SU825522A1 - Method of preparing n-(aminothio)phthalimides - Google Patents

Description

The invention relates to an improved method for producing Ν- (aminothio) phthalimides of the general formula

IX, W5 where 1C and R ^ - alkyl C ^ -C ^, cyanoalkyl,

C ^ -C ^, cyclohexyl, or R ^ and R ^ together with the N atom form a morpholine residue, which are used as moderators of premature vulcanization.

A known method of producing N- (aminothio) -phthal imides by the interaction of the corresponding aminosulfene chlorides with phthalimide in tetrahydrofuran at 0-10 ° C in the presence of a tertiary amine as an acid acceptor. Aminosulfene chlorides are prepared by chlorination of the corresponding N, Ν * bis-aminodisulfides in toluene or carbon tetrachloride at 0 ° C and are used without isolating from the reaction mixture. The yield of Ν- (amino; thio) phthalimides does not exceed 61% £ 11.

The disadvantages of the method are the relatively low yield of final products, the use of expensive tetrahydrofuran, as well as the use of various solvents at different stages of the process, which creates certain difficulties in the process of separation of these solvents after the reaction. The low yield of final products due to the reaction in a heterogeneous system due to the poor solubility of phthalimide in tetrahydrofuran significantly prevents the widespread distribution of Ν- (aminothio) phthalimides and the industrial introduction of this method. Due to the low yield, large quantities of starting materials remain unused, the regeneration of which is practically impossible.

The purpose of the invention is to increase the yield of target products and simplify the process.

825522 4 le recrystallization from alcohol yield

46.6 g (84.7%), mp 104-106 ° C.

Found,%: N 15.08; S 11.58. Calculated,%: N 15.26; S 11.65.

Example 4. Obtaining N- (n-butyl-p-cyanoethylaminothio) phthalimide.

Obtain analogously to example 1 at 0-10 ° C from 24.2 g (0.2 mol) of n-butyl-β-cyanoethylamine 54.5 g of the product and recrystallized from alcohol. Yield 50.8 g (83.9%), mp. 1О7-1О9 ° С.

Found,%: N 13.81 ;. S 10.34. Calculated,%: N 13.86; S 10.56. · Example 5. Obtaining M- (cyclohexyl-p-cyanoethylaminothio) phthalimide.

Obtain analogously to example 1 from 30.4 g (0.2 mol) of cyclohexyl-p-cyanoethylamine 58.7 product and recrystallized from alcohol.

Yield 56.0 g (85%), mp. 107109 ° C.

Found,%: N 12.7; S 9.58.

Calculated,%: N 12.76; S 9.73. ·

Example 6. Obtaining 1CH- [di (3-cyanoethyl) aminothio] phthalimide.

Get analogously to example 1 of

24.6 g (0.2 mol) of di- | 3-cyanethylamine 58.1 g of the product and recrystallized from alcohol. Yield 54.8 g (91.3%), mp. 132-132.5 ° C.

Found,%: N 18.64; S 10.59. Calculated,%: N 18.60; S 10.63. Thus, due to the good solubility of the reagents in chlorobenzene, this process proceeds in a homogeneous medium, which contributes to an increase in the yield of the product to 82-92%. In addition, it becomes possible to replace expensive and scarce tetrahydrofuran with cheaper and affordable chlorinated hydrocarbons, such as chlorobenzene.

The use of chlorobenzene as a solvent both in the preparation of target products and in the production of chlorothio-I-phthalimide eliminates the process of separation of a mixture of solvents.

Claims (6)

