiator is azobisisobutyronitrile.