PREPARATION AND SOME REACTIONS OF CYCLOPROPYLDIAZOMETHANE AND CYCLOPROPYLMETHYLDIAZOTATE

The synthesis of cyclopropyldiazomethane (CDM) is described. Hydrolysis of CDM with aqueous acid or base, or with distilled water afforded cyclopropylcarbinol, cyclobutanol, and allylcarbinol in a distribution similar to that observed in the aqueous nitrous acid deamination of cyclopropylcarbinylamine (i.e., cyclopropylcarbinyl/cyclobutyl was 1·0-1·4). Cyclopropylmethyldiazotate, I, afforded, upon hydrolysis, the same alcohols in a similar distribution. CDM was not an important precursor of the alcohols formed upon hydrolysis of I. The esters formed upon reaction of CDM and of I with ethereal benzoic acid were investigated. Both reactions gave a mixture of cyclopropylcarbinyl, cyclobutyl, and allylcarbinyl benzoates. The mixture was rich in cyclopropylcarbinyl benzoate (i.e., cyclopropylcarbinyl/cyclobutyl was ca. 5-8). Reaction of I and ethereal benzoyl chloride afforded the same esters in a similar distribution, and also, N-cyclopropylmethyl-N-nitrosobenzamide as a minor product. Thermolysis, in ether, of the nitrosamide also afforded the benzoate esters in a similar distribution. Intermediates capable of accounting for the products and their distribution are discussed. © 1968.