CS266277B1 - Process for preparing alkylaryl sulfides - Google Patents

Abstract

The solution relates to a method for preparing alkylaryl sulfides of the general formula where R represents methyl to tetradecyl, isopropyl, isobutyl and secondary butyl by reacting sodium arylthiolate with linear and branched haloalkanes, where halogen can be chlorine, bromine, iodine in a water and benzene environment, in the presence of interfacial catalysts derived from N,N'-bis(alkyldimethyl)-1,6-hexanediammoniumdibromides, where alkyl represents butyl to hexadecyl for 10 to 60 min, at temperatures of 20 to 80 °C. The final compounds are useful as intermediates in organic synthesis in the preparation of biologically active surfactant-type compounds.

Description

The invention relates to a process for the preparation of alkylaryl sulfides of the general formula

who R is butterfly to tolradecyl, isopropyl, isobutyl and secondary butyl. The compounds are used to modify biologically active compounds in the preparation of biologically active compounds.

It is known that alkylaryl sulfides can be prepared in several ways, such as e.g. substitution bimolecular reaction of arylthiolate with haloalkanes in polar medium with average yields around 70%, addition of thiols to unsaturated compounds in the presence of Lewis acids with yields ranging from 50 to 90%, reduction of sulfones and sulfoxides to sulfides in yields up to 70% and some less used procedures.

Recently, a process for the preparation of compounds of a similar type using interfacial catalysis methods is also gaining in importance. For example. 1- and 2-octylphenyl sulfide and neopentylphenyl sulfide were prepared in this manner in yields of about 90% in water, at temperatures of 40 to 70 ° C, for 10 to 180 minutes using tributylhexadecylphosphonium bromide as an interfacial catalyst *. The literature (e.g. Landinin D., Angelamaria M., Rampoldi A., J. Org. Chem. 51, 3 187 (1986) states that organic monoammonium salts, especially at higher temperatures and in a basic environment, are not very suitable for this type of reaction. There is no data in the literature on the use of bis or polyammonium salts as interfacial catalysts for the preparation of alkylarylsulphides.

The preparation process according to the invention uses the reaction of linear and differently branched haloalkenes (halogen is chlorine, bromine, iodine) with thiophenolate anion in a water-benzene ^{medium in the presence of N, N -} bis (alkyldimethyl) -1,6-hexanediammonium dibromides, where alkyl is butyl to hexadecyl at. temperatures of 20 to 80 ° C, for 10 to 60 minutes to give alkylphenyl sulfides in high yields. The preparation process according to the invention uses a hitherto unknown method for the preparation of alkylarylsulphides using bisammonium salts as interfacial catalysts. The advantage of the process according to the invention is that the products are formed in high yields both under mild reaction conditions and at higher temperatures, regardless of which halogen derivative is used.

The selected examples illustrate but do not limit the method for preparing the alkylarylsulfides of the invention.

Example 1- and d 1

Dissolve 0.1 mol of thiophenol in 100 ml of aqueous sodium hydroxide solution, add an equal volume of benzene, N, N-bis (dodecyldimethyl) -1,6-hexanediammonium dibromide in an amount of 0.01 mol and 0.1 mol of 2-bromobutane. With stirring under an inert gas atmosphere, the reaction mixture is kept at 20 ° C for 60 min. The benzene layer is separated, washed with water, dried, the benzene is distilled off and the product, which is sec-butylphenyl sulfide, is distilled off in vacuo: m.p. in. 108-109 ° C / 1.6 kPa; = 1,543 4; = 0.54 (Alufol impregnated with silicone oil, detection with 0.1 molar aqueous solution of KMnO 2, chloroform-methanol-water developing system 5: 15: 1), yield 85%.

Example 2

The procedure is the same as in Example 1, except that 1-bromododecane was used instead of 2-bromobutane in the reaction, the concentration of the interfacial catalyst was 0.03 mol, temperature 40 ° C, reaction time 30 min. The yield of 1-dodecylphenyl sulfide was 90%; t. in. 154-155 ° C / 0.05 kPa; t. t. 32-33 ° C; Rf = 0.16. Γ

CS 266 277 Bl

Example 3

The procedure is the same as in Example 1, except that 1-chlorobutane is used instead of 2-bromobutane in the reaction, the concentration of the interfacial catalyst is 0.005 mol; temperature 80 ° C; 15ρ 15 min; 1-butylphenyl sulfide yield 91%; t. in. 118-119 ° C / 1.3 kPa;

P r í I; I a <1 Ί

The procedure is the same as in Example 1, except that iodomethane was used instead of 2-bromobutane in the reaction, the concentration of the non-phase catalyst was 0.001 mol, reaction time 10 min, reaction temperature 25 ° C, yield 94%; t. in. phenylmethyl sulfide was 188 ° C; ηβθ - 1,585 5; 0.60.

Claims (1)

P R E Γ) M U T OF THE INVENTION Process for the preparation of alkyl aryl sulfides of general formula wherein R is methyl to tetradecyl, isopropyl, isobutyl and secondary butyl, characterized by. that a sodium arylthiolate of the formula is reacted with a halokane of the general formula wherein R is the same as above and X is chlorine, bromine, iodine in water and benzene in the presence of an N, N'-bis (alkyldimethyl) -1,6-hexanediammonium dibromide interfacial catalyst of the general formula CH, CH, I ³ ! ³ _ R'-N ⁺ - (CH 2), - ⁺ N-R'2 Br I 2 6। ch ₃ ch ₃ wherein R 'is butyl to hexadecyl, for 10 to 60 minutes at 20 to 80 ° C.