SU1168558A1 - Method of obtaining alkyl-substituted 6-cyanotetrahydro-1,3-oxazine-2-thione - Google Patents

Abstract

METHOD FOR OBTAINING ALKYL SUBSTITUTED 6-1 SCHANOTETRAHYDRO-1,3-OXAZIN-2-TION OF THE GENERAL FORMULA „RI C N A L, RH N S N. R, - C, SF-alkyl; where fK ,, K, and independently each other hydrogen or C-alkyl, characterized in that, A-isothiocyanatoketo and the general formula O and R, 1 R: (L K have the indicated values, where they are reacted with acetone cyanohydrin at room temperature in the presence of catalytic amounts of alkali. a 00 ate ate 00

Description

This invention relates to organic chemistry, in particular to a method for producing new alkyl-substituted 6-cyanoglucose-1-3-oxazin-2-thiones, which can be used in the synthesis of biologically active compounds with a wide spectrum of action.

The purpose of the invention is to obtain new alkyl-substituted 6-cyanotetrahydro-1, 3-oxazin-2-thiones, which can be used for synthesizing biologically active compounds.

PRI me R 1. 4,4,6-Trimethyl-6-cyanotetrahydro-1, 3-oxazin-2thion.

To a mixture of 6.53 g (0.042 mol) of 4-isothiocyanato-4-methyl-2-pentanone and 4.42 g (0.05 mol) of acetone cyanohydrin at room temperature and vigorous stirring was added a solution of O, 10 g (0.002 mol) potassium hydroxide in 0.5 ml of methanol. After 3-5 minutes, the reaction mixture crystallizes, 7 ml of ether are added to it and stirred for 15 minutes, then the precipitate is filtered, washed on the filter with ether (2x7 ml), water (7 ml), dried in a vacuum desiccator over anhydrous calcium chloride.

Obtain 7.47 g (97.6%) of the desired product, so pl. 182-183s (from alcohol

Found,%: C 52.39; H 6.59; N 14.87; S 17.01.

CjHjjN OS

Calculated,%: C 52.15, H 6.56; N 15.20; S 17.40.

IR (-,): 1550 (CSNH), 3160 (NH).

PMR spectrum (cG, MD): 8.63 (1H, s., NH), 2.31 (1H, d.,, 1.96 (1H, d.,), 1.82 (MN, s.,), 1.35 (3N, s.), 1.34 (3N, s.).

PRI mme R 2. 6-Methyl-b-cyanoterahydro-1, 3-oxazin-2-tion.

Similarly, from 4.15 g (0.032 mol of 4-isothiocyanato-2-butanone, 3.28 g (0.038 mol) of acetone cyanohydrin and 0.20 g (0.005 mol) of sodium hydroxide in 1 ml of ethyl alcohol, 3.73 g (74, 6%) of the desired product, mp. 138-139C (from alcohol).

Found,%: C 45.88; H 5.11, N 17.55; S 20.07.

CfeHeNjOS

Calculated,%: C 46.13; H 5.16, N 17.93; S 20,52.

IR (V, cm): 1570 (CSNH), 3160 (NH).

PRI me R 3. 4,6-Dimethyl-6-cyatetrahydro-1, 3-oxazin-2-thione.

Similarly, from 2.58 g (0.013 mol of 4-isothiocyanato-2-pentanone, 1.85 g (0.02 mol) of acetone cyanohydrin and 0.1-0 g (0.002 mol) of potassium hydroxide in 0.5 MP of methanol, 2 are obtained 30 g (75.2%) of the desired product, mp 193-194 ° C (from alcohol).

Found,%: C 49.19, H 5.86, N 16.34; S 18.57.

C ,, OS

Calculated,%: C 49.39; H 5.92; N 16.46; S 18,84.

IR (v,): 1560 (CSNH), 3160 (NH).

PMR spectrum (cA, ppm): 8.42 (1H, s., NH) - 3.91 (1H, m, H); 2.34 (1H, DD, H); 2.83 ZN, s., S-CH 1.76 (1H, dd, nL; 1.32 (ZN, s., C - CH3).

PRI me R 4. 4,4,5,6-Tetramethyl-6-cyanotetrahydro-1, 3-oxazin-2

Similarly, from 6.93 g (0.04 mol) | 4-isothiocyanato-3,4-dimethyl-2-pentanone, 4.13 g (0.048 mol) of acetone cyanohydrin and 0.10 g (0.002 mol) of potassium hydroxide in O, 5 ml of methanol receive 7.30 g (91.0%) of the desired product, so pl. 173-175s (from alcohol

Found,%: C 54.23; H 7.00; N 13.97; S 16.01.

CgHt + NjOS

Calculated,%: C 54.52; H 7.12; N 14.13; S 16.17.

IR spectrum (l),): 1360 (CSNH), 3160 (NH).

EXAMPLE 5 4,4,5-Trimethyl-6-cyano-6-ethyl tetrahydro-1, 3-oxazin-2-thione.

Similarly, from 5.15 g (0.028 mol of 5-isothiocyanato-4,5-dimesh1-3-hexanone, 2.84 g (0.033 mol) of acetone cyanohydrin and 0.20 g (0.003 mol) of potassium hydroxide in 1 ml of methanol, 4 are obtained , 90 g (83.7%) of 4,4,5-trimethyl-6-cyanotetrahydro-1, 3-oxazin-2-thione, mp 220-221 ° C (from alcohol).

Found,%: C 56.39; H 7.55; N 12.86; S 14.73.

Calculated,%: C 56.57; H 7.60,

N 13.19; S 15,10.

3t16ff55B4

IR spectrum (l), cm): 1570 (CSNH), 2.07 (1H, q, H D, 1.93 (1H, dc p.

3155 (NH) CHCH), 1.51 (MN, s.,,);

PMR spectrum (cf, MD): 9.14 (1H, l7A1 (3N, s.), 1.2b (3N,

c., w); 2.21 (1H, q.q., CHCHj), tp,,); 1.23 (ЗН, д.,)

Claims (1)

METHOD FOR PRODUCING ALKYL SUBSTITUTED 6-CYANOTETRAPSCHRO-1,3-OXAZIN-2-THIONES of the general formula “R, C = N’ ” ΉS Η where R _f is CC ₄ -alkyl; R ₂ , R ₃ h R ₊ - independently from each other, hydrogen or C ^ - C * -alkyl, characterized in that I ^ -eothiocyanato ketone of the General formula Ri N ~ C = S where 1C-R ₊ have the indicated meanings; they are reacted with acetone cyanohydrin at room temperature in the presence of catalytic amounts of alkali.