Reaction of biphenylene with butyl-lithium gives a mixture of 1- and 2-lithiobiphenylene in the approximate ratio of 20 : 1. This mixture has been used to prepare the following 1-substituted biphenylenes: pentanoyl, methoxycarbonyl, carboxy, acetyl, formyl, hydroxymethyl, bromo-methyl, methyl, hydroxy, methoxy, acetoxy, allyloxy, carboxymethoxy, and iodo.