SU362021A1 - METHOD OF OBTAINING BIS- (sy-OXYALKYL) -TETRAALKYL-DYSYLOXANE ETHERS OF HYDRAZINCARBONE - Google Patents

Description

 The invention relates to a method for producing organosilicon carbofuctional hydrazino esters, which can be used as a starting material for a number of new compounds, including nolymers. The purpose of the invention is to develop a process for the preparation of new compounds of the general formula: NOR NHCHjCIlC-0 (CH2) n Si-O -Si (CHi) nOC -SPCHNMN RRRR R, R,, CH ,; , CH „C. n l-3. The interaction of hydrazines with organosilicon compounds, in particular with trialkylsilyl monocarboxylic acid esters, is known to produce silyl hydrazidines. However, bis- (co-oxyalkyl) tetraalkyl disiloxane esters of a, p-unsaturated acids were not involved in such a reaction. The proposed removal procedure is that organosilicon carbo-functional hydrazino esters are obtained by adding adducting hydrazine or its derivatives on the activated double bond of the bis- (co-hydroxyalkyl) tetraalkyl disiloxane esters of the unsaturated sites. The reaction is best carried out at a temperature of 60-90 °, without solvent, in the presence of 30-50% excess of hydrazine or its derivatives. As a result of the reaction, bis- (shgidroksyalkyl) - tetraalkyldisiloxane esters of hydrazinocarboxylic acids are obtained with a yield of up to 40%. The resulting compounds are light yellow liquids with a strong odor, their composition and structure are confirmed by elemental analysis, IR and PM spectra. In the IR spectra of the obtained compounds (I-IV) there are intense absorption bands due to the stretching vibrations of the KS group (3230-3215 sip), and the absorption is observed, characteristic of the stretching vibrations of the Si-CH3 group (1250) (). Si-O- Si (1090-1020 c. "- t), C 0 (1750-1730 cl), the absorption bands corresponding to the stretching vibrations of the C С double bond (1680, are absent. The PMR spectrum of bis- ((o-hydroxymethyl) - tetramethyldisiloxane ester of hydrazinoisobutyric acid has characteristic signals, one of which with a chemical shift of 0.09 M. Methanol. corresponds to protons apt groups of silicon and silicon, the second-b of 1.05 ppm corresponds to protons of methyl groups at the carbon atom, the third b 3.07 ppm corresponds to the protopes of methylene groups at the crempie atom, the fourth signal with chemical shift b 5 , 47 ppm refers to the protons at the nitrogen atom. The distribution of protons along the integral curve corresponds to the proposed formula. As can be seen from the above, the proposed method for the synthesis of silicon-functional complexes monomers is characterized by the simplicity of the reaction. Example 1. In a three-necked flask supplied with a stirrer, thermometer and reflux condenser, 6 g (0.02 mol of acrylate bis - (co-hydroxymethyl) - tetramethyl disiloxane and 3.6 g (0.06 mol) M, N-dimethylhydrazine) are loaded The reaction is carried out at a temperature of 24 hours. Then the reaction mixture is distilled under vacuum. At a temperature of 150-152 ° C (1 mm Hg), 2.2 g (26.6% yield) of bis are released. - (co-hydroxymethyl) - tetramethyldisiloxane ester L, L-dimethylhydrazinopropionic acid with ng 1.4604 Found: C 45.45; H 8.27; N 12.9; Si 14.03. Ci6H38OsN4Si2. Calculated,% : C 45.49; P 9.0; N 13.12; Si 13.12.

Example 2. 6 g (0.02 mol) of acrylate-bis (n-hydroxymethyl) -tetramethyldisiloxaia and 10.8 g (0.1 mol) of N-phenylhydrazine are heated to 50 ° C with continuous stirring for 12 hours. Then, distillation under vacuum of the reaction mass at 139-142 ° С (1 mmHg), 4 g (yield, 39.5%) of bns- (hydroxymethyl) - tetramethyl disiloxane N-phenylhydrazino-propionic acid ester was isolated.

20

D - 1.5664.

C n% found: C 55.70; H 7.23; N 10.85; Si 9.96.

C26n38O5N4Si2 ..

Subject invention

Claims (2)

1. A process for the preparation of bis - ((y-hydroxyalkyl) tetraalkyldisyloxy esters of hydraziparboxylic acids, characterized in that hydrazine is reacted with bis ((0 - oxyalkyl) - tetraalkyldisiloxane ester of a, 3-unsaturated acids to isolate the target product by known methods. 2. A method according to claim 1, characterized in that the process is carried out by heating to 60-90 ° C. Calculated,%: C 55.59; H 7.33; N10.81; Si 10.81. Example 3. 8.25 g (0.025 mol) of methyl acrylate-bis- (co-hydroxymethyl) -tetramethyldisiloxane and 4 g (0.125 mol) of hydrazine are heated to 80-90 ° C with continuous stirring for 12 hours. Then, distillation under vacuum of the reaction mass at 110-112 ° C (1 mmHg), 2 g (yield 21%) of bis- (co-hydroxymethyl) - tetramethyldisiloxane hydrazinoisobutyric acid ester with Pau 1.4748 was isolated. Found,%: C 42.80; H 8.59; N 14.43, Si 14.47. Ci4H34O5N-4Si2. Calculated,%: C, 42.70; H 8.65; N14.31; Si 14.31. Example 4. The reaction of methacrylate-bis (with hydroxymethyl) -tetramethyldisiloxane (6.5 g; 0.05 mol) with N, N-dimethylhydrazino j (9.6 g; 0.15 mole) is carried out according to the method In Example B, described in Example L, at 160-162 ° C (1 mm Hg), 3 g (yield 13%) of bis (co-hydroxymethyl) - tetramethyldisiloxane ester of N, N-dimethylhydrazine-isomeric acid with 1.4513 is isolated. C 48.67; H 9.06; N 12.45; Paydepo, Si 13.03; C, 8H4205N4Si2. Calculated,% C 48.3; H 8.95; N 12.5; Si 12.5.