84783-07-3Relevant articles and documents
Rearrangements and Fragmentations of Phenyl Styryl Sulfides 2-Labelling studies
Dijkstra, P. J.,Weringa, W. D.
, p. 430 - 438 (1982)
Metastable molecular ions of phenyl styryl sulfides may decompose by loss of CH3., SH., CHS., C6H5., C6H6 or C7H7..Labelling with carbon-13 and deuterium gave information about the mechanisms of these reactions.It appears that extensive rearrangements occur prior to most of these fragmentations.In the case of phenyl β-styryl sulfide both phenyl groups and both vinyl carbon atoms are found in the C7H7 fragment in comparable amounts.For phenyl α-styryl sulfide this fragmentation leads more specifically to the loss of the S-phenyl group and the β-vinyl carbon atom.It was concluded that rearrangements occur, partly via symmetric diphenyl ethene sulfide structures, to benzyl phenyl thione ions, from which the fragmentation occurs.For the loss of CHS. an earlier proposed mechanism was confirmed.From both compounds the S-phenyl ring can be lost as C6H5. or C6H6 as well as the C-phenyl ring.Fragmentation occurs from one of the initial structures as well as from benzyl phenyl thione.Loss of CH3. is thought to occur after ring closure with formation of dihydrobenzothiophenes followed by ring opening by rupture of a C-S bond.While phenyl β-styryl sulfide shows a strong tendency towards isomerization to a symmetric structure like 1,2-diphenylethene sulfide, phenyl α-styryl sulfide easily rearranges in an electrocyclic reaction with formation of benzyl phenyl thione.
A useful method for configuration assignement of vinyl sulfides; stereochemical reassessment of the radical addition of benzenethiol to alkynes
Benati, Luisa,Capella, Laura,Montevecchi, Pier Carlo,Spagnolo, Piero
, p. 1035 - 1038 (2007/10/02)
A comparative analysis of the 1H NMR spectra of (E)- and (Z)-phenyl and alkyl sulfides and their corresponding sulfones provides a useful method for establishing their configuration.Although by employing this method we generally confirm our previous configurational assignement for benzenethiol/alkyne adducts, those for (E)- and (Z)-3-(phenylsulfanyl)hex-3-ene and 4-phenylsulfanyl)oct-4-ene, are shown to have been assigned incorrectly.In the light of the present results it is concluded that radical addition of benzenethio to alkynes at 100 deg C generally proceeds with trans-selectivity.This conclusion is the reverse of our earlier claim for the effect that benzenethiol adds to terminal alkynes and alkylphenylacetylenes in a trans-stereoselective mode, but in a cis-stereoselective mode to dialkylacetylenes bearing (rather) bulky alkyl groups.
