SU791741A1 - Method of preparing ditertiary alkylthioenine glycols - Google Patents

Description

lization with a yield of 88-95%. The process time is 8-16 hours.

The new method is characterized by the following advantages: the production of new compounds of formula 1, with a high yield, one-step process and its manufacturability, cheapness and availability of raw materials, regeneration of ammonia used and ease of isolation of the target products.

Example 1. Synthesis of 2,7-dimethyl-3-ethylthio-3-octene-5-in-2, 7-diol (1a)

To a solution of 3.71 g (O, 074 mol) of diacetylene in 200 ml of liquid ammonia was added 0.6 g (0.015 mol) of powdered caustic soda, then 11.6 g (0.2 mol) of acetone was slowly added. The mixture is stirred for 4 hours at (-30) -33 ° C), after which 6.2 g (0.1 mol) of ethanethiol are added and stirring is continued for another 8 hours (the ratio of diacetylene: ketone: thiol is 1: 2, 7: 1,3). Ammonia evaporating during the reaction is collected in a cooled trap and returned to the reactor. At the end of the experiment, ammonia is evaporated and collected. into a trap. The residue is dissolved in 150 ml of benzene, the precipitate is filtered off. From the filtrate, by evaporation of benzene to 50 ml and addition of 100 ml of hexane by crystallization, 16.2 g (95.6% based on hydrated diacetylene) diol (1a) were isolated, m.p. 67-68 ° C.

Found,%: C 63.03; H 8.69; 5 14.00.

С / (2 И

Calculated,%: C 63.12; H 8.83;

S 14.04.

Example 2. Synthesis of 2,7-dimethyl-3-propylthio-3-octene-5-in-2, 7-diol (16).

 To a solution of 0.6 g (0.012 mol) of diacetylene in 90 ml of liquid ammonia is added 0.1 g (0.0025 mol) of sodium hydroxide and slowly 1.6 g (0.028 mol) of acetone. The mixture is stirred for 3 hours at (-30) -X-33 ° C, 1.1 g (0.145 mol) of propanethiol (diacetylene: ketone: thiol ratio is 1: 2.3: 1.2) are added and the mixture is stirred for another 5 hours. Ammonia evaporating during the reaction is collected in a cooled trap and returned to the reactor. At the end of the experiment, the ammonia was evaporated, the residue was dissolved in 50 ml of benzene, and the precipitate was filtered off. Benzene is evaporated and 2.78 g (95.3% (based on diacetylene) diol (1 b), m.p.) are recovered by recrystallization from hexane. 340 ° C. ,

Found,%; C, 64.11; H 9.16; 5 13.15.

C jjHrjQOaS Calculated,%: C 64.44; H 9.15; S 13.20.

Example 3. Synthesis of 2,7-dimethyl-3-isopropylthio-3-octene-5-in-2, 7-diol (1 in).

To a solution of 0.91 g (0.018 mol) of diacetylene in 85 ml of liquid ammonia was added 0.2 g (0.005 mol) of powdered sodium hydroxide and 2.90 g (0.05 mol) of acetone was added dropwise. The mixture was stirred for 4 hours at (-30) (-, then 1.64 g (0.022 mol) of isopropanethiol (the ratio of diacetylene: ketone: thiol was 1: 2.7: 1.2) was added and the mixture was stirred for another 7 hours. during the reaction, the ammonia is collected in a trap cooled by liquid ammonia and returned to the reactor. At the end of the experiment, the ammonia

evaporated, the residue was dissolved in 100 ml of benzene, the precipitate was filtered off. The filtrate is evaporated to a volume of 40 ml and 50 ml of hexane is added, 4.47 g (86.6% in

calculated on taken diacetylene diol (1c), m.p. 64-65 C.

Found,%: C 64.35; H 9.30; S 13.26.

ib lii Nm calculated,%: C 64.44; H 9.15; S 13.20.

Example 4. Synthesis of 2,7-dimethyl-3-butylthio-3-octene-5-in-2, 7-diol (1 g),

To a solution of 0.6 g (0.012 mol)

diacetylene in 85 ml of liquid ammonia is added 0.1 g (0.0025 mol) of sodium hydroxide and 1.6 g (0.028 mol) of acezone. The mixture is stirred for 3 hours at (-30) (-33cJ, then 1.4 g is added

(0.016 mol) of butanethiol (diacetylene: ketone: thiol ratio is 1: 2.3: 1.3) and stirring is continued for another 7 hours. Ammonia evaporating during the reaction is collected in a trap and returned to the reactor. At the end of the experiment, the ammonia is evaporated, the residue is filtered off and 2.75 g (89.4% based on the taken diacetylene) diol (1 g) are isolated, b.p. mm

Hg, p 1.5210.

