SU1252326A1 - Method of producing alkyl-substituted 6-oxytetrahydro-1,3-thiazin-2-thiones - Google Patents

Description

The invention relates to organic chemistry, and more specifically to an improved method for producing alkyl-substituted 6-hydroxytetra-ylro-1,3-thiazine-2nol, with a reaction time of 2 hours, 5.4 g (47.2%) are obtained (5,6-t methylene-6- oxentrahydro-1,3-ty 2-tnon) -A-spirocyclohexane with t

thiones, which are used as bio-5 116 - 11 C (acetone - hexane).

Found,%: C 57.3; H 7.9; N C, H g, N08.1

gically active compounds, rubber additives, as well as intermediates in organic synthesis.

The purpose of the invention is to increase output and expand the range of target products and simplify the process technology.

Example 1. 4,4,6-Trimethyl-6-oxytetrahydro-1,3-thiazin-2-thione.

To a solution of 1.8 g of sodium hydrosulfide in 16 ml of methanol, while stirring at room temperature, 3.16 g of 4-methyl-4-isothiocyanato-2-pentanone in 8 ml of methyl alcohol is added. After 2.5 hours, the reaction mass is carefully acidified with 10% hydrochloric acid (pH 3-5) and poured into 50 ml of water. The precipitated crystalline precipitate is filtered off after 0.5 h, filled with water (25 ml) and hexaioma (25 ml), dried on a filter, and then in a vacuum desiccator.

3.2 g (83.2%) of 4,4,6-trimethyl-6-hydroxytetrahydro-1, 3-thiazin-2 are obtained.

Thiona, m.p. 113 - 114 ° C (acetone - hexane).

IR spectrum (suspension in a vase. Oil), 9, cm: 1535 (thioamide), 3100 (N-H), 3260 (-OH).

PRI mme R 2. 4,4,5,6-Tetramethyl-6-hydroxytetrahydro-1,3-thiazin-2-thione.

Analogously to Example 1, 1 g of 3,4-dimethyl-4-isothiocyanato-2-pentanone in 2 ml of methanol and 0.49 g of sodium hydrosulfide in 4.4 ml of methanol give 0.814 g (67.9%) of the duration of the reaction for 1 hour. 4,4,5,6-tetramethyl-6-oxytetrahydro-1,3-thiazin-2 thione with m.p. 94 - 94.5 ° C (acetone - hexane)

Found,%: C 46.59; H 7.33; S 31.68.

C8H, gNOS2

Calculated,%: C 46.8; H 7.36; S 31 23.

IR spectrum (suspension in vase oil), cm: 1535 (thioamide), 3090 (N-H), 3230 (-OH).

PRI me R 3. (5,6-Tetramethylene-6-oxytetrahydro-1,3-thiazin-2-thione) - 4-spirocyclohexane.

As in Example 1, 10 g of 2- (1-isothiocyanatocyclohexyl) cyclohexanone in 20 ml of methanol and 11.2 g of sodium hydrosulfide in 100 ml of methanol give 5.4 g (47.2%) for 2 hours (5, 6-tetramethylene-6-oxentrstragidro-1,3-thiaen-2-tnon) -A-spirocyclohexane with m.p.

116 - 11 C (acetone - hexane).

five

0

five

0

Found,%: C 57.3; H 7.9; N 5.2, C, H g, N08.1

Calculated,%: C 57.5; H 7.8; N5,2. IR (suspension in vase oil),: 1535 (thioamide), 3090 (N-H), 3230 (-OH).

PRI me R 4. 4,4,5-Trimethyl-6-ethyl-6-hydroxytetrahydro-1, 3-thiazin-2-thion.

Analogously to example 1, 1 g of 3,4-dimethyl-4-isothiocyanato-3-hexanone in 2 ml of methanol and 0.49 g of sodium hydrosulfide in 4.4 ml of methanol with a process time of 1 hour, 0.70 g (59.1 g %) 4,4,5-trimethyl-6-ethyl-6-hydroxytetrahydro-1,3-thiazine-2-thione with m.p. 79 - (acetone - hexane).

Found,%: C 49.4; H 7.6; N 6.4.

,, nosi

Calculated,%: C 49.3; H 7.8; N 6.39.

IR spectrum (suspension in vase, oil), cm: 1535 (thioamide), 3100 (N-H),. 3270 (-OH).

PRI me R 5. 5,6-Dimethyl-6-hydroxy-tetrahydro-1,3-thiazin-2-thione,

To a solution of 3 g of sodium hydrosulfide in 20 ml of methanol, with stirring, 5.527 g of 3-methyl-4-isothiocyanato-2-butanone in 5 ml of methanol are added dropwise. After 0.5 h, 10% hydrochloric acid is added to the reaction mass until acidic (pH 3-5) and left in the refrigerator overnight. The next day, the precipitated crystals are filtered, washed with water (20 ml) and ether (20 ml), dried on a filter, and then in a vacuum desiccator.

3.7 g (58.8%) of 5,6-dimethyl-6-hydroxytetrahydro-1,3-thiazin-2-thione are obtained with m.p. 71 - 72 C (acetone - hexane).

Found,%: C 40.43; H 6.24; S 36.37.

 Nos.

Calculated,%: C 40.65; H 6.25; S 36.1 /.

IR spectrum (suspension in vase oil) 55 -J, cm: 1360 (thiomide), 3070 (N-H), 3340 (-OH).

PRI me R 6. 4,4,6-Trimethyl-6-hydroxytetrandro-1, 3-thiazin-2-thion.

five

0

five

0

3125

To a solution of 1.8 g of sodium hydrosulfide in 16 bp of ethyl alcohol, under stirring at room temperature, 3.16 g of A-methyl-4-isothiocyanato-2-pentanone in 8 ml of ethyl alcohol are added. After 1.5 hours, the reaction mass was carefully acidified with 10% hydrochloric acid and poured into 50 ml of water. The precipitated crystalline precipitate after 0.5 h, filtered, washed

Editor I. Derbak

Compiled by A.Dovgilevich

Tehred M. Morgental Proofreader T. Kolb

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VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod, Projecto st., 4

64

water (23 ml) and hexane (25 ml), dried on the filter, and then in a vacuum desiccator.

Get 3,11 g (80,9%) 4, D, 6-three methyl-6-hydroxytetrahydro-1, 3-tiaein-2J)

Thiona, m.p. 113 - 11A C.

The sample mixed with the sample obtained in Example 1 does not depress the melting point.

Claims (1)

METHOD FOR PRODUCING ALKYL SUBSTITUTED 6-0XYTETHRAGIDR0-1, 3-THIAZIN2-THIONES of the general formula where R ¹ is C-alkyl, R ² , R ³ and R ^{4 are} independently water-water atoms. kind or C ₄ _ ₄ -alkyl, or R * and R ² together - tetramethylene, or R ³ and R * together - pentamethylene, reacting the corresponding y5-isothiocyanatoketone with a sulfur compound at room temperature in a lower alcohol medium, characterized in that , in order to increase the yield and expand the assortment of target products and simplify the process, a common compound is used as the corresponding ^ 5-isothiocyanatoketone where R ', R ² , R ³ and R ⁴ have the indicated meanings, sodium hydrosulfide and the resulting reaction are used as sulfur compounds mixture about ops mineral acid solution. SU,., 1252326