SU513976A1 - Isolation method — or —anabazine - Google Patents

Description

one

The invention relates to the improvement of the method of isolating 1- or dl-anabasin, which can serve as starting materials in the synthesis of physiologically active compounds.

A method of isolating 1-anabasine is known, which consists in the fact that racemic anabazine is optically active with 1-6,6-dinitro-2, 2-diphenic acid, and a mixture of 1- and d-6,6-dinitro-2, obtained The 2-diphenocoates are divided into optical antipodes by repeated recrystallization from methanol, and further, by treating 1-6,6-dinitro-2,2-diphenoate with hydrochloric acid, 1-anabazine is obtained. However, this method is a long and laborious process and requires the use of an expensive preparation (optically active 1-6,6-dinitro-2,2-diphenoic acid).

In addition, there is a known method for producing dl-nabazine, which concludes that anabazine sulphate solution is heated at 200 ° C for 120 hours. When anabasin is produced from technical anabasine sulfate, specific rotation, anabazine is always understated, i.e. partially racemized anabasin.

In order to simplify the process of isolating pure 1- or dl-anabazine according to the proposed method, benabyl chloride acts on anabazine. The resulting N-benzoylanobazine is reacted with picric acid, and the resulting mixture of picrates is separated by recrystallization from an organic solvent into picrate 1- and dI-N-benzoylanabazine picrate, followed by the action of an oxide

aluminum is converted separately into 1- or dlM-benzoylanobazine. which are converted into the desired product by treatment with hydrochloric acid.

According to the proposed method, the initial anabasine is obtained from a technical anabasine sulfate by a known nitrosation method. The picrates of 1- and dl-N-benzoyl-ananabazine are separated by recrystallization from an organic solvent (mainly from acetone), and then converted into 1-st dl-K-benzoyl-abbasin by passing through an alumina column. Subsequent treatment with 25% HC results in optically active (-) and inactive (dl-) anabasine, having a correspondingly -82.0 ° and O.

The proposed method is distinguished by the simplicity and availability of the starting reagents and eliminates the use of the second optically active compound for separating the mixture of 1 st dl-anabasine into separate components.

The proposed method allows to obtain fnsiologic active compounds based on the levorotatory 1-atsabazine and the racemate of anabazine. An example. Getting 1-anabasno.

50 g (0.18 gmol) of X-beisoylmabazine with

m.p. 82-83 ° C, -105.0 ° and, 80 (thin-layer chromatography solvent system here and hereinafter - chloroform: methanol 24: 1), obtained by benzoylation of natural anabasine, having so-called kin. 98- 99 ° C / 0.6 mm Hg. Art. At 1.5430, -64.0 ° and 1 (0.61, by the action of benzoyl chloride by a known method, dissolved in 100 ml of methanol and a saturated solution of picric acid in methanol (55 g of picric acid) added dropwise to the solution. in 200 ml of methanol).

The precipitation is sucked off and dried in a vacuum desiccator.

86 g of N-benzoylanabazine nicrate are obtained. The output is quantitative, so nl. 160-180 ° C.

80 g of a mixture of picrate- and dl-N-benzoylanabazino B (mp. 160-180 ° C) and 300 ml of acetone are heated under reflux on a sand bath for 30 minutes. At the same time, a part of N-benzoilanabazine nicrate does not dissolve, the undissolved precipitate is filtered off and dried. After recrystallization from acetone, picrate of dl-N-.benzoyl-ananabazine with m.p. 190-195 ° C, yield 20 g (25%).

Found,%: C 55.13; H 4.3.

Calculated%: C 55.5; H 4.46.

From the acetone mother liquor remaining after precipitation, 55 g of picrate of 1-N-benzoyl-ananabazine with t. 140-145 ° С (from acetone), output 68%.

Found,%: N 13,61; 13.60.

Calculated,%: N 14,14.

four

20 g (0.004 g / mol) picrate of l-N-benzoyl-ananabazine will be placed in a column with alumina and the column will be washed with dry acetone until the reaction to alkaloids is negative. 8 g (80%) of l-N-benzoylanabazine are obtained with t. Il. 82-83 ° C. , 0 °; , 81.

8 g of l-N-benzoylanabazine (0.03 g / mol) are hydrolyzed with a 25% HC1 in a sealed ampoule. The output of 1-anabasin 3.5 g (61%), ni, 1,5430, t. Kip. 105-107 ° C / 1 mm Hg. Art.,, 0 ° :. Rf 0.61.

PRI mme R 2. Getting dl-Anabasin.

According to the above procedure, 4.5 g (60%) of dl-N-benzoyl anabazine with m.p. of 15 g (0.03 g / mol) of picrate of dl-N-benzoyl anabazine is obtained. 92-93 ° С,, 81, then by hydrolysis of the latter, 1.5 g (53%) of dl-anabasine are obtained, t. Bale. 95-97 ° / 0.5 mmHg Art. p 1.5430; Rf 0.60.

Claims (1)

Invention Formula The anabasine-based 1 or dl-anabazine release method is distinguished by the fact that, to simplify the process, anabasine is acted with benzoyl chloride, the resulting Nbenzoyl-ananabazine is reacted with picric acid dl-N-benzoylanabazine nicrate, after which, by the action of alumina, they are transformed separately into 1-or dl-Nbenzoyl-ananabazine, which are converted into a target product by treatment with hydrochloric acid.