DE1227890B - Process for the preparation of 1-oxa-2-thia-cyclobutane-2, 2-dioxides - Google Patents

Description

Process for the preparation of 1-oxa-2-thia-cyclobutane-2,2-dioxides It has been found that 1-oxa-2-thiacyclobutane-2,2-dioxides are obtained if carbonyl compounds of the general formula are used in which R- CCl3, -CBr, - CF3 or- CCl2CH2CH3 and R 'denotes hydrogen or alkyl, in the presence of tertiary aliphatic amines with sulfonic acid halides of the general formula in which R "denotes hydrogen or alkyl and R" denotes hydrogen, alkyl, aryl or halogen.

The fl-sultones are then created according to the following scheme: The reaction probably goes through the stage of the not yet isolated sulfenes (cf. for example G. Opitz and H. Adolph, Angew.

Chemie, 74, p. 77 [1962]).

The reaction is expediently inert towards the components organic solvents (ether, benzene, chloroform, carbon tetrachloride, etc.) carried out at temperatures between -30 and + 130 ° C.

Isolation of the products of the process according to the invention can by distillation or

Recrystallization of the resulting precipitate take place.

The products of the method according to the invention are used as end or intermediate products in the plastics, crop protection and pharmaceutical sectors.

Example 1 14.7 g of chloral are dissolved in 100 ccm of absolute ether and mixed with 11.4 g of methanesulfonyl chloride.

Into this solution is added dropwise with stirring over the course of 1 hour a nitrogen atmosphere at 0 to 10 "C a solution of 10.1 g of triethylamine in 50 cc of absolute ether, stirred for a further 14 hours at room temperature and then sucked from the precipitated amine hydrochloride, which is then extracted well with ether. When the ethereal mother liquor is evaporated, 4-trichloromethyl-1-oxa-2-thia-cyclobutane-2,2-dioxide is crystallized the end. After recrystallization from ether-petroleum, 9 g of pure β-sultone (42.3 O / o the theory); 98 to 100 "C; IR-lrso, = 1210, 1390 cm-1.

If you work in xylene at 130 "C, the yield of ß-sultone is between 35 and 380 / o of theory.

Example 2 56.2 g of bromal are dissolved in 100 cc of carbon tetrachloride dissolved and mixed with 46 g of methanesulfonyl chloride. Then it is added dropwise under nitrogen at -30 "C 40.4g triethylamine in 50ccm carbon tetrachloride and stirs for 14 hours at room temperature.

After the precipitate has been suctioned off, it is treated with absolute ethyl acetate extracted and the combined mother liquors evaporated and distilled in vacuo. Yield of 4-tribromomethyl-1-oxa-2-thiacyclobutane-2,2-dioxide 29 ovo of theory; Bp 0.4-0.5 = 103 ° C; IR- # SO2 = 1190, 1390 cm-1.

Example 3 If one sets similarly; as described in Example 1, chloromethanesulfonyl chloride with chloral, 4-trichloromethyl-3-chloro-1-oxa-2-thia-cyclobutane-2,2-dioxide is obtained in the above yield. Bp 0.9 = 107 to 112 "C, m.p. 81 ° C (ligroin), IR- # SO2 = 1205, 1400 cm-1.

With trimethylamine as the acid acceptor, the yields are the same Magnitude.

Example 4 gives benzyl sulfochloride with chloral among those in the example 1 described reaction conditions in addition to stilbene in 13% yield so far 4- trichloromethyl -3- phenyl -1-oxa-2-thia-cyclobutane-2,2-dioxide (IR- # SO2 = 1200, 1400 cm-1).

Claims (1)

Claim: A process for the preparation of 1-oxa-2-thiacyclobutane-2,2-dioxides, characterized in that carbonyl compounds of the general formula are used in which R-CCl3, -CBr3, -CF3 or -CCl2CH2CH3 and R 'denotes hydrogen or alkyl, in the presence of tertiary aliphatic amines with sulfonic acid halides of the general formula in which R "denotes hydrogen or alkyl and R" denotes hydrogen, alkyl, aryl or halogen. References Considered: U.S. Patent No. 2,852 554.