SU715580A1 - Method of preparing silicon acetylenic carbonylic compounds - Google Patents

Description

An improved process for the preparation of silicon acetylene carbonyl compounds of the general formula

R SiC sCCOR

where R is an alkyl;

R is hydrogen or alcohol,

Silylacetylene aldehydes and ketones are widely used in organic synthesis or as biologically active substances.

A known method for producing silicon acetylene carbonyl compounds, for example aldehydes, consists in the oxidation of silylethinylcarbinols with chromic anhydride in sulfuric acid 1.

However, this reaction proceeds under stringent conditions. The initial and synthesized silylacetylenes are easily osmolymed under synthesis conditions, and the presence of an aggressive medium makes it difficult to use the process

The aim of the invention is to simplify the process for the synthesis of silicon acetylene carbonyl compounds.

This goal is achieved due to the fact that the silylethenyl carbinol is reacted with an oxidizing agent, namely with chlorochromatompyridini, in an organic solvent medium, preferably methylene chloride,

A distinctive feature of the process is the use of pyridinium chlorchromate as the oxidizing agent. The product is isolated by filtration through alumina and then distilled in vacuo.

0

The reaction proceeds as follows.

 WHCrO Ce

55.o

SiHC-CHOH

H NHCrOjCe

R

C-COR

2-Triethyl.syp.-2-propyn-1-al (R CaHj, R H), not described

Earlier, it was obtained with a yield of 86%. Other silylethinylcarbonyl compounds can be obtained in a high yield by this method.

The use of pyridinium chlorochromate as an oxidizing agent makes it possible to obtain the desired carbonyl compounds with a high yield under mild conditions.

The described method has several advantages:.

Pyridinium chlorochromate is an easily available oxidizing agent that is stable during long-term storage;

OCIs e chl o hrrmat OWtrfipH of di при ay flows under m-h conditions (methylene chloride, room temperature), which exclude an aggressive environment, which is especially important when using this method in prichishennosti;

the reaction time is reduced (if oxidation with chromic, anhydride in sulfuric acid takes 2-6 hours, according to thin-layer chromatography, the proposed process ends in 2 hours; tt flSteHHe oxidant from the reaction product is filtered through a layer of alumina, at the same time, purification of the carbonyl compound 6 of hr65 of resinous impurities takes place, and after removing the solvent, the chromatographically pure product of the reaction is obtained in almost quantitative yield, somewhat decreasing Tate vacuum distillation.

Example 1 A solution of 6.5 g of 3-triethylsyl-2-pr6pin-1-ol in 10 ml of dry methylene chloride is added dropwise to a suspension of 16.5 g of pyridinium chlorochromate in 100 ml of suhsego methylene chloride in a stream of arton in 10 ml of dry methylene chloride, the reaction mixture is stirred within 2 h, poured 100 ml of dry sulfuric ester, the solution is decanted and filtered through a 10-cm aluminum oxide column, Solvent

The mixture is distilled off in a water bath, the residue is distilled in vacuo.

5.5 g (86%) of 3-triethylsis are obtained. lil-2-propyne-1-al, t, kip, 7172 C / 10 mm Hg; 1.4658.

9.74; Found: C, 64.26; 64.32; H

9.74; Si 16.50; 16.58,

C e-OSi

Calculated,%: C 64.22; H 9.59; Si 16.69.

IR spectrum 1240. (C Hj-Si), 1670 (), 2160 (),

Example 2, Similarly, receive 3-trimethylsilyl-2-propyne-1-ap with a yield of 75%, so Kip, 42 ° C /:

/ 16 mm Hg, St; n |, °. 1.4420,

-Example 3, by oxidation of 4-trimethylsilyl-3-butyn-2-ol under the same conditions, 4-trimethylsilyl-3-butin-2-one is synthesized with a yield of 8%, 48s / 15 mm Hg, Art .; PC ° 1,4432,

Claims (1)

Invention Formula The method of obtaining silicon-acetylenic carbonyl compounds by reacting silylethynylcarbinol with an oxidizing agent in an organic solvent medium, characterized in that, in order to simplify the process, pyridinium chlorochromate is used as the oxidizing agent Sources of information taken into account in the examination 1, USSR Author's Certificate No. 170494, cl. From 07 F 7/08, 1965 (prototype), ...