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A reinvestigation was made of thiophene polymerization by trifluoroacetic acid with the aim of elucidating the structure of the oligomer product. Comparison of spectral and molecular weight data was made with corresponding data for thiophene polymer generated by means of aluminum chloride and for trimer prepared from thiophene–phosphoric acid. We conclude that the solid product from thiophene–trifluoroacetic acid is best represented by the following structure: In addition, the major product is the known liquid trimer: Our designation is in disagreement with that of Wassermann et al., who proposed a structure having aliphatic unsaturation.

Reaction of 1-azidoadamantane with aromatic substrates in the presence of aluminium chloride gave the corresponding 3-aryl-4-azahomoadamantane, presumably m a an imine intermediate ALKYL azides are reported to undergo reactions involving elimination of nitrogen gas, azide ion, or both, in the presence of aluminium chloride and benzene The resulting products were N-alkylanihnes, imines from rearrangement, or alkylbenzeiies The imines apparently did not participate in Friedel-Crafts alkylation We report the first reaction of an alkyl azide with aromatic compounds catalysed by aluminium chloride, resulting in rearrangement followed by aminoalkylation of the aromatic reagent When 1-azidoadamantane (1) was exposed a t 80 "C for 1.25 h to aluminium chloride in the presence of an aromatic resulted With sulphuric acid, 3-hydroxy-4-a~ahomo-Acknowledgement is made to the donors of the Petroleum adamantane is formed l2 Analogously, l-NN-dichloro-Research Fund, administered b y the American Chemical aminoadamantane, on rearrangement with aluminium Societv, for support of this research chloride, followed by treatment with nucleophiles, such as water, alcohol, thiols, or aromatic compounds, gave the corresponding 3-substituted-4-azahomoadamantantanes l3(Recezved, 4th December 1979, C o m 1270 )

Reaction of 3-azidohomoadamantane with aromatic substrates catalyzed by aluminum chloride at 80 °C gave the corresponding (1-adamantylcarbinyl)arene in >90% yield. The reaction proceeds exclusively with elimination of azide ion. Competitive reaction with toluene (T)-benzene (B) gave an average kT/kB of -14/1. The results indicate that a straightforward primary cation is probably not the actual attacking electrophile. The possible intervention of a bridged ion is discussed.

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