SU386950A1 - ENELIOTENA I - Google Patents

Description

METHOD OF OBTAINING ADAMANTHYLALKYLGALOIDSYLANES

one

The invention relates to the production of new organosilicon compounds with adamantylamine radical of the general formula

AdRSiR "Cl3-",

where Ad-1 is adamantyl radical;

ganosilane in the presence of catalysts Friedel-Crafts reaction with heating, for example, up to 30-200 ° C according to the scheme

AdH + H, С CH (CH,) „SiR;„ Cl-m X

A1С1з

(CH.) + 2SlR Cl3 "

t °

R is alkylene; R-alkyl; n 1-3.

Synthesized organosilicon compounds with an adamantylamine radical can be used as monomers to produce new polysiloxane materials of various structures and modifications of known polysiloxane materials.

The reaction to add hydrocarbons to unsaturated chlorosilanes in the presence of catalysts of the Friedel-Crafts reaction, for example aluminum trichloride, is widely known. However, adamantane has not previously been introduced into such a reaction.

The proposed method consists in the interaction of adamantane with an unsaturated organic or 0.1;

R is alkyl;

t 1-3.

The proposed method for the synthesis of organosilicon compounds with an adamantylamine radical is characterized by simplicity, since

the synthesis is carried out in one stage with good yields, and the starting compounds (adamantane, unsaturated silicon compounds and aluminum trichloride) are quite available substances.

Example 1. 1-Adamantyl-1-ethyltrichlorosilane.

In a three-neck flask with a capacity of 250 ml, equipped with a blender, an effective reflux condenser and a thermometer, were placed

27.2 g (0.2 mol of adamantane, 32.3 g (0.3zhol) of vinyltrichlorosilane, and 13.3 g (0.1 mol) of aluminum trichloride. During the transfer, heat was released and the temperature of the reaction mixture rose to 35 ° C. To complete

reaction temperature for 2 hours raised to 110 ° C. Aluminum chloride was filtered off and the filtrate was distilled in vacuo. Received 30 g (50% of theoretical) 1-adamantyl-1-ethyltrichlorosilane with so Kip. 140-14GS / 3.5 mmHg v .; 1.5135; df 1.2374. MRo: found 72.40; calculated 74.48. Found,%: C, 48.11; 47.76; H 6.39; C1 35.5; 35.5; Si 9.3; 9.73. Cl2Hi9Cl3Si Calculated,%: C, 48.38; H 6.43; C1 35.75; Si 9.43. The structure of the obtained compound was confirmed by the data of IR and NMR spectroscopy. Example 2. Analogously to Example 1, a mixture of 19.4 g (0.14 mol) of adamantane and 9.5 g (0.07 mol) of aluminum chloride is prepared. 44.2 g (0.14 mol) of isopropenyltrichlorosilane was added dropwise to the mixture while stirring for 1 hour, maintaining the temperature of the reaction mixture with the rate of addition of chlorosilane. To complete the reaction, the temperature of the reaction mixture is raised to 30 ° C for 30 minutes. 16.5 g of sodium chloride and then 200 ml of n-hexane are added to the cooled reaction mixture. The hexane solution is drained from the solid, the hexane is distilled off, and the residue is distilled in vacuo. Received 14 g (32% of theoretical) p - (adamantyl) - propyltrichlorosilane with m. Bale. 154-155 ° C / 2 mm Hg. v .; 1.5190; df 1.2621. Found%: C1 33.6. Ci3H2iCl3Si Calculated,%: CI 34.1. Example 3. Analogously to Example 1, 40 g (0.28 mol of methyl vinyl trichlorosilane) are added to the mixture of 27.2 g (0.2 mol) of adamantane and 11 g (0.08 mol) of aluminum chloride with stirring over 1 hour. the mixture was raised to 78 ° C. The reaction mixture was heated for an additional 1 hour, raising its temperature to 10 ° C, then cooled, and 23 g (0.4 mol) of sodium chloride and 200 ml of n-hexane were added. hexane, and the residue is distilled in vacuum. 27.5 g (50% of theoretical) of p- (adamantyl) -ethylmethyldichlorosilane with m.p. 158 ° C / 4 mm Hg; 1.5081; mp 36-37 ° C. Found: C1 25.4; 25.6. Cl3H22Cl2Si Calculated: C1 25.6. Example 4 Under the conditions of Example 1, a mixture of 27.2 g (0.2 mol) of adamantane and 6.6 g (0.05 mol) of aluminum chloride added 45 g (2.1 mol) of methylallyl dichlorosilane to the mixture during 30 minutes with stirring. The temperature of the mixture rose to 50 ° C. The mixture was heated to 120 ° C for 30 minutes, cooled, 16 g of phosphorus oxychloride and 30 ml of hexane were added. After distillation of the reaction products, 25 g (42% of theoretical) of methyl p- (1-adamantyl) propyl dichlorosilane with m. 1 bp is obtained. 143 ° C / 1,5l4l RT. v .; “20 1 5070; df 1.0930; MRo; found 79.29; calculated 79.32. Found,%: C 58.00; 57.82; H 8.23; 8.22; C1 24.32; 24.38; Si 9.61; 9.60. Ci4H24Cl2Si Calculated,%: C 57.75; H 8.24; C1 24.34; Si 9.62. In the experiment, 8 g (13% of theoretical) of 1,3-by-7- (dichloromethyl) -propyl adamantane with m.p. 203 ° C / 1.5 mmHg v .; 1.5102; df 1.1615; MNV: found 115.98; calculated 116.28. Found,%: C 48.02; 47.96; H 8.36; 8.39; C1 32.05; 31.72; Si 12.40; 12.38. Cl8H33Cl4Si2 Calculated: C, 47.82; H 8.40; C1 31.37; Si 12.39. The subject matter of the invention is 1. A method for producing adamantyl alkyl halidesilanes, characterized in that adamantane is reacted with unsaturated rganosilanes in the presence of the Friedel Crafts catalyst when heated with the following release of the desired product by known methods. 2. A method according to claim 1, characterized in that the process is carried out at a temperature of 30-200 ° C.