SU499265A1 - The method of obtaining acetylene derivatives of silicon or germanium - Google Patents

Description

one

The invention relates to the field of synthesis of organic compounds of silicon or germanium, in particular to a method for producing acetylenic derivatives containing a trialkyl (aryl) -silyl (germyl) group in a triple bond, of the general formula

CESEC,

where E is silicon, germanium.

R is alkyl, aryl,

X - substituents of various types, for example, alkyl, vinyl, acetylenyl, aryl, hydrogen, halogen, alkoxy, alkylthio, perfluoroaryl (alkyl), cyan, acetyl, formyl, carbalkoxy, nitro, dialkylamino, trialkylsilyl, - germyl.

Acetylene derivatives of elements of the IVB group can be widely used for the production of polymeric materials with high thermal, benzo and oil resistance and retaining their characteristics at low temperatures in semiconductor manufacturing.

A known method for the synthesis of acetylenic derivatives of silicon or germanium by the interaction of trialkyl (aryl) halosilanes or hermanes with the corresponding acetylenic tin compounds according to the scheme

(C, H,) 3GeBr-f (CH,), SnCECOC, H, X - (CH3) s5pBr4- (C, H,) sGeCECOC, H,

This reaction proceeds due to the increased nucleophilicity of the carbon atom of the Sn-Csp bond, which is created due to the positive mesomeric effect of the ethoxy radical and can only be used to obtain derivatives of the alkoxyacetylene type, where E-Si, Ge, and therefore cannot be used as a general method for the preparation of the proposed compounds .

The purpose of the invention is the creation of an experimentally simple method for the synthesis of acetylene derivatives of silicon or germanium, which allows a significant increase in the yield of the target product (85-95%) and is not available to other compound methods.

According to the invention, acetylenic derivatives of silicon or germanium are obtained by reacting a trialkyl (aryl) halosilane or -Herman with a trialkylstaninyl acetylene derivative in an aprotic dipolar solvent such as hexamethylphosphoric triamide (HMPA) or dimethyl sulphoxide

(DMSO), etc.

