SU1576522A1 - Method of obtaining 12e-tetradecen-9-in-1-ol - Google Patents

Abstract

The invention relates to unsaturated acyclic alcohols, in particular to the preparation of 12 E-tetradecene-9-yn-1-ol - sex pheromone mill moth. The goal is to increase output. The preparation is carried out by metallization of 1- (2-tetrahydropyranyl) oxy-9-decin in succession by equimolar amounts of ethylmagnesium bromide and copper iodide (1+). The obtained organometallic derivative is reacted with crotyl bromide followed by acid hydrolysis. The process is carried out in a mixture of tetrahydrofuran and diethyl ether, taken in a volume ratio (1-4): 1, at 5-30 ° C. The yield of the target product is 55-80 wt.% While maintaining the quality of the product. 1 tab.

Description

6.75 g (50 mmol) (crotyl bromide, allowing the mixture to warm to 20 ° C, and maintain it at this temperature with stirring for 4 hours. Next, 100 ml of a saturated solution of ammonium chloride is poured into the mixture and the product is extracted in three portions m diethyl ether, 200 ml each,

The combined ether extract is evaporated. In the residue, 12E-tetradecen-9 yl-1-ol tetrahydropyranyl ether is obtained, which is dissolved in 120 ml of methanol, 20 ml of water and 3g TSOH are added and the mixture is stirred at room temperature for 15 hours, after which the solvent is distilled off. 500 ml of diethyl ether are added to the residue, washed with 100 ml of saturated sodium bicarbonate solution and dried over sodium sulfate. Then, the resulting mass is evaporated. After purification by liquid chromatography on silica gel (eluent hexane: diethyl ether 7: 3), 8.32 g (80 wt.%) Of the desired product are obtained, the refractive index is 1.4739,

Examples 2-11. The results of the synthesis of 12E-tetradecene-9-yn-1-ol depending on the conditions of the condensation reaction (the ratio of solvents, temperature and duration of the reaction) are given in the table.

The proposed method allows to increase the yield of the target product from 29% by a known method to 55-80% while maintaining the quality of the product. The method is one-step,

The best results are achieved when the ratio of solvents

five

0

five

0

five

0

diethyl ether 1: (3-1) and 10-20 ° C. Changing these parameters reduces the yield of the target product at the same reaction time,

The determining factor in the synthesis of the target product is the use of copper-containing intermediate on the basis of 1- (2-tetrahydropyranyl) ox-9-decin. The use of a lithium derivative intermediate leads to a decrease in the pheromone yield by up to 29%. The use of a less basic intermediate than lithium concentrations of the intermediate product, a magnesium-containing substance reduces the yield of the target product up to 10%. The copper derivative, despite its practical insolubility in the solvent mixture used, and low basicity, allows for high yields of the desired product.

Claims (1)

Invention Formula The method of producing 12E-tetradecene-9-yn-1 ol by metallation of 1- (2-tetrahydropyranyl) oxy-9-decin by reacting the obtained metallographic derivative with crotyl bromide in an organic solvent medium, followed by acid hydrolysis, characterized in that In order to increase the yield, metalation is carried out successively with equimolar amounts of ethylmagnesium bromide and copper iodide (I), and the process is carried out in a mixture of tetrahydrofuran and diethyl ether, taken in a volume ratio of (1–4): 1 with temperature 5-30 C.