SU1165682A1 - Method of obtaining 2,2-diethyl-1,3-dioxa-2-silacylohexanes - Google Patents

Abstract

1. METHOD OF OBTAINING 2,2-DKETHIL-1, 3-DIOXA-2-SIPA11ICLOGEXANES of the general formula /, ЕН ;;) (с, н,), Ra -о Дз where R, Or CHj, R3,, R: j - identical or different H, or CH3, by reacting difunctional daethylsilane with an oxygen-containing organic compound, characterized in that diethyl-di (ethylthio) silane is used as a difunctional diethylsilane to increase the yield, and 2-ETOXI-1,3-dioxacyclohexane o is used as the oxygen-containing organic compound. general formulas

Description

The invention relates to organosilicon chemistry, more specifically to an improved method for producing substituted 2,2-diethyl-1,3-dix-2-strongcycloge1): sanovs of the general formula ...

, Rh.

Rlfti (C2H5) 2

about

"9 R,

where R, R, Niley CH,

R, R - the same or different П,

or SN.-,

which can be used as heat carriers, structuring additives, hydrophobic impregnation for bricks, and as intermediate products in organic synthesis -.

 A known method for producing 2,2-diethyl-1,3-diox-2-silicyclic hexanes by the interaction of equimolar amounts of diacetoxydiethylsilane and glycol in the medium of ether or chloroform is l.

The main disadvantages of the method are the low yield of the target product 61%, the reaction time is significant for 2 hours, the explosion and fire hazard of the process, since sulfuric ether is used as a solvent.

The closest to the technical essence of the present invention is a method for producing 2,2-diethyl-1,3-diox-2gsylacyclohexanes, including 5,5-dimethyl-2,2 diethyl-1,3-diox-2-strongcyclohexane, by the interaction equimolar amounts of diethyldichlorosilane with a glycol solution in triethylamine or pyridine cooled to 5-10 ° C with stirring under nitrogen atmosphere. The hydrochloride formed is filtered off and washed with ether. The ether and solvent (10 mol of solvent per 1 mol of glycol) are distilled off at atmospheric pressure, and the reaction product is distilled under reduced pressure 2.

The disadvantages of this method are low product yield (about 75%), the need to cool the mixture, the complexity of the process, due to its multi-stage, the use of explosive, flammable substances - sulfur ether. In addition, compounds of general formula I, where R, R CH, were not obtained.

The aim of the invention is to increase the yield, expand the range of target products and simplify the process.

The goal is achieved by the proposed method of obtaining compounds of formula I, consisting in

that difunctional diethylsilane, namely diztil-di (ethylthio) silane, is subjected to interaction with oxygen-containing organic compound, namely with 2-ethoxy-1,3-dioxacyclohexane of the general formula

Rh

where R-R have the indicated meanings, and the process is carried out in the presence of p-toluenesulfonic acid at 16-20 ° C.

Preferably, diethyl di (ethyl thio) silane and 2-ETOXY-1,3-dioxacyclohexanes should be taken in a molar ratio of (1.3-1.5): (0.8-1.0), respectively, and Toluenesulfonic acid in the amount of 0.2-0.3 g per 1 mole of 2-ETOXI-1,3-dioxacyclohexane. ,

Example 1. At 160 g (1 mol) of 5,5-dimethyl-2-ethoxy-1,3-dioxane, 313.5 g (1.5 mol) of diethyl di (ethylthio) silane is added and 0.2 g is added. paratoluenesulfonic acid (P-TSC) After 30 minutes, diethyl diethoxy silane is distilled off from the reaction mixture under reduced pressure and 173 g of 5,5-dimethyl-1,3-dioxa-2-silicyclohexane (92% code) are isolated by distillation. Conversion of initial reagents is practically quantitative -.100%. Next

ethyl thio-orthoformate is recovered (90% yield). .

The structure of the obtained compound, confirmed by elemental analysis, molecular refraction and NMR spectra.

Calculated,%: C 57.4A; .H 10.63; C 17.00; Si 14.93 ,. W 52.50. .

Found,%: C 57.50; And 10.70;

