Conformational properties of the N-tosylsulfilimines of dibenzothiophene, phenoxathiin, and thianthrene

Robert F X Klein, Paris D N Svoronos, Vaclav Horak, Geoffrey B. Jameson, Tibor Koritsánszky, A. Kálmán

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Abstract

The X-ray and MNDO-derived structures and aromatic solvent induced shifts (ASIS) of the N-(p-toluene-sulfonyl)sulfilimines of dibenzothiophene (1e), phenoxathiin (2e), and thianthrene (3e) are reported. In 1e, the dibenzothiophene ring system remains essentially planar, with the phenyl rings inclined only 3.7°. The sulfilimine substituent is pseudoaxial (pa′). In 2e, the phenoxathiin ring system is gently folded in a "boat" conformation with the phenyl rings inclined 16.9°; the Cremer and Pople puckering factors are Q = 0.267 (3) Å, φ = 179.6 (6)°, and θ = 104.5 (6)°. The substituent is pa′. In 3e, the thianthrene ring system is sharply folded in a "boat" conformation with the phenyl rings inclined 52.7° (Q = 0.842 (6) Å, φ = 179.9 (4)°, and θ = 92.9 (4)°). The substituent is pseudoequatorial (pe′). In each structure, the substituent is asymmetrically oriented with respect to the vertical plane bisecting the central ring. ASIS analysis of the peri hydrogens of 1e-3e establishes that the solid state substituent orientations of all three derivatives are maintained in solution (1e, δCDCl3 - δC6D6 = +0.46 ppm; 2e, +0.18 ppm; 3e, -0.13 ppm). MNDO calculated ΔHf of the respective pa′ vs pe′ conformers suggest that the stereochemistry observed in the crystal structures may be thermodynamically favored (ΔΔHf: 1e, (spontaneous convergence to pa′); 2e, 0.66 kcal mol-1 favoring pa′; 3e, 0.76 kcal mol-1 favoring pe′).

Original languageEnglish
Pages (from-to)3259-3263
Number of pages5
JournalJournal of Organic Chemistry
Volume56
Issue number10
Publication statusPublished - 1991

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Boats
Conformations
Stereochemistry
Toluene
Hydrogen
Crystal structure
Derivatives
X rays
dibenzothiophene
sulfilimine
phenoxathiin
thianthrene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Klein, R. F. X., Svoronos, P. D. N., Horak, V., Jameson, G. B., Koritsánszky, T., & Kálmán, A. (1991). Conformational properties of the N-tosylsulfilimines of dibenzothiophene, phenoxathiin, and thianthrene. Journal of Organic Chemistry, 56(10), 3259-3263.

Conformational properties of the N-tosylsulfilimines of dibenzothiophene, phenoxathiin, and thianthrene. / Klein, Robert F X; Svoronos, Paris D N; Horak, Vaclav; Jameson, Geoffrey B.; Koritsánszky, Tibor; Kálmán, A.

In: Journal of Organic Chemistry, Vol. 56, No. 10, 1991, p. 3259-3263.

Research output: Contribution to journalArticle

Klein, RFX, Svoronos, PDN, Horak, V, Jameson, GB, Koritsánszky, T & Kálmán, A 1991, 'Conformational properties of the N-tosylsulfilimines of dibenzothiophene, phenoxathiin, and thianthrene', Journal of Organic Chemistry, vol. 56, no. 10, pp. 3259-3263.
Klein, Robert F X ; Svoronos, Paris D N ; Horak, Vaclav ; Jameson, Geoffrey B. ; Koritsánszky, Tibor ; Kálmán, A. / Conformational properties of the N-tosylsulfilimines of dibenzothiophene, phenoxathiin, and thianthrene. In: Journal of Organic Chemistry. 1991 ; Vol. 56, No. 10. pp. 3259-3263.
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abstract = "The X-ray and MNDO-derived structures and aromatic solvent induced shifts (ASIS) of the N-(p-toluene-sulfonyl)sulfilimines of dibenzothiophene (1e), phenoxathiin (2e), and thianthrene (3e) are reported. In 1e, the dibenzothiophene ring system remains essentially planar, with the phenyl rings inclined only 3.7°. The sulfilimine substituent is pseudoaxial (pa′). In 2e, the phenoxathiin ring system is gently folded in a {"}boat{"} conformation with the phenyl rings inclined 16.9°; the Cremer and Pople puckering factors are Q = 0.267 (3) {\AA}, φ = 179.6 (6)°, and θ = 104.5 (6)°. The substituent is pa′. In 3e, the thianthrene ring system is sharply folded in a {"}boat{"} conformation with the phenyl rings inclined 52.7° (Q = 0.842 (6) {\AA}, φ = 179.9 (4)°, and θ = 92.9 (4)°). The substituent is pseudoequatorial (pe′). In each structure, the substituent is asymmetrically oriented with respect to the vertical plane bisecting the central ring. ASIS analysis of the peri hydrogens of 1e-3e establishes that the solid state substituent orientations of all three derivatives are maintained in solution (1e, δCDCl3 - δC6D6 = +0.46 ppm; 2e, +0.18 ppm; 3e, -0.13 ppm). MNDO calculated ΔHf of the respective pa′ vs pe′ conformers suggest that the stereochemistry observed in the crystal structures may be thermodynamically favored (ΔΔHf: 1e, (spontaneous convergence to pa′); 2e, 0.66 kcal mol-1 favoring pa′; 3e, 0.76 kcal mol-1 favoring pe′).",
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AB - The X-ray and MNDO-derived structures and aromatic solvent induced shifts (ASIS) of the N-(p-toluene-sulfonyl)sulfilimines of dibenzothiophene (1e), phenoxathiin (2e), and thianthrene (3e) are reported. In 1e, the dibenzothiophene ring system remains essentially planar, with the phenyl rings inclined only 3.7°. The sulfilimine substituent is pseudoaxial (pa′). In 2e, the phenoxathiin ring system is gently folded in a "boat" conformation with the phenyl rings inclined 16.9°; the Cremer and Pople puckering factors are Q = 0.267 (3) Å, φ = 179.6 (6)°, and θ = 104.5 (6)°. The substituent is pa′. In 3e, the thianthrene ring system is sharply folded in a "boat" conformation with the phenyl rings inclined 52.7° (Q = 0.842 (6) Å, φ = 179.9 (4)°, and θ = 92.9 (4)°). The substituent is pseudoequatorial (pe′). In each structure, the substituent is asymmetrically oriented with respect to the vertical plane bisecting the central ring. ASIS analysis of the peri hydrogens of 1e-3e establishes that the solid state substituent orientations of all three derivatives are maintained in solution (1e, δCDCl3 - δC6D6 = +0.46 ppm; 2e, +0.18 ppm; 3e, -0.13 ppm). MNDO calculated ΔHf of the respective pa′ vs pe′ conformers suggest that the stereochemistry observed in the crystal structures may be thermodynamically favored (ΔΔHf: 1e, (spontaneous convergence to pa′); 2e, 0.66 kcal mol-1 favoring pa′; 3e, 0.76 kcal mol-1 favoring pe′).

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