New liquid crystalline compounds based on 2-arylthiophenes and 2-(biphenyl-4-yl)thiophenes

Abstract

Abstract A general and versatile route to the 2-alkyl-5-(4′-cyanophenyl)thiophenes was established, involving the condensation of an aryl vinyl ketone with an aldehyde in the presence of a thiazolium catalyst (Stetter procedure) to give a 1,4-diketone which with Lawesson's reagent undergoes ring-closure to give the corresponding arylthiophene. In the final step the exchange of a bromo substituent on the phenyl ring for a cyano group is accomplished by copper(I) cyanide in N,N-dimethylforamamide at reflux. The same sequence afforded 2-alkyl-5-(4″-cyanobiphenylyl)thiophenes. Several of the 1,4-diketones were obtained by conjugate addition of nitroalkanes to aryl vinyl ketones, and treatment of the γ-nitroketones with silica gel-supported potassium permanganate. Three alkyl 5-(4-cyanophenyl)thiophene-2-carboxylates were prepared by condensing β-chlorovinylaldehydes with thioglycolates. The cyanophenylthiophenes exhibited only monotropic phases, but incorporation of an additional phenyl ring provided cyanobip...