SU781202A1 - Method of thiocarbamate production - Google Patents

Description

The invention relates to the improved preparation of thiocarbg1mat of the general formula I R — O — C — NH — R, where R is normal or iso-alkyl; alkyl C-Cd, alkyl, phenyl, cyclehexyl, oxyalkyl Cy-C2 which are used as intermediates in organic synthesis, herbicides, flotation reagents, lubricant additives, plasticizers of rubber vulcanization accelerators for the preparation of various emulsions and drugs. A known method for the preparation of thiocarbamates by xanthylation of S-amines (with xanthogenic acids when heated in a water bath, after which the target product is purified, the methyl: ercaptan distilled in a vacuum as a by-product of the reaction) the main substance 50-90 low yield of the target product (d 80%), as well as great difficulties in cleaning the finished product from the formation of mercaptans, which make it difficult during the flotation of the mineral in factories. Even samples of high concentration of the main substance (90%) of thiocarbamate have the disgusting smell of methyl mercaptan and cannot be used in concentration plants of the USSR according to sanitary standards. as intermediates of organic synthesis. The distillation of the mercaptan is carried out first at atmospheric pressure and then in vacuum. This complicates the process technology, increases its staging, creates the need to use additional technological equipment. The purpose of the Invention is to simplify the method. Postaleina's goal is achieved by obtaining obi thiocarbamates (by its formula by reacting an amine with a bis (alkylxamtoheic) derivative of xaitoheic acid with a sulfide of the general formula II R OC - (S) - S, - (S) - OCR, where R - has the above X values - from 1 to 4, in the presence of catalytic amounts of acetic acid. In addition, acetic acid is used in an amount of 0.02-0.04 mol ha-mole of bis (alkyl xanthogen-) sulfide. - The process proceeds easily at room temperature or with heating, in organic solvent sludge in water. 30 min the reaction, 94-99% v1hod thiocarbamates. Catalytic amount of acetic acid promote the shift reaction equilibrium towards amines ksantilirovani form tiokar Bamat prevent obtaining as by-products produ GOVERNMENTAL thiourea and gidrolitichvekoo. decomposition during the reaction of bis {alkilksantogen) sulfides. Synthesized thiocarbamates do not contain foul-smelling volatile substances. The method is suitable for KeffBTlKJrfH of primary and secondary aliphatic amines, hydroxyalkyl ions, aniline and its substituted, cyclic-group amines. Example 1. To 0.2 MOL of butyl amine in 50 ml of water was added 0.1 m of bis- (isopropyl xanthogen) monosulfide and 0.004 mol of acetic acid, and placed for 0.5 h at 50-bC. The oil layer was separated. from water and get 33; 0 g (94.0%) of N-butyL-o-isoprop thiocarbamate. The physicochemical properties and the result of the analysis of the synthesized substances are given in the jB table. Example 2. 0.1 mol of bis- (isopropyl xanthogen) monosulfide, 0.0041 м mol of acetic acid is added to 0.2 mol of p-oxyl methylaniline in 50 ml of alcohol and stirred at rnMnat (temperature is 40 minutes. Reeye mass is cooled to 0®C and 21.4 g (95.1%) of Nsi; methyl-o-isopropylthiocarban 11 is filtered out. Example 3. To a 0.2 mL of an amine in 50 ml of water, add 0.1 m of bis- (isopropylxanthogen) MO-bulphy yes, 0.00416 mol of acetic acid and stirred for 30 min at 60-65 C. The oil layer is removed and 33.05 g (98.0%) of M-allyl-o-butylthiol-carbamate is obtained. Example 4. K Oh, 2 mol cyclohexyl1 mine In 50 ml of benzene, 0.1 mol of bis (ethylene xanthogen) monosulfide, 0.004 mol of acetic acid is added to

781202 lots and stirred at 50-60s for 30 minutes. After removal of the solvent, 35.6 g (96.15%) of N-cyclohexyl-o-ethylthiocarbamate are obtained. Example 5. KO, 4 mol of methylamine in 75 ml of water were added O, 1 mol of bis- (isopropylxanthogen) disulfide, 0.002 mol of acetic acid, sodium hydroxide and stirred at 70-80 ° C for 30 minutes. The reaction mass is filtered, the masses are separated, and 25.3 g (98.9%) of N-methyl-o-isopropylthiocarbamate are obtained. Example 6. To 0, 2 mol of ethanolamine in 50 ml of alcohol, 0.1 mol of bis (i-amoamyl xanthogen) disulfide, 0.002 mol of acetic acid is added and stirred at the same temperature for 40 min. After filtration and removal of the solvent, 35.63 g (94%) of N-hydroxyethyl-o-isoamylthiocarbamate is obtained. Example 7. K 0.1 mol of bis (isopropyl oxitogen) disulfide in 50 ml of benzene at 18–22 ° C is added 0.2 mol of aniline in 25 ml of benzene, 0.002 mbl of acetic acid and react for 40 min at the same temperature. The sulfur precipitate is filtered off, the reaction mass is cooled down and 37.2 g (95.5%) of N-phenyl-o-isopropylthiocarbamate are isolated by filtration. Example 8. The reaction of bis (isopropylxanthogen) trisulfide with ethylamine is carried out as described in Example 1. 27.8 g (94.1%) of M-ethyl-o-isopropylthiocarbamate are obtained. Example 9. The reaction of bis (isopropylxanthogen) of trisulphide with a {sphene was carried out as described in Example 2. 35, -5 g (91.1%) of N-phenyl-o-isopropylthiocarbamate were isolated. Example 10. The reaction of bis (isopylxavtogen) tetrasulfide with butyl Min is carried out as described in Example 1. 33.82 g (95.0%) of H-butyL-O-isopropylthiocarbamate are obtained. II g. And measure 12. The reaction of bis (ethyl xanthateic) tetrasulfide with cyclohexyl N is carried out as described in Example 4. 36.2 g (96.7%) of H-cycloGl-o-ethylthiocarbamate are obtained. The process for the preparation of thiocarbamates is carried out with stoichiometric charges of reagents in a minimum amount of organic solvent or water for a process duration of 30-40 minutes. The yield of the finished product 94-99%. Obtaining a product does not require complex technological process design. During the synthesis, the release of AlkylMercap1gia is exceeded.

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Claims (1)

1. US patent No. 3590996, cl. 209-166, published. 1971 (prototype). ,