Reactions of spiro[2.3]hexane-5-carbonyl chloride with phosphorus(III) acids esters

Abstract

We have previously shown that the reaction of bicyclo[4.1.0]heptane-7-carbonyl chloride with medium esters of phosphorous and arylphosphonous acids occurs with the retention of the small carbocycle [1]. In continuation of this work it is interesting to study the behavior of carbonyl compounds of spirohexane series in the Arbuzov reaction [2]. Due to the high energy strain of these spiranes one could expect unusual reaction course affording new types of organophosphorus compounds. We found that spiro[2.3]hexane-5-carbonyl chloride I reacts readily with phosphorous and arylphosphonous acids esters. When an equimolar ratio of reagents was used under mild conditions (0–20°C), the attack of the P-nucleophiles occurs on the carbon atom of the carbonyl group. As a result, the reaction produces dialkyl spiro[2.3]hexane-5-carbonyl phosphonates IIa–IIc or alkylarylspiro[2.3]hexane-5-carbonyl phosphinates IId–IIf. DOI: 10.1134/S1070363213060303