Scalable Synthesis of Naphthothiophene and Benzodithiophene Scaffolds as π-Conjugated Synthons for Organic Materials

Abstract

The synthesis on a gram-scale and the full characterization of naphtho[1,2-b]thiophene and benzo[1,2-b:6,5-b']dithiophene 4-carboxylate esters bearing 2-octyldodecyl side chains, and their stannylated and brominated derivatives, suitable for their insertion into π-conjugated polymers is described. The fully soluble and processable synthons are obtained through a cascade sequence of reactions, namely direct arylation and cross aldol condensation, which create an effective pathway for the annulation and π-extension of suitable, commercially available reagents. The newly reported synthesis are compared, whenever possible, using ‘green chemistry metrics’ with literature synthesis, showing dramatic improvements.

Key words

direct arylation - cross aldol condensation - annulation - heterocycles - organic materials

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