ORGANIC OXALATES .2. FORMATION OF BIBENZYLS BY PYROLYSIS OF BENZYL OXALATES

Several benzyl oxalates were converted to the corresponding bibenzyls in good yield by pyrolysis in the gas phase. Since oxalates are readily prepared from benzyl alcohols, pyrolysis of oxalates offers a convenient way of converting benzyl alcohols to bibenzyls. Pyrolyses of the unsymmetrical oxalates, benzyl p-chlorobenzyl oxalate and benzyl benzyl-α,α-d2 oxalate, indicate that the mechanism of the reaction requires statistical scrambling of the benzyl groups, which is consistent with the formation of benzyl radicals. Gas-phase pyrolysis of oxalates appears to be a means of generating relatively stable radicals, such as benzyl radicals, in the absence of any very reactive radicals or molecules. © 1968, American Chemical Society. All rights reserved.