Direct Syntheses of Tetrathiafulvalene and Bis(ethylenedithio)tetrathiafulvalene By a Non-Coupling Route from 1,4,5,8-Tetrathianaphthalene

1,3,5,8-Tetrathianaphthalene (2, TTN; 1,4,5,8-tetrathiatetralin) has been synthesized in one step from 4,5-bis(benzoylthio)-1,3-dithiole-2-thione (1) and cis-dichloroethylene in high yield. TTN (2) is readily converted into tetrathiafulvalene (2, TTF) upon tetralithiation or bis(ethylenedithio)tetrathiafulvalene (4, BEDT-TTF) upon tetralithiation, sulfur insertion into the carbon-lithium bond pairs and subsequent capping of the reactive intermediate with 1,2-dibromoethane. The rearrangement of TTN allows for a facile synthesis of TTF and a novel non-coupling route to BEDT-TTF.