ISSN:
1042-7163
Keywords:
Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Stable benzene-fused polysulfide compounds, 3,4-dihydro-1,2,5-benzotrithiepins (1a-c), have been prepared, and the structure of 1a has been determined by X-ray crystallographic analysis. While the electrophilic oxidation of compounds 1 with m-chloroperbenzoic acid gave the corresponding 3,4-dihydro-1,2,5-benzotrithiepin 5-oxides (2) in moderate yields, the oxidation of 1 with N-bromosuccinimide afforded a mixture of 5-oxides 2, unexpected, inseparable 3,4-dihydro-1,2,5-benzotrithiepin 2,2-dioxides (3), and 3,4-dihydro-1,2,5-benzotrithiepin 1,1-dioxides (4). Semiempirical PM3 calculations were carried out, and the computed HOMO of 1a suggested a significant favoring of electrophilic reactions at the sulfur atom at the 5-position. The treatment of 5-oxides 2 with acetyl bromide or oxalyl dibromide as halogenating reagents gave 2,2-dioxides 3 and 1,1-dioxides 4, suggesting that an intramolecular halogen transfer from the 5-position (sulfide moiety) to the 1- and 2-positions (disulfide moiety) took place in the reactions.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hc.520060117
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