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A number of 2‐N‐alkylamino‐ or 2‐N‐phenylamino‐, 2‐N, N‐dialkylamino‐, and 2‐N‐alkyl‐N‐phenylaminothiophenes have been prepared in good yields by adding a solution of tert‐butylalcohol and potassium tert‐butoxide in dimethylsulfoxide to a solution of the adduct from a lithiated 1‐alkyne, RCH2C≡CLi, or the lithiated allene, tBuCH=C=CHLi, and isothiocyanate, R′N=C=S, in tetrahydrofuran and subsequently hydrolyzing the reaction mixture or quenching it with methyl iodide.

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