SU360768A1 - - Google Patents

Description

METHOD OF OBTAINING THIOCARBAMINE ETHERS

This invention relates to a process for the preparation of new thiocarbamic acid esters of the general formula

E-CH. R

.7 II

NCSR, 1

where R is a cycloalkyl group containing from 3 to 5 carbon atoms which may be substituted by Ci-C4 alkyl groups, RI may have the same meaning as R, or it may be a Ci-C4 alkyl group substituted by Ci -C-alkoxy, Ci-C4-alkythio, cyano or carbethoxy; R2-Ci-Sb-alkyl group, which can be used as biologically active compounds.

A known method for the preparation of thiocarbamic acid esters is the interaction of amines with chlorothiol acid esters.

The proposed method is based on a known chemical reaction, however, the use of new starting compounds makes it possible to obtain a compound with improved properties.

ACIDS

2. I-CH

NH

R

subjected to interaction with the ester of chlorothiol acid of formula

5. R2SC

ten

C1

where R, RI and R2 are as defined.

The reaction is carried out at temperaura 25-110 ° C, preferably in the range from 35 to 80 ° C in the presence of solvents, for example Cs-C-hydrocarbons, such as benzene, toluene,

xylene, etc., ketones, ethers such as diethyl ether, tetrahydrofuran, dioxane, esters such as ethyl acetate and methyl acetate and an acid acceptor, preference is given to solvents such as benzene, tetrahydrofuran and ethyl acetate.

The reagents are taken in a 1: 1 molar ratio, and the acid acceptor (triethylamine) is taken in a 10% molar excess, although it can be taken either molar equivalent or greater

This and other acid acceptors, such as (trimethylamine, pyridine, sodium carbonate or potassium).

Example 1. Getting S-ethyl-N-cyclopropylmethyl-K-propylthiocarbamate.

To a stirred solution of 11.3 g (0.1 mol) of cyclopropylmethylpropyllamine and 11 g (0.11 mol) of triethylamine in 250 ml of benzene was added dropwise a solution of 12.6 g (0.1 mol) of ethyl ester of chlorothiougly acid in 75 ml of benzene, the reaction is exothermic and the temperature is maintained below 35 ° C. After addition of the solution and subsequent stirring for 30 minutes, the mixture was heated under reflux for 1 hour, cooled and filtered. The filtrate is washed twice with water, dried (Na2 SO4), the solvent is distilled off and distilled in vacuo. As a result of the distillation, 14.7 g of a colorless liquid were isolated, i.e. 70 ° C / 0.3 m, m Hg. Art. Analytically, the nitrogen content in the resulting product is -7.53% (calculated 6.98% for CzoHigNSO). The structure obtained in this, in this and in all subsequent examples of them is established by the methods of infrared spectroscopy and / or NMR.

Example 2. Getting Z-ethyl-Y-to-butyl N-cyclopropylmethyl.

To a stirred solution of 9.0 g (0.07 mol) of cyclopropylmethylbutylamine and 8.0 g (0.079 mol) of triethylamine in 150 ml of benzene were added dropwise 9.0 g (0.07 mol) of ethyl chlorothiol acid in 70 ml benzene, then the mixture is heated under reflux for 2.5 hours. The subsequent processing is carried out analogously to example 1. As a result of vacuum distillation, 12 g of colorless liquid was isolated, i.e. bale. 109-11G C / 0.5. “Well.

Calculated for CiiH2iNOS content of N 6.51.

Found N 6.89.

Example 3. Obtaining 5-ethyl-S-isobutyl N-cyclopropylmethylthiocarbamate.

The compound is obtained according to Lreemer 1. A colorless liquid is isolated by distillation, i.e. 85-95 ° C / 0.1-0.2 mm.

C, 60.47; H 9.77; N 6.51.

Found C, 62.40; H 10.20; N 6.48.

Example 4. Obtaining 3-ethyl-M-cyclopropylmethyl - N-3 - methyl mercaptopropylthiocarbamate.

The compound is obtained in the same way as orimer 1. A colorless liquid is isolated by distillation, i.e. 120 ° C / 0.1-0.2 mm.

C, 53.45; H 8.50; N 5.67.

Found C, 54.22; H 8.76; N 6.75.

Example 5. Getting Z-ethyl-Y-cyclopentyl-L1-ethylthiocarbamate.

C, 61.47; H 9.77; N 6.51.

Found C, 61.99; H 9.79; N 7.05.

Example 6. Synthesis of 3-ethyl-N-ethyl-N-tetrafurfufurylthiocarbamate. The compound was prepared according to Example 1. A colorless liquid was isolated by distillation, i.e. b.p. 93-96 ° C / 0.1 mm.

C, 52.67; H 9.27; N 6.88.

Found With 55.81; H 8.87; N 6.68. Example 7. Synthesis of 3-propyl-N-1-methylcyclopropylmethyl - N-prop lthiocarbamate.

The compound was prepared according to Example 1. A colorless liquid was separated by distillation, i.e. 85-110 ° C / 2.3-2.5zhzh. C, 62.83; H 10.11; N 6.11.

Found C, 59.38; H 9.85; N 7.66.

Example 8. Synthesis of 3-propyl-M-cyclopropylmethyl-N-propylthiocarbamate.

The compound was prepared as in Example 1. A colorless liquid was isolated by distillation, i.e. b.p. 103 ° C / 1.5 mm.

C, 61.35; H 9.88; N 6.50.

Found C, 61.81; H 9.62; N 6.40.

Example 9. Getting Z-shropil-N-propyl-M-tetrahydrofurfurylthiocarbamate.

The compound was prepared according to Example 1. A colorless liquid was isolated by distillation, m.p. 128-129 ° C / 1.5 mm.

C 58.74; H 9.45; N 5.71. Found C, 59.17; H 9.11; N 5.74.

Example 10. Getting Z-ethyl-Y-ethyl-M1-methylcyclopropylmethylthiocarbamate.

The compound was prepared as in Example 1. A colorless liquid was isolated by distillation, i.e. b.p. 84 ° C / 1.4 mm.

C, 59.66; H 9.51; N 6.96.

Found C, 59.98; H 9.16; W 6.52.

P. | Rimer I. Synthesis-3-ethyl-Y-propylN-tetrahydrofurfurylthiocarbamate. The compound was prepared according to Example 1. A colorless liquid was separated by distillation, i.e. 80-100 ° C / 0.05 mm.

C, 57.15; H 9.09; N 5.92.

Found C, 57.53; H 9.49; N 5.50.

Subject invention

Method for preparing thiocarbamic 50 acid esters of general formula

KS

 I NCSR

TO,

where R is a cycloalkyl group containing from 3 to 5 carbon atoms, which may be substituted with Ci-C4 alkyl groups;

RI may have the same meaning as R, or it may be a Ci-C4 alkyl group substituted by a Cj-C4 alkoxy, Ci-C4 alkylthio, cyano or carbethoxy group; Rs-Ci-Sb-alkyl group, different

,, 3.

E, where R and Ri have the indicated meanings, is subjected to -interaction with chlorothiol acid ester of the general formula </ BR> where R2 has the indicated value, followed by separation of the target product by known techniques.