D. Gravel, Christian Leboeuf
Mar 1, 1982
Citations
0
Influential Citations
17
Citations
Journal
Canadian Journal of Chemistry
Abstract
The synthesis from diphenylmethane of 4,4-diphenyl-γ-thiopyran and 4,4-diphenyl-γ-thiopyran-1,1-dioxide is described. Upon direct photolysis at 254 nm the γ-thiopyran derivative undergoes rearrangement to a mixture of 5,6-diphenyl-2-thiabicyclo-[3.1.0]hexene and 2,4-diphenyl-α-thiopyran. The corresponding 1,1-dioxide derivative on the other hand undergoes, upon direct photolysis at 254 nm or sensitized (acetone) photolysis at 350 nm, rearrangement to 6,6-diphenyl-2-thiabicyclo[3.1.0]hexene-2,2-dioxide accompanied by a solvent addition product: 3-methoxy-4,4-diphenyl-2,3-dihydro-γ-thiopyran-1,1-dioxide. The results, along with those observed for 4,4-diphenyl-γ-pyran studied in this series, and other literature results are rationalized in terms of Zimmerman's reacting chromophore simulation using the Mobius–Huckel concept to evaluate competing excited state energies of the isoconjugate chromophores.