jo016393h_si_002.pdf (31.99 kB)
Synthetic Procedure for Various Selenium-Containing Electron Donors of the Bis(Ethylenedithio)tetrathiafulvalene (BEDT-TTF) Type
journal contribution
posted on 2002-05-15, 00:00 authored by Kazuo Takimiya, Tetsuya Jigami, Minoru Kawashima, Mie Kodani, Yoshio Aso, Tetsuo OtsuboSix selenium variants of BEDT-TTF have been successfully synthesized by a newly developed
synthetic method that involves a combination of two key reactions for the construction of two kinds
of heterocyclic rings: the first is a one-pot formation of 1,3-dichalcogenole-2-chalcogenones from a
common starting material, THP-protected 2-(ethynylthio)ethanol, leading to the inner five-membered
rings, and the other is the annelation of the outer six-membered heterocyclic ring onto the inner
ring by an intramolecular transalkylation reaction on a chalcogen atom. This method turned out
to be widely applicable to the syntheses of the electron donors of bis(ethylenedithio)- and
bis(ethyleneselenothio)-substituted types. However, synthetic attempts to form analogous donors
of the bis(ethylenediseleno)-substituted type from THP-protected 2-(ethynylseleno)ethanol were
unsuccessful. This is attributable to the predominance of side-reactions via a seleniranium
(episelenonium) salt over the desired six-membered ring formation by transalkylation via a
seleninium salt.