SU1643518A1 - Method of production of 1,8-octanediol - Google Patents

Abstract

The invention relates to polyhydric alcohols, in particular the preparation of 1,8-octanediol, which is a key synthon in the synthesis of a number of pheromones. The goal is to increase the yield of the target product. The preparation is carried out by the reaction of diisobutyl aluminum hydride with 1.7-octanedienes at 20–30 ° C for 4–8 h in the presence of a catalyst. The components of the latter are introduced in the following sequence: zirconium tetrachloride, then butyl alcohol and tetrabutoxy zirconium, and these reagents and catalyst components are taken in the following molar ratios: (260-200): 100: (1-3):: (4 -12) :( 1-31. The resulting mass is subjected to air oxidation for 1 hour at (-5) - (+ 30) ° C, oxygenated for 4 hours at 40-50 ° C and then a guide Rolled with water. The process is carried out in an inert organic solvent. 1 ta bl.

Description

The invention relates to an improved method for the preparation of 1,8-octanediol, which is a key synthon in the synthesis of a number of pheromones, for example, 9 Z-hexadetsal - a component of the pheromone of the cotton boll, Helithis ar-migera Hbn, and 9E-12E-tetradecadium nyl-1-acetate - pheromone mill moth, Plodia interpunctella.

The purpose of the invention is to increase the yield of 1,8-octanediol.

Example 1. A 0.1 L glass reactor mounted on a magnetic stirrer was charged in an inert gas atmosphere of 0.0466 g (0.0002 g-mol) of ZrClij. 0.0592 g (0.0008 g-mol) is added dropwise to

0.5 ml of hexane, stirred for 5-8 minutes to form a homogeneous solution. Then 0.0766 g (0.0002 g-mol) Zr (OC4H9) 4, 3.3 g (0.23 g-mol) in 3 ml of hexane and 1.1 g (0.010 g-mol) 1 are added, 7-octadiene and stirred at 25 ° C for 6 hours. The reaction mass is diluted with 20 ml of hexane and air is bubbled through it with vigorous stirring, maintaining the temperature in the range (-5) - (+5) ° C. The reaction mass is oxidized for 0.5 h at 20 a-30 ° C, then with oxygen at 40-50 ° C for 4 h. 10 ml of water are added to the reaction mass, the organic layer is separated, the aqueous is extracted

ether, the solvent is distilled off. 1.40 g (96%) of 1,8-octanediol are recovered. Melting point 61-62 ° C. Found,%: C 65.62; H 12.18.

c6n, 8oЈ.

Calculated,%: C 65.75; H 12.33.

Examples 2-15. The oxidation of the reaction mass is carried out under the conditions of Example 1. The conditions of the method are listed in the table.

Example 16. Conditions and ratio of reagents are similar to Example 1. The resulting reaction mass is diluted with 20 ml of hexane and air is bubbled into the atmosphere for 0.5 h at 0 ° C with vigorous stirring, then oxidized for 0.5 h at 25 ° C and oxygen at 45 ° C for 4 hours

After treatment of the reaction mass (analogously to Example 1), 1, 40 g (96%) of 1,8-octanediol is isolated.

Example 17. The conditions and the ratio of the reactants are the same as in Example 1. The resulting reaction mass is oxidized for 0.5 hours with air at -15 ° C, then 0.5 hours at 10 ° C and oxygen for 4 hours at 30 ° C.

1.16 g (80%) of 1,8-octanethiol was isolated.

Example 18. The conditions and the ratio of the reactants are similar to those in Example 1. The resulting reaction mass is oxidized.

0.5 h with air at + 15 ° С, then 0.5 h at 40 ° С and oxygen for 4 h at 60 ° С.

1.13 g (78%) of 1,8-octanediol was isolated.

Claims (1)

The proposed method allows to increase the yield of 1,8-octanediol to 80-98% against 43% in the known. Invention Formula A method of producing 1,8-octanediol using an organometallic compound in an inert organic solvent, characterized in that, in order to increase the yield of the target product, diisobutylaluminium hydride is used as the metal-organic compound, which is reacted with 1.7-octane diene. at 20–30 ° C for 4–8 h in the presence of a catalyst, the components of which are introduced in the following sequence: zirconium tetrachloride, then butyl alcohol, and tetrabutoxy zirconium, and the indicated reagents and components the catalyst is taken respectively in the following molar ratios (260-200): 100:: (1-3) :( 4-12) :( 1-3), the resulting reaction mass is subjected to air oxidation for 1 hour at (- 5) - (+30) ° С, oxygen for 4 hours at 40-50 ° C and then hydrolyzed with water.