Reactions of 3-Benzylidene-3H-1,2-dithioles and 3-Alkyl-1λ4,2-dithiol-1-ylium Salts with Isonitriles: A Synthesis of 1,6aλ4-Dithia-6-azapentalenes

1,6aλ⁴-Dithia-6-azapentalenes ( 7a )–( 7h ), ( 12a ), and ( 12b ) have been synthesized by the reaction of 5-aryl-3-benzylidene-3H-1,2-dithioles with isonitriles in the presence of phosphoryl chloride and by the reaction of 3-benzyl- and 3-methyl-1λ⁴, 2-dithiol-1-ylium salts with isonitriles. Possible mechanisms for these reactions are discussed. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8 : 479–485, 1997     

1λ5,3λ5-Diphospholium ions

One example each is given for the reaction of bromoacetylenes and ethynyl-phenyliodonium tosylates with bis(diphenyl phosphino)methane. The yellow crystalline 1:1-addition products are diphospholium salts. They readily and selectively hydrolyze to give 2-phosphinoylethenyl phosphonium salts.     

1λ6,2,4-Thiadiazetidine und 1,2λ6,3-Oxathiazetidine

1λ⁶,2,4-Thiadiazetidines and 1,2λ⁶,3-Oxathiazetidines From the reaction of the sulfur triimides (RN?)₃S ( 2a R?(CH₃)₃C, 2b R?(CH₃)₃Si) with pentafluoroazapropene ( 11 ) the appropriate 1λ⁶,2,4 thiadiazetidines ( 13a, 13b ) are formed, while from ClSO₂N?CCl₂ ( 14 ) and 2a (CH₃)₃C? N?C?N? SO₂Cl ( 17 ) is isolated. 2b and hexafluoroacetone ( 18 ) give the rather unstable 1,2λ⁶,3-oxathiazetidine ( 20 ).     

1, 2λ5-azaphosphinines and a new 1λ5, 3λ5-. Diphosphinine

The 1,2-azaphosphinine, 9 , and the 1,3-diphosphinine, 10 , can be isolated from a mixture resulting from the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and ethyl isothiocyanate. The reaction of 1 with phenyl isothiocyanate yields the 1,2-azaphosphinine, 16 . Mechanisms for the formation of the compounds 9 , 10 , and 16 are suggested. The properties, the NMR, mass, and IR spectra, and the molecular and crystal structures of 9 and 10 are described and discussed.     

Elucidation of the stereochemistry of thiirane formation from a 1λ4,2‐dithietane bearing two chiral carbon centers

A tetracoordinated sulfurane bearing a 1λ⁴,2‐dithietane moiety, whose 3‐ and 4‐positions were chiral carbon centers, was synthesized. Its thermolysis gave the corresponding thiirane as a single diastereomer, whose configuration and stereochemistry were determined. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:412–417, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20630