SU385954A1 - METHOD OF OBTAINING ETHYLENE a-KETOSPIRTS - Google Patents

Description

one

The invention relates to a process for the preparation of ethylene a-ketospirits, which can be used as intermediates in organic synthesis.

A known method of producing ethylene a-ketospirit-3-b) ten-n-2-ol-1 by isomerization of the corresponding diatomic peptide alcohol in a water-methanol solution in the presence of a mercury salt as a catalyst.

The desired product is isolated by known techniques.

The disadvantage of this method is the presence of by-products that reduce quality. The yield of the target product to 4%.

In order to increase the yield and expand the assortment of the final product, a method for the production of ethylene a-ketospirits has been proposed, namely, that the corresponding diatomic acetylene alcohol is subjected to isomerization in absolute ethanol or acetonitrile in the presence of a mercury salt as a catalyst when heated to no more than 30 ° C.

The desired product is isolated by known techniques. Tsaru with a known alcohol obtained not described in the literature.

The yield of the target product is 85-90%.

Example 1. Preparation of propenyloxyethyl ketpna (4-hexene-one-3-ola-2).

To a solution of 10 g of dimethylbutyniol in 50 ml of absolute ethyl alcohol is added a solution of 2 g of nitric acid mercury in 12 ml of abs. ethyl alcohol at a temperature of 20-25 ° C. The reaction mixture is stirred at 25 ° C for 2 hours, filtered and the solvent is evaporated. The residue was distilled with steam, extracted with ether, and dried with magnesium sulfate. After evaporation of the ether, a mobile liquid is obtained, i.e. 43.5 ° C / 8 mm Hg Art., djo - 0.9907, n2 ° 1.4484.

Found, they say. weight: software; 108

Calculated by SbH1O02 114;

Found MR: 30.20

Calculated

SN.CHN CH-C-SI-CHZ 30.80 P I

Oh he

Yield 9 g (90%). Semikarbazon, so pl.

196-198 ° С 2,4-dinitrofepilgidrazon, t. Pl.

213-215 ° C. Example 2. Obtaining butenyloxypropyl ketone (5-octene-on-4-ol-3). To a solution of 10 g of diethylbutyniol in 50 ml

absolute ethyl. alcohol is added

a solution of 2 g of nitric mercury in 12 ml of abs.

ethyl alcohol at a temperature of 20-25 ° C.

The reaction mixture is stirred at 25 ° C for 2 hours, filtered and the solvent is evaporated.

The residue is distilled with steam, extracted with ether, and the lye is dried. After evaporation of the ether, an oil of j 0.9023 is obtained; nj; 1.4220; Found, they say. weight: 137; 136 Calculated CsNmOg 142 Found, MR: 40; 230 Calculated СНзСН2СН СН-С-СИ-СНг-СНз 40.114 II I О ОН Yield 8 g (80%) 2,4-dinitrophenylhydrase, it, so pl. 118-120 ° C. Example 3. Preparation of styryloxybenzyl ketone (1,4-diphenyl-4-butene-one-2-ol-1). To a suspension of 10 g of diphenylbutynedioton in 50 ml of absolute ethanol is added a solution of 2 g of nitric acid mercury in 12 ml of abs. ethyl alcohol at a temperature of 20-25 ° C. The reaction mixture is stirred at 25 ° C for 2 hours, filtered and the solvent is evaporated. 30 ml of abs are added to the residue. ether and left for one hour at - | -18 ° C, filtered from mercury compounds and the solvent is evaporated. An oil is obtained, djg 1.1403, nJ5 1.5710. Found, MR: 71.5 Calculated CeHsCH CH-C-CH-CsHs 70.2. Yield 7.5 g (75%) 2,4-dinitrophenylhydrazone, m.p. 221-222 ° C. Example 4. Obtaining tsobutenyloxysispropyl ketone (2,5-dimetzl-4-hexene-on-3-olc 2). To pacfEop 10 g tetramethylb utiindole in 50 ml abe. ethyl alcohol added a solution of 2 g of mercuric acid nitrate in 12 ml of abs. Ethyl alcohol spraying Ave. and a temperature of 20-25 ° C. The reaction mixture is stirred at 25 ° C for 2 hours, filtered and the solvent is evaporated. The residue is distilled from water with steam, the distillate is extracted with ether, and the extract is dried with magnesium sulfate. After evaporation of the ether, an oil is obtained, 0.9724, n | 1.4355. Found, they say. weight; 137, 139, Calculated 142. Found, MR: 39.20, Calculated СНз СН-С-С-СН, 40,114. Yield 9 g (90%) 2,4-dinitrophenylhydrazone, so pl. 186-188 ° C. The subject matter of the invention is a method for producing ethylene c-ketospirits by isomerization of a dihydric acetylenic alcohol in a solvent, in the presence of a mercury salt as a catalyst, followed by isolating the target product with known techniques, in order to increase the yield and expand the assortment of the final product, as absolute ethanol or acetonitrile are used as solvents.