Features of the reaction of 7,7-dichlorobicyclo[4.1.0]heptane with phosphorus trichloride

Abstract

Halo derivatives of bicyclic hydrocarbons have not been explored in the Kinnear–Perren–Clay reaction [1, 2]. We showed for the first time that 7,7-dichlorobicyclo [4.1.0]heptane (I) react with equimolar amounts of phosphorus trichloride and anhydrous aluminum trichloride under mild conditions. Two phosphonic dichlorides were formed (δР 46 and 51 ppm) in a 1 : 1 ratio upon controlled hydrolysis of the intermediate complex. According to the IR spectrum, they are unsaturated compounds (νС=С 1630 and 1640 сm). The Н NMR spectrum shows multiplets at 5.66–6.00, 4.55, 3.44 and 0.95–2.55 ppm, implying the presence of ring ethylene and methylene protons and РСН protons. These data together with the elemental analysis allowed the products to be assigned the structures of isomeric [2-(chloromethylene)cyclohexyl]phosphonic (II) and [chloro(cyclohex-1-enyl)methyl]phosphonic (III) dichlorides. DOI: 10.1134/S1070363208060364