SU953817A1 - Process for preparing bis-(2-alkeneoxythyl)-sulfoxides - Google Patents

Abstract

METHOD OF OBTAINING BIS

Description

The invention relates to a new method for producing new bis - ^ - alkenoxyethyl) sulfoxides of the general formula (R0CH ₂ CH ₂ ) ₂ 50, where R - CHD = CHCH _D -, CH ₃ CH.-CHCH ₂ - or COH ₅ CH = CHCH2-, which have biological activity and can find application in medicine.

The literature describes the principle. the possibility of obtaining compounds that are close in structure to the described sulfoxides of formula 1, for example bis (2-methoxyethyl) sulfoxide or bis (2-ethoxyethyl) sulfoxide, by reacting the corresponding 15 absolute alcohol solutions of alkali, sodium golyate with divinyl sulfoxide during boiling [1] .

However, in this way it is not possible to obtain new compounds of formula 1, since unsaturated alcohols ⁴ do not react with divinyl sulfoxide under the conditions of the known method.

The aim of the invention is to develop a method for producing new unsaturated sulfoxides of the formula 1, which would have valuable properties.

This goal is achieved by the fact that divinyl sulfoxide (DICO) is reacted with the corresponding unsaturated alcohol in the presence of a mixture of potassium tert-butoxide with dimethyl sulfoxide (DMSO) at a temperature of 35125 ° С as a catalyst. Yield 76-93%.

The process is 6-8 hours.

The use of this catalytic system makes it possible to use commodity alcohols as initial ones without preliminary dehydration and to obtain target products with high yields (up to 93%). ''

After distillation of the unreacted alcohol from the reaction mixture, the bis- (2-alkenoxyethyl) sulfoxide formed is isolated by conventional methods. Target products are colorless oily liquids, well, soluble in most. organic solvents insoluble in water.

Thus, the described method is versatile, one-stage, simple technological execution, does not require the use of special equipment, allows to obtain target products with high yields, and also provides for the regeneration of excess alcohol.

Example!. Bis- (2-allyloxyethyl) sulfoxide.

To a mixture of 27.0 g (0.46 mol) of allyl alcohol, 0.58 g of tert-butoxy; yes of potassium and 0.6 ml of DMSO, heated to '50

85 ° С, 14.9 g (0.146 mol) of DVCO are added dropwise with stirring and the mixture is heated for 8 hours. After cooling, excess (9.0 g or 97%) of allyl alcohol is distilled off from the reaction mixture. 24.2 g of bis- (2-allyloxyethyl) sulfoxide are obtained from the residue by distillation in vacuo, yield 7b%, ‘bp. 159 ° C / 2 mmHg ’.; P. 1.4939, 1.0701.

Found,%: C 54.88; H8.38? | S 14.23.

Calculated,%: From 55.04? H, 8.26; S 14.67.

PIR spectrum (b, ppm): 5.88 (= CH multiplet); 5.17 (= CH ₂ -multiplet)} ,, 3.97 (= C-OCH ^ -multiplet); 3.76 (-OSH _? - multiplet) ^ 2.90 (-5 CH ₂ - multiplet

Example 2. Obtaining bis - (2-,

-krotyloxyethyl) sulfoxide.

7.45 g (0.073 mol) of DICO was added dropwise with stirring into a solution of 18 g (0.249 mol) of crotyl alcohol, 0.29 g of potassium tert-butoxide and 0.3 ml of DMSO, heated to 100 ° С and continued to be heated for 6 hours. After treatment according to Example 1, 7.8 g (98%) of crotyl alcohol is isolated and 14.6 g of bis (2-crotyloxyethyl) sulfoxide are obtained, yield 81%, 'bp. 150 ° C / 1.10 ^L mm Hg ; I ™ 1.4038 *,

1.0430. .®

Found,%: С 58.41, ’Н 9.10, '13.33. ·

Calculated,%: C 58.53; H 8.94; 13.00. ’

PMR spectrum (b, ppm): 5.46 (-CH = CH multiplet); 3.95 (-C-OCH ₂ multiplet); 3.70 (-OSND-triplet); 2.81 (- BSNd multiplet); 1.70 (CH ^ - doublet).

_O'g

Example 3. Preparation of bis- [2- (β '-phenyl) allyloxyethyl} sulfoxide.

To a mixture of 32.34 g (0.241 mol) of cinnamon alcohol, 0.37 g of potassium tert-butoxide and 0.5 ml of DMSO / heated to 125 ° C, 5.1 g (0.05 mol) of DVCO are added dropwise with stirring and continued heat bh. After the treatment according to Example 1, 17.8 g (95%) of cinnamon alcohol are isolated and 17.2 g of [2- (β-phenyl) allyloxyethyl] sulfoxide are obtained, yield 93%; t.kip. 169 ° C / / 1'10 ^? mmHg. 1.5920;

1.1567. ^B

Found,%: C 71.12? H 7.15? S 8.83.

Calculated,%: C 71.35? H, 7.03; ‘8.65.

PMR spectrum (b, mp): 7.18 (Sonosinglet); 6.15 (-CH = CH - multiplet); 4.01 (zC-OCH "z-doublet);'3.73 (-OSH _? -Triplet)? 2.85 (-5 CH ₂ multiplet)

Oh s

ВНИИПИ Order 8241/7 Circulation 418 Subscription

Branch of the PPP Patent / Uzhgorod, Project 4,

Claims (1)

METHOD OF BIS- (2-ALKENOKSIETIL) sulfoxides of general ^formulas (ROCH-jCH ^ SO, where 'R - CH = CHCH _{g A} -, CH SNzSNSN or C ₆ NuSN CHCH = _d -, l and m of h and, The fact is that divinyl sulfoxide is reacted with the corresponding unsaturated alcohol in the presence of a catalyst of a mixture of potassium tert-butoxide with dimethyl sulfoxide at a temperature of 85-125 ° C. if)