SU126887A1 - The method of obtaining 1-hydroxymethylpyrrolizidine - Google Patents

Description

v.

N9 126887- 2 EXAMPLE o-12-heterrahydrofuryl) -6thyrolactone- (111).

10 g of dibutyrolactone (II) in 100 ml of anhydrous methanol is hydrogenated at room temperature and 6 .. atm. pressure over skeletal nickel catalyst. In two hours about 2.1 liters of hydrogen are absorbed. The catalyst is filtered off, the methanol is distilled off: the residue is not distilled, collecting the fraction with T. kin. 92-95 ° (1-1.5 mm.

5.2 g (52%) of the dihydro compound (III) are obtained in the form of a colorless, mobile liquid, which, after the repeated distillation, has a bale.

2020

78-79 ° (0.8-1. Il); s / -1.1692; , 4759.

4, 7-tribrom-3-carbmegoxyheptane (V)

A solution of 10 g of 3- (2-tetrahydrofuryl) -butyrolactone (III) in 125 ml of hydrobromic acid (, 79) is heated in a sealed vial for 5 hours at 100 °. The resulting crude oil is extracted with benzene. The extract is washed with water, dried with magnesium sulfate. After distillation of benzene, 23.5 g of oily 1, 4, 7-tribromo-3-carboxyheptane are obtained, which are dissolved in 60 ml of anhydrous methanol and 1. 6.5 ml of thioiyl chloride are added while stirring and cooling. The resulting solution was kept at room temperature for 48 hours, methanol was distilled off and the residue was evaporated with dry benzene. 22.5 g of 1, 4, 7-tribromo-3-carbmethoxyheptane (V) are obtained in the form of a viscous oil, insoluble in water and decomposable during attempted distillation.

Pyrrolizidin-1-carboxylic acid methyl ester. (Vi)

22.5 g of crude 1, 4, 7-tribromo-3-carbmethoxyheptane V in 175 ml of G1 absolute methanol is saturated with ammonia at 0 °. The resulting solution is heated in an autoclave at 130-140 ° for 4 hours. The reaction mixture is evaporated to a small volume and anhydrous methanol is added to a total volume of 150 ml. The resulting solution is washed with hydrogen chloride and injected over 3 hours. The methanol is distilled off and the residue is evaporated with dry toluene. Patched oil is dissolved in 60 ml of thionyl chloride. The reaction mass is stirred at 25-30 ° for 5 hours. The precipitate formed is filtered off, washed with absolute methanol. The filtrate is evaporated, the residue is dissolved in 10 L1L of cold water, alkalized with potash, and the product is extracted with ether. The ether solution is dried with sodium sulfate, the ether is distilled off and the residue is distilled, collecting the fraction with m.p. 79-80 ° (4 mm). 3.5 g (32%) are obtained, counting on the compound (III) of pyrrolizidin-1-carbopic acid tetyl ester (VI) as a colorless MOBILE liquid With the smell of amine, which, after repeated SWITCHING, has t. 57 ° (0.8-1 mm); d - 1,0706; “,. - 1.4770.

After three times recrystallization from alcohol, the picrate has a melting point of pl. 140-142 °.

1-hydroxymethylpyrrolizidine (di-tpaxelclnta.nudun), (VII)

To a solution of 1.6 with lithium aluminum hydride in 55 ml of ether, with stirring, but also add 3.2 g of nirrolizidine-1-carboxylic acid (VI) methyl ester in 50 ml of absolute ether over 30 minutes. The reaction mass is stirred at boiling for 1.5 hours and then; good cooling conditions are decomposed successively with 2 ml of water, 1 ml of 20% sodium hydroxide, 6 ml of water, 7 ml of 40% sodium hydroxide. The product is thoroughly extracted with ether. Ether solution

2020