Preparation and some reactions of bis(thioacyl) sulfides

Abstract

Reaction of dithioic acids with dicyclohexylcarbodiimide has been found to give the corresponding bis(thioacy1) sulfides 1 in good yield, which are very useful thioacylating reagents under mild reaction conditions. Most of the aromatic thioanhydrides (1, R = aromatic) are fairly stable green crystals at room temperature, but the aliphatic ones (1, R = aliphatic) are unstable purple oils which dimerize at room temperature to give the dithietanes 5. The reactions with nucleophiles are discussed. Darstellung und einige Reaktionen von Bis(thioacy1)sulfidenDurch Umsetzung von DithiocarbonsBuren mit Dicyclohexylcarbodiimid wurden die Bis-(thioacy1)sulfide 1, die niitzliche und unter milden Reaktionsbedingungen einsetzbare Thioacylierungsmittel sind, dargestellt. Die aliphatischen Thioanhydride (1, R = Aliphaten) sind thermisch labile und feuchtigkeitsempfindliche purpurne Ole, die bei Raumtemperatur zu den Dithietanen 5 dimerisieren, wlhrend die meisten aromatischen Derivate (1, R = Aromaten) tiefgriine, einigermanen stabile Kristalle bilden. Einige Reaktionen mit Nucleophilen werden diskutiert. Bis(thioacy1) sulfides 1, the trithio analogues of acid anhydrides, are attractive compounds of spectroscopical and synthetical interest, especially in thioacylation.Their remarkable instability and sensitivity towards moisture, however, have prevented the isolation and characterization since the first description of 1 [R = (C2H,C0J2CHj by Wenzella) in 1900. Recently, we reported the first isolation of some simple bis(thioacy1) sulfides *) 1. In this paper, we describe more detailed preparation methods and some reactions with nucleophiles. Results and DiscussionFor the preparation of 1 the following five routes have been investigated in detail: a) Desulfurization of bis(thioacy1) disulfide with triphenylphosphine or trialkylphosphite.

Unusual Saddle‐like Structure of (2‐MeOC6H4CS)2S: Theoretical Studies and Comparison with its Oxygen Isologues

“…The spectroscopic data and physical properties were in good agreement with that of the authentic sample which was prepared from the condensation reaction of the corresponding carbodithioic acid with dicyclohexylcarbodiimide 3b…”

A dithietane of 2-methylpropanedithioic acid

“…This reaction occurs with a large evolution of H 2 S and the formation of the dithiethane, (I), as shown in the reaction scheme. A similar compound was obtained by reaction of the same dithioacid with dicyclohexylcarbodiimide (Kato et al, 1982). The crystal structure determination was undertaken to establish the conformation of the reaction product, (I), and to understand the process of its formation.…”

The improved synthesis, Diels-Alder reactions, and desulfuration of trithio-1,8-naphthalic anhydride

“…Kato [4] found that aliphatic thioanhydrides (1, R ‫ס‬ aliphatic, see Scheme 1) are highly unstable, whereas aromatic ones (1, R ‫ס‬ aromatic) are fairly stable. Cava [5][6][7] reported the first cyclic trithioanhydride, trithio-1,8-naphthalic anhydride (3, , and he found that 3 is very stable.…”