DE1261501B - Process for the production of beta-hydroxyalkyl-ethyl-sulfides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WlW PATENTAMT Int. CL:

C07c

EDITORIAL

German class: 12 ο -23/03

Number:
File number:
Registration date:
Display day:

1261 501
B89197IVb / 12o
4th October 1966
February 22, 1968

The invention relates to a process for the preparation of / 3-hydroxyalkyl-ethyl-sulfides general formula

Process for the production of
/ ϊ-hydroxyalkyl ethyl sulfides

R,

OH

where R is hydrogen or methyl, by reaction of the corresponding / 3-hydroxyalkyl mercaptans with ethylene.

It is known from Russian Chemical Reviews, Vol. 32, (1963), pp. 400 to 404, that by Implementation of mercaptans with olefins thioethers is obtained. In this process is in the presence of catalysts, e.g. B. of acids such as sulfuric acid; Bases, such as tertiary amines, Friedel-Crafts catalysts, such as boron trifluoride etherate, peroxides and sulfur worked. The catalysts are used in amounts of 10 to 15 percent by weight, based on olefin (see E. E. R e i d, S. O. Jones, J. Amer. Chem. Soc. 60, 2455, [1938]). This process has the particular disadvantage that it is prepared according to it Must separate reaction products from the catalysts used in order to obtain pure process products to obtain. In addition, in many cases the yield is only moderate because it is often undesirable Form by-products.

Both the German patent 740 247 and Reid (loc. Cit., P. 32) describe the necessity the addition of catalysts (peroxides), with no peroxide formation in the case of ethylene is described. French patent 1,393,251 also describes the addition of Catalysts, while the German patent specification 684 239 only olefins with at least 6 carbon atoms used as starting materials, according to German patent 740 247 mostly peroxides form and thus already contain the catalyst.

Ethylene does not form peroxide under the conditions of the invention (cf. Houben - Weyl, Methods of Organic Chemistry, Vol. 8, p. 12; Scott, Atmosphere Oxidation and Antioxidants, Elsevier Publ. Comp., 1965, p. 66 ff.) , since the oxygen attacks the carbon atom in the α-position to the double bond of an olefin. As a work in Journal of the American Chemical Society, vol. 60, p. 2455, 6th paragraph, teaches, there is a reaction between ethylene and mercaptans, e.g. B. ethane thiol, in the absence of catalysts even under difficult conditions (10 hours at 180 ⁰ C) does not take place; a formation of the reaction kataly applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, 6700 Ludwigshafen

Named as inventor:

Dr. Kurt Schneider, 6703 Limburgerhof;

Dr. Harry Distler,

Dr. Gerhard Klatt, 6700 Ludwigshafen, Germany

Sating peroxides of ethylene were not observed. Without the addition of catalysts, e.g. B. Peroxides, even the very reactive p-thiocresol is not reacted with olefins (loc. Cit., P. 2453, 3rd paragraph; with regard to the reactivity of p-thiocresol in comparison to ß-hydroxyalkyl mercaptans, cf. Russian Chemical Review, Vol. 32, p. 401, Table 1, and Reid, Organic Chemistry of Bivalent Sulfur, Vol. II [1960], p. 29).

It has now been found that ß-hydroxyalkyl-ethyl sulfides the general formula

- CH ₂ - CH ₃

ΛΙΤΤ / ^ XJ <

OH

wherein R is hydrogen or methyl, by reacting the corresponding /? - hydroxyalkyl mercaptans with ethylene at elevated pressure advantageously obtained when the reaction is performed at temperatures of 80 to 250 ⁰ C.

The new process has the great advantage that these | S-hydroxyalkyl-ethyl-sulfides are not contaminated either by a catalyst or by undesired by-products. The ß-Hy droxyalkyl-ethyl-sulfides produced in this way can be used directly for other reactions without further purification. They can be used as raw materials for the production of valuable insecticides.

One works in the temperature range from 80 to 250 ° C, preferably at temperatures between 100 and 180 ° C. It is necessary to carry out the procedure using pressure. Included the pressure can be the autogenous pressure of the reaction mixture at the particular reaction temperature correspond. However, it is also possible at higher rates

809 509/343

Press, ζ. B. up to 300 atm to work. The starting materials can be used to carry out the process Submit in the reaction vessel and then bring the mixture to the desired reaction temperature heat. But you can also z. B. submit the corresponding ß-hydroxyalkyl mercaptan, Heat up to the desired reaction temperature and then add the ethylene.

Inert organic compounds can be used as the solvent, e.g. B. aromatic hydrocarbons such as benzene, toluene, the xylenes, or chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, chloroform, carbon tetrachloride or trichlorethylene. In general, if you want to work in the presence of solvents, the after. Process to be produced ß-Hy droxyalkyl-ethyl-sulfide. As a rule, a 10 to 90 percent strength by weight solution of the corresponding / 5-hydroxyalkyl mercaptan is used.

The parts given in the following example mean parts by weight.

example

40 parts of 3-hydroxyethyl mercaptan are placed in a pressure vessel and 15 parts of ethylene are injected, with shaking at 150 ° C. and 100 atmospheres. After a reaction time of 16 hours, the reaction mixture is let down. Are obtained (yield: 95% of theory) of 52 parts of ethyl (ß-hydroxyethyl) sulfide by Kp.2o = 81 ⁰ C.als colorless liquid.

Claims (1)

Claim: Process for the production of /? - Hydroxyalkyl-ethyl-sulfides the general formula R - CH - CH ₂ - S - CH ₂ - CH ₃ OH wherein R is hydrogen or methyl, the corresponding ß-hydroxyalkyl mercaptans with ethylene at elevated pressure, characterized in that is carried out by reacting the reaction at temperatures from 80 to 250 ⁰ C. Considered publications:
German Patent Nos. 684 239, 740 247;
French Patent No. 1,393,251;
EE Reid, "Organic Chemistry of Bivalent Sulfur", Vol. II (1960), p. 31.