The "acetylene zipper" reaction of diacetylenic hydrocarbons by the action of lithium 2-amino-ethylamide in the absence of ethylenediamine as solvent was studied. The isomerization conditions were found for synthesis of α- and β-long-chain diacetylenic alcohols by consecutive reactions of lithium 1,3-alkadiynides with oxiranes and ketones. The reactions with 2-acetyl- and 4-benzoylpyridines gave both α-diacetylenic alcohols and products of their isomerization in which the conjugated triple bonds were displaced to the 3,5-position.