title: Thionations using a P4S10-pyridine complex in solvents such as acetonitrile and dimethyl sulfone.
abstract: Tetraphosphorus decasulfide (P(4)S(10)) in pyridine has been used as a thionating agent for a long period of time. The moisture-sensitive reagent has now been isolated in crystalline form, and the detailed structure has been determined by X-ray crystallography. The thionating power of this storable reagent has been studied and transferred to solvents such as acetonitrile in which it has proven to be synthetically useful and exceptionally selective. Its properties have been compared with the so-called Lawesson reagent (LR). Particularly interesting are the results from thionations at relatively high temperatures (∼165 °C) in dimethyl sulfone as solvent. Under these conditions, for instance, acridone and 3-acetylindole could quickly be transformed to the corresponding thionated derivatives. Glycylglycine similarly gave piperazinedithione. At these temperatures, LR is inefficient due to rapid decomposition. The thionated products are generally cleaner and more easy to obtain because in the crystalline reagent, impurities which invariably are present in the conventional reagents, P(4)S(10) in pyridine or LR, have been removed.
authors.affiliation: Unit of Organic Chemistry, Department of Biosciences at Novum, Karolinska Institute, SE-141 57 Huddinge, Sweden. jan.bergman@ki.se
authors.forename: Jan
authors.initials: J
authors.lastname: Bergman
authors.forename: Birgitta
authors.initials: B
authors.lastname: Pettersson
authors.forename: Vedran
authors.initials: V
authors.lastname: Hasimbegovic
authors.forename: Per H
authors.initials: PH
authors.lastname: Svensson
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D000577:Amides / Q000737:chemistry; D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010758:Phosphorus / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013450:Sulfones / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D000577:Amides; D011725:Pyridines; D012997:Solvents; D013450:Sulfones; D010758:Phosphorus; D013455:Sulfur; C025910:dimethyl sulfone; C023666:pyridine; D004121:Dimethyl Sulfoxide; C032159:acetonitrile