General Method for the Preparation of Substituted Tetrathiafulvalenes and Directing Effects of Substituents

A general method for the synthesis of substituted tetrathiafulvalenes is described in which tetrathiafulvalene (TTF) or a substituted derivative of TTF is metalated with butyllithium or lithium diisopropylamide and then reacted with appropriate reagents to give a wide variety of new substituted tetrathiafulvalenes. Electron-donating substituents were found to deactivate the adjacent proton, while electron-withdrawing substituents activated the adjacent proton; thus the sequence in which the substituents are introduced can be utilized to control the structure. Multilithiation, temperature effects, and mode of addition are also discussed in relation to their effects upon substitution patterns. © 1979, American Chemical Society. All rights reserved.