Improved Synthesis of Tetrakis(2‐thienyl)methane

Abstract

An improved synthesis of tetrakis(2‐thienyl)methanes, where an aromatic nucleophilic substitution is the key reaction for the introduction of the fourth 2‐thienyl group, has been developed, thus, reaction of tris(2‐thienyl)methyl anion with 2‐fluoro‐5‐cyanothiophene smoothly proceeded to give (5‐cyano‐2‐thienyl)‐tris(2‐thienyl)methane in good yield. Alkaline hydrolysis of the cyano group to carboxylic acid followed by decarboxylation at 180°C in quinoline in the presence of copper(I) oxide afforded the parent tetrakis(2‐thienyl)methane in 50% total yield from the trithienylmethane.

Keywords:

• Tetrakis(heteroaryl)methanes
• Tetrakis(2‐thienyl)methane
• Aromatic nucleophilic substitution
• Decyanation

Acknowledgment

This work was supported in part by the 21st Century COE Program, Japanese Government (Creation of Integrated EcoChemistry).