SU266656A1 - METHOD FOR OBTAINING ACYLATED - Google Patents

Description

This invention relates to a process for the preparation of new acylated trichloroacetaldehyde terminals of the general formula

-.ABOUT

/

R-NH-CH-NH-С

sec

where R is mono- or disubstituted with halogen, lower alkyl, alkoxy, nitro, and / or dialkylaminoalkyl with one to four carbon atoms of alkyl atoms of one to four phenyl or unsubstituted naphthyl by reacting isocyanates of the general formula RNCO, where R have the indicated meanings, with N- (2,2,2-trichloro-1-hydroxyethyl) -formamide in the presence of tertiary amines or pyridine as a catalyst.

The resulting compounds can be used as physiologically active substances.

The reaction can be carried out in the presence of inert solvents: aliphatic and aromatic hydrocarbons — benzene, toluene, xylene, benzene, chlorinated hydrocarbons — chlorobenzene and carbon tetrachloride, ethers — dioxane, furan and dibutyl ether, acetopitrile, ethyl acetate, and the hops.

Minor amounts of tertiary amines are added to accelerate the reaction. Trialkylamines — trimethylamine and triethylamine, dialkylanilines — dimethylanilines and diethylanilines, as well as pyridines are particularly suitable.

The reaction temperature may vary widely from 0 to 150 ° C, preferably between 10 and 100 ° C.

The process is carried out with equimolar amounts of the starting materials using inert solvents and adding a small amount of tertiary amine. The end of the reaction can be set to stop the formation of carbon dioxide.

The desired product is isolated by conventional means, the reaction mixture is treated, for example, by distilling off the diluent or by filtering the precipitated substance.

The reaction products are generally already pure; they can additionally be purified by recrystallization or sublimation.

Example 1

To a mixture of 19.3 g N- (2,2,2-trichloro-1-hydroxyethyl) formamide and about 150 ml of benzene a solution of 6 g of methyl isocyanate in 100 ml of benzene is added dropwise. A few drops of triethylamine are then added to the mixture, with the release of CO2, an exothermic reaction begins. First, a clear solution is obtained, from which colorless crystals fall out after a short time. Stir for some time at a temperature of approximately 35-40 ° C, cool at the end of the evolution of CO2 to room temperature and suck off. The residue on the suction filter is recrystallized from benzene, and receive colorless crystals, melting at 90 ° C. Output about 16 g.

Example 2

0

-NH-CH-NH-C

on

To a mixture of 19.3 g of M- (2,2,2-trichloro-1-hydroxyethyl) formamide and about 250 ml of acetonitrile are added dropwise, placing a solution of 11.9 g of phenyl isocyanate in approximately 75 ml of acetoiitrile and then added to the mixture 3 triethylamine drops. When CO2 is formed, the temperature of the solution rises to approximately 35-40 ° C. The solution is allowed to stand until the formation of C02 is stopped at this temperature and then evaporated in vacuo. The solid residue is recrystallized from chlorobenzene and washed with additional carbon tetrachloride, and colorless crystals are obtained, melting at 99 ° C. The yield is about 20 g.

9.3 g of N- (2,2,2-trichloro-1-hydroxyethyl) -formamide are stirred with about 200 ml of acetonitrile and a solution of 15.5 g of 4-chlorophenyl isocyanate in 100 g of acetonitrile is added dropwise, while two to four cannes of pyridine. A clear solution is obtained which is stirred at a temperature of 35-50 ° C until the formation of CO2 ceases. Then evaporated in vacuo. dry and recrystallize the solid residue from toluene. Approximately 28 g of colorless crystals are obtained, which melt at 80 ° C.

15

Example 4

NH-CH-NH-C

20

H CH

193 g of M- (2,2,2-trichloro-1-hydroxyethyl) -formamide are stirred in approximately 1.5 l of acetonitrile and a solution of 189.5 g of 3,4-dichlorophenyl isocyanate in 500 ml of acetonitrile is added to the mixture. Approximately 0.5 ml of triethylamine is then added dropwise to the mixture, which is then heated to a temperature of about 50-60 ° C with strong formation of CO2. At this temperature, the mixture is stirred for approximately 1.5-2 hours and finally evaporated to dryness in vacuo. The solid residue is recrystallized from benzene or a mixture of methanol and water, and receive 300 g of colorless crystals. Melting point 120 ° C.

NH-GH-SH-S

and

Ss

40

As described in Examples 1-4, the compounds listed in the table can be prepared.

R-NH CH-NH-CH CC1 3

, iji C1 cVl, .j. with. -HY, O-Y // Subject of the Invention. Method for the production of acyl-irovine trichloro 1-acetaldehyde terminals of the general formula, Q5 R-NH-CH-NH-C - TTT I, where R means a myo- or disubstituted halogen, lower alkyl. , alkoxy-, nitroO .N-OCYS CHj F Bg Bg HN G and / or dialkylamino group with the number of carbon atoms of alkyl from one to four phenyl or unsubstituted naphthyl. characterized in that the isocyanates of the general formula RNCO, where R has the indicated meanings, are reacted with N- (2,2,2-trichloro-1-hydroxyethyl) -formamide in the presence of tertiary amines or niridine as a catalyst, followed by isolation of the target product with known tricks