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1,2,4-Dithiazole-5-ones and 5-thiones as efficient sulfurizing agents of phosphorus(iii) compounds - a kinetic comparative study.
MedLine Citation:
PMID:  23052107     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The sulfurization efficiency of 25 3-substituted-1,2,4-dithiazole-5-ones and 5-thiones towards triphenyl phosphite in acetonitrile, DCM, THF and toluene at 25 °C was evaluated. All the 1,2,4-dithiazoles are much better sulfurizing reagents than commercially available agents (PADS, TETD, Beaucage's reagent). The most efficient sulfurizing agents in all solvents are 3-phenoxy (), 3-phenylthio () and 3-ethoxy-1,2,4-dithiazole-5-one () whose reactivity is at least two orders of magnitude higher than that of other 1,2,4-dithiazoles. Contrary to a previous report, the sulfurization with does not yield carbonylsulfide and ethyl cyanate as the additional reaction products but unstable ethoxythiocarbonyl isocyanate which has been trapped with 4-methoxyaniline. Similar trapping experiments have proven that the site of attack is at the sulfur adjacent to the C[double bond, length as m-dash]O group for compounds and . The reaction pathway involves rate-limiting initial nucleophilic attack of the phosphorus at sulfur followed by decomposition of the phosphonium intermediate to the corresponding phosphorothioate and isocyanate/isothiocyanate species. The existence of the phosphonium intermediate during sulfurization of triphenyl phosphine with 3-phenyl-1,2,4-dithiazole-5-thione () was proven using kinetic studies. From the Hammett and Brønsted correlations and from other kinetic measurements it was concluded that the transition-state structure is almost apolar for the most reactive 1,2,4-dithiazoles whereas a polar structure resembling a zwitter-ionic intermediate may be more appropriate for the least reactive 1,2,4-dithiazoles. The extent of P-S bond formation and S-S bond cleavage is very similar in all reaction series but it gradually decreases with the reactivity of the 1,2,4-dithiazole derivatives.
Authors:
Oleksandr Ponomarov; Andrew P Laws; Jiří Hanusek
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-10-10
Journal Detail:
Title:  Organic & biomolecular chemistry     Volume:  -     ISSN:  1477-0539     ISO Abbreviation:  Org. Biomol. Chem.     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-11     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101154995     Medline TA:  Org Biomol Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
University of Pardubice, Faculty of Chemical Technology, Institute of Organic Chemistry and Technology, Studentská 573, 532 10 Pardubice, The Czech Republic. Jiri.Hanusek@upce.cz.
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