SU259074A1 - METHOD OF OBTAINING DIACETYLENE ONE AND DUAL ATTRACTS OF PIPERIDINE SERIES CONTAINING / Mr.-DIETHINYLBENZENOL GROUP - Google Patents

Description

This invention relates to a process for the preparation of new diacetylenic one- to two-atom alcohols of the piperidine series containing / r-diethynylbenzene group of the type

С С-СБН4-С С СНз

CH,

The synthesized compounds, as well as the method itself, are new and can be used as medicinal antiviral preparations, herbicides, defoliants, growth-stimulating preparations, and also as intermediate compounds in the synthesis of a number of physiologically active substances.

The method consists in that derivatives of piperidone-4, for example 1,2,5-trimethylpiperidone-4, are subjected to condensation with p-diethynylbenzene in a liquid ammonia or organic solvent in the presence of powdered caustic excrement at -30 to + 5 ° C .

peridol-4 (IV). In a three-necked flask equipped with a stirrer and an addition funnel, 400 ml of liquid ammonia, 4.31 g (0.077 mol of powdered caustic potash, are added and a solution of 9.8 g (0.077 mol (I) ha-diethyl benzene in 60 ml of dry sulfuric ether is added. After stirring within 1 hour, a solution from 10.85 g (0.077 mol) (II) of 1,2,5-trimethylpiperidone-4 in 100 ml of dry is added dropwise

ether, after which the mixture is stirred for another 4 hours and decomposed into potassium hydroxide by adding 4.1 g (0.077 mol of porous ammonium chloride. To evaporate the ammonia, the reaction product is left to stand overnight

c, ether (500 ml, after which the precipitate of potassium chloride is filtered off, dissolved in water, the aqueous solution is extracted with ether. The combined ether extracts are concentrated and then chromatographed on a column

with alumina in the solvent system benzene - n-heptane-methanol (5: 5: 1). By separating 1 g of the product mixture, 1.1 g (55%) (III) of bis- (1: 2,5-trimethyl) was obtained 4-oxypiperidyl-4) -n-diethynylbenzol with m, mp, 212 ° C (decomposition); (benzene-methanol); Rf 0.1.

In the IR spectrum, characteristic bands of the OH group (3400) were found, the absorption bands of the acetylene bond are absent due to the strong symmetry of the molecule, Dihydrochloride

Also obtained 0.3 g (15%) (IV) 1,2,5trimethyl-4 - ((3-l-diethylenbepzol) - piperidol-4; mp 135-136 ° С (from beryzol); Rf 0.3.

Absorption bands were found in the PC spectrum: - C C (2110 p.i-1), - € 11- (3230 cl) AND OH groups (3400.

Hydrochlorde has t. Pl. 17GS (decomposition).

A total of 12.39 g (60%) of bis- (1,2,5-trimegyl-4-hydroxypiperidyl-4) p-diethynylbenzene and 4, 13 g (20%) of 1,2,5-trimethyl- were isolated from the reaction mixture. 4 - (pp-diethynylbenzene) - neridol-4.

Elementary analysis:

I. Found, o / ,,: With 76.52; H 9.02; N 6.36.

S2bNzbM202

Calculated, o / o: C 76.43; H 8.88; N 6.85.

II. Found, N 5.60; C1 14.90. C2SHOY202-2HC1 Calculated, N 5.81; C1 14.72.

III.Found,%: C 83.47; H 8.18; N 5.06. CisHaiNO

Calculated, o / o: C 80.66; H 7.91; N 5.23.

IV. Found, o / o: N 4.53. CisHaiNO-HCI Calculated,%: N 4.6 i.

Note 2. Synthesis of bis- (1,2,5-trimethyl-4-hydroxypiperidyl-4) -p-diethylenebenzene and 1,2,5-trimethyl-4 - (p-d-diethynenenbenzene) -piperidol-4.

To a suspension of 11.2 g (0.2 mol of powdered caustic potash in 100 ml of absolute sulfuric ether at 0-5 ° C are introduced 12.6 g (0.1 m, ol} / g-diethylnenzene in 40 ml absolute ether. Then, for 1 hour, while stirring, add 14.1 g (0.1 mol} of 1,2,5-trimethylpiperidone-4 to 100 ml of absolute ether. The mixture is stirred for 8 hours and decomposed with water. The ether layer the aqueous layer is extracted with ether. The combined ether extracts are neutralized with carbon dioxide, dried over potash and concentrated. The reaction product is separated by chromatography on a column ke with alumina in the solvent system benzene - n-heptane-

methanol (5: 5: 1). In total, 16.28 g (617 °) of bis- (1,2,5-trimethyl-4 - hydroxypiperidyl-4) - //.- diethylbenzene; m.p. 212 ° C (decomposition) and 5.87 g (22%) 1,2,5trimethyl-4 - (p - "- diethinylbenzene) - piperidol-4; m.p. 135.5-136С.

An elementary analysis of 1,2,5-trimethylpiperidone-4 obtained by condensation with p-diethynylbenzene in the presence of powdered caustic potassium in an absolute ether medium, glycol and alcohol is fully consistent with the data calculated for them.

Subject invention

The method of producing diacetylenic mono- and dihydric alcohols of the niperidine row, containing them in the p-diethynylbenzene group, characterized in that the piperidone-4 derivatives, for example 1,2,5-trimethylneri-Don-4, are reacted with p-diethylbenzene in the presence of powdered potassium hydroxide in an environment of liquid ammonia or an organic solvent at a temperature of from -30 to -f 5 ° C with nedyushuyush, they release the reaction products are known.