C Not defined, Si 15.00, MR 52.80. Sana (yield 92%). Conversion of initial reagents 100%. Example 15. Analogously to Example 1, the mixture of reagents was carried out at 16 ° C. 163 g of 5,5-dimethyl-2,2-diethyl-1, 3-diox-2-silacyclohexane were isolated (yield 92%). Conversion of initial reagents 100%. Example 16. Similarly to Example 1, the mixture of reagents was carried out at 10 ° C. 162 g of 5,5-dimethyl-2,2-diethyl-1, 3-diox-2-silacyclohexane were isolated (yield 86%). Conversion of initial reagents 92%. Example 17. Similarly to Example 1, the mixture of reagents was carried out at 30 ° C. 171 g of 5,5-dimethyl-2,2-diethyl-1, 3-dirks-2-silacyclohexane (yield 91%) were isolated. Conversion of initial reagents 100%. . It follows from the above examples that the optimum synthesis temperature is 16-20 ° C. Outside this interval, the yield of the target product decreases (examples 16 and 17). Example 18. Similarly to Example 1, 313.5 (1.5 mol) diethyl di (ethylthio) silane and 0.2 are added to 160 g (1 mol) of 4,4-dimethyl-2-ethoxy-1, 3-dioxane. g P-tsk. After 30 minutes, the theoretical amount of diethylthiethoxysilane was distilled off from the reaction mixture under reduced pressure and distilled off. 176 g of 4,4-dimeti-2-diethyl-1, 3-dioxa-2-silacyclohexane (output 94%). Conversion of initial reagents 100%. Further distillation gave ethyl thioformate (yield 90%). The structure of the obtained compound is confirmed by elemental analysis and molecular refraction data. Calculated,%: C 5.44; H10.63 O 17.00. Si 14.93, r8. C, H, 0, Si. C 57.50; H 10.40; Found,%: O Undetermined. Si 15.00; , 85. Example 19. Analogously to Example 1, 1323 g (1 mol) of 2-ETOXI-1,3 Dyrxane were added 313.5 g (1.5 mol of diethyl dimethyl) and 0.2 g of P-TSC was added. After 30 minutes the theoretical amount of diethyl diethoxysilane is distilled off from the reaction mixture under reduced pressure and distilled by distillation 150 g of 2,2-diethyl-1, ca-x -sylcyclohexane (yield 93%). Conversion of the starting reagents is quantitative. ). The structure of the obtained compound is confirmed by the data of elemental analysis and molecular refraction. Calculated,%: C 52, 46; H 10.06; O 19.96; Si 17.52; MR J, 43.44. CyHifcOzSi, C 52.50t H 10.10, Found, / O Not Ref .: Si 17.501, 56. Example 20 Analogously to Example 1, to 174 g (1 mol) of 4,4,6-trimethyl-2-ethoxy-1, 3-dioxane, 313.5 g (1.5 mol) of diethyl di (ethylthio) silane and 0.2 rfi-TCK. After 30 minutes, the theoretical amount of diethyl diethoxysilane is distilled off from the reaction mixture under reduced pressure and 194 g of 4,4,6-trimethyl-2,2-diethyl-1,3-dioxane-2-c1-cyclohexane is isolated by distillation (yield 96 %). Conversion of initial reagents is practically quantitative - 100%. Ethylthio-orthoformate (90% yield) was isolated by further distillation. The structure of the obtained compound is confirmed by elemental analysis and molecular refraction data. Calculated,%: C 59.35; H 10.96, O 25.81, - Si 13.88; 28 Found,%: C 59.50; H 11.0 O Not defined; Si 13.90-, 50. Example 21. Analogously to Example 1, 313.5 g (1.5 mol) of diethyl (ethylthio) silane and 0.2 g of P-1 are added to 146 g (1 mol) of 4-methyl-2-ethoxy-1, 3-dioxane. Tsk. After 30 minutes, the theoretical amount of diethyldiethoxysilane is distilled off from the reaction mixture under reduced pressure and distilled into distillation 165 g of 4-methyl-2,3-diethyl-1, 3-diox-2-silicyclohexane (yield 95%). Conversion of starting reagents 100 % Further distillation gave ethylthio-orthoformate (yield 90%). The structure of the obtained compound is confirmed by the data of elemental analysis and molecular refraction.

7 11656828

Calculated,%: C 55.17; H 10.33 / Use of the proposed method 18.37; Si 16.13; ba allows an increase in the yield of 1,3-diMRo 48, 28.ox-2-silacyclohexanes from 45-75 to

CoHioO, Si.92-96%, simplify the process and get

Q o Z ...,, --....,

Found,%: C 55.20, H 10.40,. . 5 new s, not known before soy0 Not defined. Si 16,10, dinene. ,20.

Claims (3)

1. METHOD FOR PRODUCING 2,2-DIETHYL-1,3-DIOXA-2-SSH1ACYCLOGEXHEXANES of the general formula ____ / I R AND $ 1 (C ₂ H ₅ b where R, R (= H or CH ₃ , R ₂ , R ₃ - the same or different H, or CH ₃ , by reacting difunctional diethylsilane with an oxygen-containing organic compound, characterized in that, in order to increase yield, expand the range of target products and simplify the process, diethyl di is used as difunctional diethylsilane (ethylthio) silane, and 2-ethoxy-1,3-dioxacyclohexane of the general formula is used as the oxygen-containing organic compound Η H, where R, R (, R ₂ , R2 have the indicated meanings, and the process is conducted in the presence of i-toluenesulfonic acid at 16 ~ 20 ° С. 2. The method of pop. 1, characterized in that diethyl-di (ethylthio) -silane and 2-ethoxy-1,3-dioxacyclohexane are taken in a molar ratio of (1.3-1.5) :( 0.8- 1,0). 3. The method of pop. 1, characterized in that p-toluenesulfo-acid is taken in an amount of 0.2-0.3 g per 1 mol of 2-ethoxy-1,3-dioxacyclohexane. 1 1165682 2