SU941359A1 - Process for producing methylnealkyl derivatives of cyclohexanone - Google Patents

Description

(St) METHOD FOR PRODUCING METHYLENE IOALKYL DERIVATIVES OF CYCLOGEXANON

one

The invention relates to a new method for producing new 1-5 diketone derivatives, namely, to a method for producing methanethioalkyl derivatives of cyclohexanone of the formula

AT

dHj-idHzis- -CH

where R is a hydrogen atom or methoxy group,

which can be used in the synthesis of biologically active compounds,

A known method for producing methyleneamino derivatives of 1,5-diketones of the formula

and

) (n

ten

15

by the interaction of 1,3-Diphenyl-1- (2-oxocyclohexyl) -3-propanone with dimethylamine and formaldehyde in ethyl alcohol in the presence of Cl.

However, methylene-derivative 1,5-diketones cannot be obtained in this way.

The aim of the invention is a new method for producing new methanethioalkyl derivatives of cyclohexanone, which can be used in the synthesis of biologically active compounds.

The goal is achieved in that the derivatives of cyclohexanone of the formula .R

where R has the indicated meanings, is reacted with vf-butanethiol and formaldehyde in ethyl alcohol in the presence of alkali at tjS-SS C.

Equimolar amounts of the corresponding derivative of 1,5-diketone, paraform, alkylthiol in ethyl alcohol are placed in a flask equipped with a stirrer, a thermometer, a reflux condenser and an addition funnel, then the solution of potassium dihydrogen in ethanol is dropped in 1 h, the reaction mixture is heated to water bath at 45-55 C for 7 h, neutralized with dilute hydrochloric acid, extracted with ether and dried with magnesium sulfate, the solution is filtered, the solvent is removed at room temperature, the residue is poured over a small The number of alcohol, the resulting alcohol under the white precipitate was filtered, dried and recrystallized.

Example 1. 1.3 Diphenyl-3- (2-oco-3-H-butylthiomethyl-1-cyclohexyl) -propanone-T,

In the four-neck; a flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel is placed 12.85 g (0, mol) 1.3 diphenyl-3 (2-oxocyclohexyl) -propanone-1, 100 ml ethanol, 1.6 g (0 , mol) paraform, 3.78 g (0.042 mol) of n-butanethiol. A solution of 2.35 g (0, mol) of potassium hydroxide in 15 ml of ethyl alcohol is gradually added over a period of 1 h. The reaction mixture is heated on a water bath for 7 hours. The reaction mixture is neutralized with diluted (1: 1) hydrochloric acid, 50 ml of ether is added and dried with calcined magnesium sulphate. The solution is filtered off, the solvent is evaporated at room temperature. The residual oil with a small amount of white crystalline substance is poured with a small amount of alcohol. Under alcohol, the oily product turns into a white precipitate. It is filtered out

10 dried and recrystallized from ethyl alcohol.

The resulting 1,3-diphenyl-3- (2-oxy-3-I-butylthiomethyl-n-thioxy) propanane-1 has so pl. 89-90 С

15. (ethanol). Yield 9.7 g (60).

Found,%: C 76, i; H 7.80; S 7.27

C2fc, H3a (s.

Calculated: C 7b, AA; H 7.89;

20 S 7.89.

Example 2, 1,3 Diphenyl-3 - (2-oxo-3-n-butylthiomethylcyclohexyl) -propanone-1.

In a four-necked flask equipped with

5 with a stirrer, a thermometer, a reflux condenser and a dropping funnel, 12.85 g (0, mol of 1,3-diphenyl-3- (2-oxocyclohexyl-propanone-1), 100 ml of ethanol, are placed,

0 1, g (0.042 mol) of paraform, G3.78 g (0.042 mol of N-butanethiol. A solution of 2.35 g (0.042 mol) of caustic potassium in 15 ml of ethanol is added dropwise over a period of 1 hour. The reaction mixture is heated on water bath for 7 hours. Then neutralized with diluted (1: 1) hydrochloric acid, ether is added ml and dried with calcined

. magnesium sulfate. The solution is filtered off, the solvent is evaporated at room temperature. The residual oil with a small amount of white crystalline substance is poured with a small amount of alcohol. Under alcohol, the oily product turns into a white precipitate. It is filtered, dried and recrystallized from ethyl alcohol.

The obtained 1, 3D-phenyl-3- (2-oxo-3-H-butylthiomethylcyclohexyl) -propanone-1 has mp, 89-90 ° C (ethanol), yield 9.68 g (59.9). Example 3. 1,3-Diphenyl-3 - (2-oxo-3-H-butylthiomethylcyclohexyl) -propanone-1.

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, 12.85 g (0, mol) of 1,3-diphenyl-3 (2-oxocyclohexyl) -propanone-1 are placed, 100 ml of ethyl alcohol, 1.6 g (0, mol) paraform, g (0, mol) N-butanethiol. A solution of 2.35 g (0, mol) of potassium hydroxide in 15 ml of ethyl alcohol is gradually added over a period of 1 h. The reaction mixture is heated in a water bath at 55 for 7 hours. The reaction mixture is neutralized with diluted (1: 1) hydrochloric acid, 50 ml of ether is added and dried with calcined magnesium sulphate. The solution is filtered off and the solvent is evaporated at room temperature. The remaining oil with a small amount of a white crystalline substance is poured with a small amount of alcohol. Under alcohol, the oily product turns into a white precipitate. It is filtered off, dried and recrystallized from ethyl alcohol.

The resulting 1,3-diphenyl-3- (2-oxy-3- -butythylthiomethyl-cyclohexyl) -propanone has so pl. 89 90С (ethanol). Yield 9.75 g (60.3%).

An example. 1-Phenyl-3-C -methoxyphenyl) -3 (2-oxo-3-H-butylthiomethylcyclohexyl) -propanone-1.

Prepared under conditions analogous to examples 1-3, from 13.6 g (0.0 mol) of 1-phenyl-3- (-methoxyphenyl) -3- (2-oxocyclohexyl) -propanone-1, 1.2 g ( 0.0 mol) paraform, 3.6 g (O, O mol) of N-butanethiol and 2.3 g (O, OTs mol) of caustic potash.

The resulting 1-phenyl-3 (-methoxyphenyl) -3- (2-oxo-3-H-butylthiomethylcyclohexyl) -propanone-1 has so pl. 129-130 ° C (ethanol). Yield 8.05 g (5% -.

Found: C 7, U; H 7.86j S 7.5.

SagNz40y5

Calculated: C 73, H 7.81} S 7.30.

Claims (1)

1. Tilichenko M.N., Pavel G.V., Chumak A.D. Reactions of 1,5-diketones. V Mannich reactions in the range of 1,5-Diketones. Aminomethylation of 1,3 diphenyl-1- (2-oxocyclohexyl) -3-propanone. - Journal of Organic Chemistry, 1971, Vol. 7, no. i, s. 704-710.