Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Synthesis and Oxidative Desulfurization of PV-Functionalized Imidazole-2-thiones: Easy Access to P-Functional Ionic Liquids*

Paresh Kumar Majhi A , Gregor Schnakenburg A , Anthony J. Arduengo III B C and Rainer Streubel A C
+ Author Affiliations
- Author Affiliations

A Institut fur Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universitat Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany.

B Department of Chemistry, University of Alabama, Tuscaloosa, AL 35487-0336, USA.

C Corresponding authors. Email: aj@ajarduengo.net; r.streubel@uni-bonn.de

Australian Journal of Chemistry 68(8) 1282-1292 https://doi.org/10.1071/CH14726
Submitted: 23 December 2014  Accepted: 13 January 2015   Published: 24 March 2015

Abstract

Selective synthesis of 4-phosphanylated imidazole-2-thiones 2d, 3a,b(b′),c(c′),d were achieved using a backbone lithiation and phosphanylation reaction protocol. The 4-phosphanylated-imidazole-2-thiones 3b(b′),c(c′) were subjected to a oxidation/phosphanylation/oxidation reaction sequence to access C4/5-bis(phosphanoyl)-substituted imidazole-2-thiones 7b,c. Oxidative desulfurization of phosphanylated imidazole-2-thiones 2d, 4a,d, and 7b,c with hydrogen peroxide afforded the first examples of room temperature imidazolium ionic liquids 8d, 9a,d, and 10b,c respectively, possessing backbone P-substituents. To study the effect of the counter anion on the physical properties, imidazolium salts with counter anions such as Cl, BF4, PF6, Tf2N, and TfO have been prepared by exchanging the counter anion of the obtained imidazolium hydrogen sulfates 8a,d and 14b with appropriate alkali or alkaline earth metal salts. All target products were characterised by various spectroscopic and spectrometric methods and by a single-crystal X-ray structure study in the case of 5a.


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