Sulfurization of thiones: 2,2,4,4-tetramethyl-3-thioxocyclobutanone

By treatment with elemental sulfur and a catalytic amount of sodium thiophenolate in acetone at room temp., the title compound 9 is converted to the bis-spiro derivatives of 1,2,4,5-tetrathiane, 13, and 1,2,3,5,6-pentathiepane, 14. The initial attack by the phenyl oligosulfide anion takes place at t...

Full description

Saved in:
Bibliographic Details
Published inLiebigs Annalen no. 7; pp. 1517 - 1523
Main Authors Huisgen, R, Rapp, J, Huber, H
Format Journal Article
LanguageEnglish
Published DEERFIELD BEACH Wiley 01.07.1997
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
CYCLOHEPTANE
CYCLOADDITIONS
sulfur heterocycles
thioketones
sulfurization
DISTONIC RADICAL CATIONS
SUPERDIPOLAROPHILES
conformational analysis
sulfur ylides
Online AccessGet more information

Cover

More Information
Summary:By treatment with elemental sulfur and a catalytic amount of sodium thiophenolate in acetone at room temp., the title compound 9 is converted to the bis-spiro derivatives of 1,2,4,5-tetrathiane, 13, and 1,2,3,5,6-pentathiepane, 14. The initial attack by the phenyl oligosulfide anion takes place at the C-atom of the thiocarbonyl group. There is C-13 NMR evidence for the twist conformation 15 of the tetrathiane ring; dynamic H-1 NMR led to Delta G(not equal) = 15.9 +/- 1.0 kcal mol(-1) for the enantiomerization. For the pentathiepane 14, twelve coalescence phenomena in the H-1 and C-13 NMR spectra point to Delta G(not equal) = 13.4 +/- 0.2 kcal mol(-1); the process is interpreted as a stereomutation on the pseudorotation circuit for twist-chair and chair. The MS of 13 reveals a diversity of fragmentation patterns with several ''thiologous'' sequences. By prolonged treatment with the thiophenolate catalyst, 13 and 14 are converted to a gamma-butyfodithiolactone 36 in a Baeyer-Villiger type reaction.
ISSN:0947-3440
DOI:10.1002/jlac.199719970730