. Found,%: C 65.25; H 9.49; S 12.30.

44 24 i Calculated,%: C 65.59; H 9.44;

S 12.48.

Example 5. Synthesis of 2,7-dimethyl-3-isobutylthio-3-octene-5-in-2, 7-diol (1d).

To a solution of 0.6 g (0.012 mol) of diacetylene in 85 ml of liquid ammonia

Claims (1)

0.16 g (0.003 mol) of potassium hydroxide is added, then added. drop 1.6 g (0.028 mol) of acetone and stir the mixture for 4 hours at f-30) (). 1.4 g (0.016 mol) of isobutanethiol (diacetylene: acetone: thiol ratio is 1: 2.3: 1.3) are added and the reaction mixture is stirred for another 8 hours. Ammonia evaporating during the reaction is collected in a cooled trap, and returned into the reactor. At the end of the experiment, the ammonia was evaporated, the residue was dissolved in 50 ml of benzene, the precipitate was filtered off, the benzene was removed and recrystallization from hexane gave 2.92 g (93.6% based on the taken diacetylene) diol (1d), t. mp 4647 ° C. Found,%: C 65.22; H 9.44; S 12,53. C 4 N. Calculated,%: C 65.59; H 9.44; S 12.48. Example 6. Synthesis of 3,8-dimethyl-4-ethylthio-4-decene-6-yn-3, 8-diol (1e). To a solution of 3.9 g (0.078 mol) of diacetylene in 250 ml of liquid ammonia, 0.77 g (0.019 mol) of powdered caustic soda, 14 g (0.19 mol) of methyl ethyl ketone are added and the mixture is stirred for 4 hours at C-30) - (Then 6.2 g (0.1 mol) of ethanethiol are added (diacetylene: ketone: thiol ratio is 1, 2.4-.1.3) and the reaction mass is stirred for another 12 hours. Ammonia evaporating during the reaction collected in a cooled trap and returned to the reactor. At the end of the experiment, the ammonia was evaporated, the residue was dissolved in 100 ml of ether, the precipitate was filtered off, the ether was removed and 15 g were isolated (95% calculated on flax) diol (1e), bp 152 kip. 153 ° C / 4 mm Hg, p | p 1.5 5335, H 9.43: Found: C 65.5 S 12.48 O H O Calculated,%: C 65.58; H 9.43; S 12.48. Example 7. Synthesis of 1,4-di- (oxycyclopentyl) -1-ethylthio-1-butene-3-ina (1g ). To a solution of 0.5 g (0.01 mol) of diacetylene in 160 ml of liquid ammonia, 0.75 g (0.0019 mol) of powdered caustic soda, a little bit 2.08 g (0.025 mol) of cyclopenta, are added and mixed mixture for 4 hours at -30} - (j-33 ° C). Then 0.68 (0.011 mol) of ethanethiol (diacetylene: ketone: thiol ratio is 1: 2.5: 1.1) is added and the reaction mixture is stirred for another 10 hours. Ammonia evaporating during the reaction is collected in a cooled trap and returned to reactor. At the end of the experiment, ammonia was evaporated, the residue was dissolved in 50 ml of ether, the precipitate was filtered off, ether was removed and 3.6 g (94.2% based on the taken diacetylene) diol (1g) were isolated, b.p. 184-18bs / 4 mm Hg, p | ° 1,5668. Found,%: C 68.51; H 8.39; S 11.48. fb 24 ° 2 Calculated,%: C 68.53; H 8.63; S 11.43. Claims of the method of producing di-Tertiary alkylthioenin glycols of the general formula cn-cc C-CnC SR he is 2 he R is ethyl, propyl, isopropyl, butyl or isobutyl and R is C2 methyl, or R is ethyl, R-methyl and R, J -ethyl, R - ethyl and RJ and R; together with the adjacent carbon atom form a cyclopentyl group, distinguished by the c and the fact that diacetylene is subjected to sequential interaction with the corresponding ketone of the formula and thiol of the formula RSH, where R, R have the indicated values, with a molar ratio of initial reagents equal to 1: (2, 3-2.7): (1.1-1.3) in the medium of liquid ammonia at a temperature of (-30 - () and in the presence of an alkali metal hydroxide in an amount of 0.19-0.27 moles per mole of starting diacetylene. Sources information taken into account in the examination 1. Nikolska A.I. and others. Synthesis of tertiary 1-alkylthio-1-ene-3-inic alcohols, Izv. AN SSSR, 1977, chemistry series, 6, pp. 1403-1406.