Thionation of Some α,β-Unsaturated Steroidal Ketones 英文参考文献.docVIP

Molecules 2010, 15, 3462-3477; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Thionation of Some α,β-Unsaturated Steroidal Ketones Natalija M. Krsti? 1,*, Mira S. Bjelakovi? 1, Milan M. Dabovi? 1 and Vladimir D. Pavlovi? 2 1 Center for Chemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Studentski trg 12-16, P. O. Box. 473, 11001 Belgrade, Serbia; E-Mails: mbjelak@chem.bg.ac.rs (M.S.B.); mdabovic@chem.bg.ac.rs (M.M.D.) 2 Faculty of Chemistry, University of Belgrade, Student ski trg 12-16, P. O. Box 158, 11001 Belgrade, Serbia; E-Mail: pavlovic@chem.bg.ac.rs (V.D.P.) * Author to whom correspondence should be addressed; E-Mail: nkrstic@chem.bg.ac.rs; Tel.: +381-11-3336-666; Fax: +3811-11-2636-061. Received: 16 April 2010; in revised form: 30 April 2010 / Accepted: 10 May 2010 / Published: 12 May 2010 Abstract: The reactions of selected α,β-unsaturated steroidal ketones with Lawesson’s reagent (LR) in CH2Cl2 and toluene under the standard reaction conditions and with a combination of phosphorus pentasulfide with hexamethyldisiloxane (P4S10/HMDO) in 1,2- dichlorobenzene (ODCB) under microwave irradiation were investigated and for this purpose several cholestane, androstane and pregnane carbonyl derivatives were chosen. Depending on the reagent and the solvent, 19 new sulfur containing compounds, including dithiones 4c and 4d, α,β-unsaturated 3-thiones 3a-e, dimer-sulfides 2a-e, 1,2,4-trithiolanes 5a-e and phosphonotrithioates 6b-e were synthesized. All newly prepared compounds were characterized by IR, 1H- and 13C-NMR spectroscopy and elemental analysis. Keywords: α,β-unsaturated steroidal ketones; α,β-unsaturated 3-thiones; Lawesson’s reagent; P4S10/HMDO; dimerization, microwave irradiation 1. Introduction Steroids are an important group of natural compounds possessing a variety of biological activities. The replacement of one