SU427944A1 - METHOD OF OBTAINING 0-TRIALKYLSTANNYL DERIVATIVES OF HALOGENACETYLENE-CARBON ACIDS - Google Patents

Description

one

The invention relates to a new process for the preparation of new o-trialkylstannyl derivatives of haloacetylenecarboxylic acids, which may be of interest as biologically active compounds.

A known method for the preparation of o-trialkylstannyl derivatives of acetylenstannanes, which consists in reacting triorganiclnanilazide with acetylenicarboxylic acid.

The process for the preparation of o-trialkylstannyl derivatives of halogen acetylenic carboxylic acids is not described in the literature.

A method for the preparation of o-trialkylstannyl derivatives of halogenoacetylenecarboxylic acids of the type RaSnOCOC CX (R is alkyl, X is halogen) is proposed, which means that C, O-bis-trialkylstannyl acetylenicarboxylic acid derivative RsSnOCOC CSnRs, where the value R is indicated, is indicated by a position, it is indicated by a position, it is indicated by a position, it is indicated by a position, it is, in the environment of an organic solvent. Yield 60-70%.

The reaction is carried out at a temperature of 5-20 ° C; after distilling off the solvent, the target product is isolated by recrystallization.

For the first time, it was possible to show that the Sn – C bond in trialkylstannyl derivatives of acetylenecarboxylic acids of the indicated type is less stable under the action of halogens than the bond

Sn-O. This principal

C, 0-bis-trialkylstannyl derivatives of acetylene carboxylic acids

it was impossible to predict in advance, based on well-known literary material.

Example 1. Z-chloro-propyn-2-oic acid triethylstannyl ester. To a solution of 2.82 g (0.006 mol) of 3-triethylstannylpronin-2-oic acid triethyl ethyl ester (C2H5) C5pOCOS SZp (C2H5) C (mp 102-104 ° C) in 10 ml of ecu, cooled to 5-10 ° C, a solution of 0.53 g (0.006 mol) of chlorine in 10 ml of ecu is added dropwise with stirring. At the end of the chlorine solution, the reaction mixture is stirred for 30 minutes and distilled from it under vacuum ecu. The solid residue is recrystallized from cyclohexane with the addition of a small amount of benzene.

Yield (S2P5) of Z5POSOC CC1 1.22 g (66.3%), so pl. 130-131 ° C.

Found,%: C 35.11; 35.13; P 4.97; 4.91; Sn 38.49; 38.53; C1 11.38; 11.31.

CsHisOaSnCl.

Calculated,%: C 34.94; P 4.89; Sn 38.37; C1 11.46.

In the IR spectrum (tablet with KBG) there are bands vc o 1580cm and 2217cm-.

Example 2. Tristilline ether

3-bromo-propyn-2-oic acid, to a solution of 4.25 g (0.009 mol)

(CaHs) aSnOCOC CSn (CaH3) s

in 10 ml of ecu, 1.44 g (0.009 mol) of bromine dissolved in 10 ml of ecu are added dropwise with stirring at room temperature. At the end of the reaction, the solvent was distilled off in vacuo. The solid residue is recrystallized from a mixture of cyclohexane with benzene.

Yield (С2Н5) З5ПОСОС СВг 2.0 g (65%). T. pl. 144-145 ° C (decomp.).

Found,%: C 30.80; 30.77; H 4.29; 4.39; Sn 33.73; 33.57; Br 22.57; 22.76.

CsHisOaSnBr.

Calculated,%: C 30.55; H 4.27; Sn 33.54; Br 22.59.

The IR spectrum (tablet with KBr) contains bands of 1580 and 2200 cm.

Example 3. Ethylstannyl ester of 3-iodopropin-2-oic acid. Obtained similarly to the bgyra OHG-g 2.0 g (0.004 mol) (C2H5) s 5pOSOS C5p (C2H5) s and 1.02 g (0.004 mol)

iodine dissolved in ether at room temperature.

Yield (C2H5) z3POSOS C1 1.04 g (65%). T. pl. 143-144 ° C (decomp.).

Found,%; C 27.63; 27.99; H 3.91; 4.08; Sn 30.06; 30.04; I 30.75; 31.52.

CgHisOsSnI.

Calculated,%: C, 26.97; H 3.77; Sn 29.61; I 31.66.

The IR spectrum (tablet with KBr) contains bands of 1580 and 2160 cm.

Subject invention

The method of obtaining o-trialkylstannyl derivatives of halogen-acetylenecarboxylic acids of the type R3SnOCOC CX (R-alkyl; X -

halogen), characterized in that the C, O-bistrialkylstannyl derivative of acetylenecarboxylic acid, Cs5pOCOS, Cpnc, where the R value is indicated above, is reacted with a halogen in an organic medium

solvent.