The reaction goes according to the scheme

RsSHlg-f RsSnCECX RsSnHIg +

+ R, 3CECX, where E-Si, Ge; Hlg-Cl, Br, I, F. It is better to take the solvent in the amount of 1-1.5 volume per volume of reagents. The reaction mass is stirred in a dry inert gas atmosphere for 0.5-2 hours at 20-100 ° C. Trialkylsnyl (germyl) halide, and this polio reacts, which is controlled by gas-liquid chromatography and NMR spectroscopy. The trialkylsilyl (germyl) acetylenes formed are isolated either by evacuating the reaction mixture (b.p. product less than or equal to bb. solvent) or by fractional distillation of the residue obtained after washing with water of the reaction mass (b.p. product over or equal to t. Kip. solvent). After drying, the solvent is again used in the syntheses, and the trialkylstannyl halides are used to obtain the starting tin-acetylenes, the methods of obtaining of which are well developed (yields of 80–90%). The reaction proceeds almost quantitatively with all the tin-acetylenes of the formula RsSnC E CX from the most reactive, where X-CP3, CBSD, OSgNb, SC2H5, C1, to low-active, where X-CH281 Mez, Mez, Example 1. In a flask equipped with a stirrer and inert for inert gas, 0.0244 g-mol trimethyl stannyl trifluoromethylacetylene and 0.01595 g-mol trimethyl chlorosilane are charged, 13 ml of HMPA are added, the mixture is heated. Stand 0.5 hours at 80 ° C; then it was isolated by vacuuming (mm Hg. Art.) 2.95 g of trimethylsilyl trifluoromethyl acetylene (yield 92% on silane), i.e. 73-74 ° C; rf ° 1.3538; d | o 0.9392. Found,%: C 43.75, 43.35; H 5.82, 5.42; Si 17 9 15 21. Calculated,%: C 43.36; H 5.41; Si 16.9. IR spectrum (drop): 2208 (С С) cm-. NMR spectrum (5% ecu): o (CH3) s31 0.20 ppm, 8CFs-26.2 ppm (rel. CPCC). The process is carried out in the same way as DMSO medium (yield 86%); previously, the product was obtained by organomagnesium synthesis in 18% yield using preparative gas-liquid chromatography. Example 2 To a mixture of 0.0331 g-mol of triethylstannyl-tertiary-butyl acetylene and 0.0265 g-mol of trimethylbromosilane, 10 ml of HMPA was added; the mass crystallizes with slight warming. After 2 h of heating at 90 ° C, 4.04 g of trimethylsilyl tertiary butylacetylene (87% yield), b.p., are evacuated from the liquid reaction mass by evacuation (5 mm Hg growth). 124,125 ° C;, 4G58; df 0.7442. Found,%: C 70.20, 70.11; H 11.23, 11.34; Si 17.70, 17.96. Calculated,%: C 70.04; H 11.76; Si 18.20. IR spectrum (drop): 2184, 2157 (C-C) cm-; NMR spectrum (5% SCC): b (cn) s51 0.11 ppm, 6 (CH3) cC 1.16 ppm. Previously obtained by an organomagnesium synthesis in the presence of CaCl with a yield of 65% and isolated by long rectification. Example 3. To a mixture of 0.0212 g-mol of trimethyl stannyl pentafluorophenylacetylene and 0.0191 g-mol of triethyl bromosilane were added 10 ml of HMPA. After 2 h of heating at 100 ° C, the solvent is washed with water, 4.86 g of triethylsilyl pentafluorophenylacetylene is isolated from the residue (yield 84%), b.p. 107 ° С (5 mm of mercury); 4 ° 1.4685; 1.1356. Found,%: C 55.09, 55.35; H 4.82; 5.23; Si 10.30. Calculated,%: C 54.89; H 4.93; Si 9.17. IR spectrum (2% CCU): 2174 (), 1512, 1500 (SatNb) cm-1. NMR-9P (15% SCC): bo 136.76; BM 163.36; bp 154.14 ppm L3-21.6; 124 1.7; 125 8.3; 1z4-20,1; 126-3.5; bs 1.5 Hz. Previously obtained as a result of multi-stage, long-term synthesis using magnesium-, copper-organic compounds and hard-to-reach bromotriethylsilyladetilene. Example 4. In a flask equipped with a stirrer and an inert gas inlet, 0.0226 g-mol of trimethyl-stanyl-trifluoromethylacetylene and 0.0188 g-mol of trimethyl-bromgerman are charged; 10 ml of HMPA is added and the mixture is heated. After heating at 80 ° C for 0.5 h, evacuate with a vacuum (Growth 5 mm Hg. Art.) 3.38 g of trimethyl germyl trifluoromethyl acetylene (yield 98% per germanium), m.p. 95-96 ° C; n2 ° 1.3803; df 1.2226. Found,%: C 33.81, 33.93; H 3.77; 3.80; Ge 32.31, 34.7. Calculated,%: C 34.20; H 4.27; Ge 34.45. IR spectrum (drop): 2200 (С С) cm-. Nuclear Magnetic Resonance Spectrum (5% CCU): 8 (mn), Ge 0.45 ppm, 8.3–27.3 ppm (rel. CPHS). Similarly, the process is carried out in DMSO medium (yield 92%). Previously, the product was obtained by organomagnesium synthesis in a yield of 14.5% and isolated by preparative gas-liquid chromatography. Example 5. To a mixture of 0.0222 g-mole of triethylstannyl-tertiary-butyl acetylene and 0.0178 g-mole of trimethyl bromgermann was added 10 ml of HMPA, the mixture was slightly heated. After heating at 80 ° C for 2 hours, 3.18 g of trimethyl germyl tertiary butyl acetylene (93% yield), m.p. b.p. were isolated by suction (5 mmHg). 139-140 ° C; ng 1,4346; f 0.9834. Found,%: C 52.87, 52.92; H 8.75, 9.14; Ge 34.77, 35.11. Calculated,%: C 54.37; H 9.12; Ge 36.51. IR spectrum (drop): 2191, 2154 (С С) cm-. NMR spectrum (5% SCC): b (cnB Ge 0.29 ppm, 8 (cN3) cC 1.18 ppm. Example 6. To a mixture of 0.0218 g-mol trimethylphenylpentafluorophenylacetylene and 0.0166

g-mole of triethyl bromgermann is added 10 ml of HMPA. After 1.5 hours of heating at 90 ° C, the solvent is washed with water, 5.92 g of triethylgermilane-fluorophenylacetylene (86% yield) is isolated from the residue (m.p.). 102 ° С (2 mm of mercury); 1.4795; df 1.3023.

Found,%: C 48.27, 48.47; H 4.70, 4.60; Ge 22.68, 21.22.

Calculated,%: C, 47.93; H 4.31; Ge 20.69.

IR (2% SCC): 2168 (C), 1508, 1497 cm-1 (CgFs). NMR spectrum (15% SCC): bo spectrum 137.24; 6m 163.65; bp 155.07 ppm

6

1z4-20,3; 126-3.1;

125 8.3;

123-22.0; 124

1.4; 1s5-1.7 Hz.

Claims (1)

Invention Formula The method of obtaining acetylenic derivatives of silicon or germanium by the interaction of trialkyl (aryl) halosilanes or -germans with a trialkylstanyl acetylenic derivative, characterized in that, in order to increase the yield of the target product and expand the field of application of the method, the process is conducted in an aprotic dipolar solvent medium.