The goal is achieved by the fact that in the method of producing N- (aminotio) phthalimides of formula (1) by reacting a compound containing a chlorothiogroup with an amine at 0-10 ° C in the presence of tertiary amines, chlorothio-M-phthalimide is used as the amine use secondary amines of the formula where R and R .. are as defined above, and proceeding is carried out in chlorobenzene. Chlortioro-M-phthalimide is obtained by chlorination of bis-phthalimidodisulfide in chlorobenzene G22 and condensed with a cyclic amine of formula (I) not vsde-1 l from the reaction mass, in the presence of a tertiary amine or an excess of the secondary amine itself as an acid acceptor .. Example 1. The creep of N- (morpho-lintio) phthalimide. A solution of 42.7 g (0.2 mol) of chlorothio, -K-phthalimide in 200 ml of chlorobenzene is added dropwise over 45-60 minutes at-5 ° C to the reaction mass of 17.4 g ( 0.2 mol) morpholine and 20.16 g (0.2 mol) of triethylamine in 200 ml of chlorobenzene. After the addition, the reaction mass is stirred for i h, poured into water, the organic layer is washed with water until neutral, separated and dried with anhydrous sodium sulfate. The solvent is distilled off under vacuum and 46.3 g of the expected product are obtained (87.7% of the theoretical) with a mp. 205-208 4; . After recrystallization from alcohol so pl. 210-212 °, yield 43.6 g (82.3%); Found,%: N 10.57; S 12.15. Calculated,%: N 10.60; S 12.13. Example 2. Preparation of N- (netil- (1-cyanoethylaminothio) phthalimide. Prepared analogously to Example 1. 1 out of 16.8 g (0.2 mol) methyl- (V-cyanoethylamine 47.3 g of product. After recrystallization from alcohol t. P8-120 s, yield 43.2 g (86.4%). Found,%: N 16.89; S 11.98. Calculated,%: N 16.08; S 12.27. Example 3. Get non-N-CsTHn- (L-cyanosln aminotio) phthalimide. It is obtained analogously to example 1 with from 19.7 g (0.2 mol) of ethn-β-cyano ethylation 49.6 g of product. After recrystallization from alcohol, yield 46.6 g (84.7%), so pl. 104-106 C. Found,%: N 15.08; S 11.58. Calculated,%: N 15.26; S 11.65. Example 4. Preparation of M- (n-butyl-cyanostilaminothio) phthalimide. Analogously to Example 1 with O-rlO C from 24.2 g (0.2 mol) of n-butyl-cyanostilamine 54.5 g of product and recrystallized from alcohol. Yield 50.8 g (83.9%), m.p. 107-109 C. Found,%: N 13.81 ;. S 10.34. Calculated,%: N 13.86; S 10,56. Example 5. Preparation of H- (cyclohexyl-p-cyanoethylaminothio) phthalimide. Prepared analogously to example 1 from 30j4 g (0.2 mol) of cyclohexyl-p-cyanoethylamine 58.7 of the product and recrystallized from alcohol. Yield 56.0 g (85%), m.p. 107109С. Found,%: N 12.7; S 9.58,: Calculated,%: N 12.76; S 9.73. Example 6. Preparation of (E-cyanrethyl) amnotioth phthalimide. 58.1 g of the product are obtained analogously to example 1 from 24.6 g (0.2 mol) of di-E-cyanoethylamine and recrystallized from alcohol. Yield 54.8 g (91.3%), m.p. 132-132 ,. Found,%: N 18.64; S 10,59. Calculated,%: N 18.60; S 10.63. Thus, due to the good solubility of the reagents in chlorobenzene, this process takes place in a homogeneous medium, which contributes to an increase in the yield of the product to 82-92%. In addition, it is possible to replace expensive and scarce tetrahydrofuran with cheaper and more readily available chlorinated hydrocarbons, such as chlorobenzene. The use of chlorobenzene as a solvent both in the preparation of the desired products and in the preparation of chloro-N-phthalimide allows one to exclude the process of separation of the solvent mixture. The invention The method of obtaining N- (aminothio) phthalimides of the general formula M-S-M: 5825522b where R and Rj - alkyl cyanoalkylamines formula , cyclohexyl, orR R and R, 2 together with the N atom ob-NH, morpholine residue is produced by inter-R the action of the compound containing 5 where R and R have the above-mentioned chlorothyl group, with the amine at 0-0 ° C, and the process is carried out in chlorine in the presence of tertiary amines, o-benzene. characterized in that, for the purpose of Sources of Information, increases in yield of target products are taken into account in the examination and. simplifying the process, as a syringe 1. US Patent 93838П4, unity, containing, chlortiogruypu, kl.260-79.5A, published. 1974 (prototype),. Chlortio-M-phthalimide is used, and in 2. Lined up for the application of the Federal Republic of Germany 1 23E02D1, secondary amine is used as amine. C 07 D 209/48, published 1975.