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Phosphorus-Containing Cyclohexanes. Nuclear Magnetic Resonance Studies and Conformational Analysis of 1,3,2-Dithiaphosphorinanes

Publication ,  Journal Article
Maryanoff, BE; McPhail, AT; Hutchins, RO
Published in: Journal of the American Chemical Society
January 1, 1981

Proton, carbon-13, and phosphorus-31 NMR spectroscopic data were obtained for a variety of tricoordinate 1,3,2-dithiaphosphorinanes as well as tetracoordinate 2-oxo and 2-thiono derivatives. The tricoordinate compounds adopt a chair conformation in which an axial orientation is strongly preferred for many polar and nonpolar P substituents (CH3, C2H2, C6H6, OCH3, Cl), but an equatorial orientation is strongly preferrd for the P-tert-butyl group. The 2-oxo compounds show a tendency to populate a twist conformation in solution, but the 2-thiono compounds do not. Single-crystal X-ray analyses of 11 derivatives (5,6,7a, 11b, 19, 20a, 22,23,24,28,31) are employed to verify structural assignments and to provide solid-state conformational viewpoints. Three 2-oxo compounds (5, 6, and 28) adopt a twist conformation in the solid state. A chloride- catalyzed chlorine-exchange process in 2-chloro-1,3,2-dithiaphosphorinanes and the stereospecificity of certain 1H and 13C NMR parameters are discussed. A general discussion of twist preferences in 1,3,2-dithiaphosphorinanes, and congeneric systems, is presented. © 1981, American Chemical Society. All rights reserved.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

January 1, 1981

Volume

103

Issue

15

Start / End Page

4432 / 4445

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Maryanoff, B. E., McPhail, A. T., & Hutchins, R. O. (1981). Phosphorus-Containing Cyclohexanes. Nuclear Magnetic Resonance Studies and Conformational Analysis of 1,3,2-Dithiaphosphorinanes. Journal of the American Chemical Society, 103(15), 4432–4445. https://doi.org/10.1021/ja00405a025
Maryanoff, B. E., A. T. McPhail, and R. O. Hutchins. “Phosphorus-Containing Cyclohexanes. Nuclear Magnetic Resonance Studies and Conformational Analysis of 1,3,2-Dithiaphosphorinanes.” Journal of the American Chemical Society 103, no. 15 (January 1, 1981): 4432–45. https://doi.org/10.1021/ja00405a025.
Maryanoff BE, McPhail AT, Hutchins RO. Phosphorus-Containing Cyclohexanes. Nuclear Magnetic Resonance Studies and Conformational Analysis of 1,3,2-Dithiaphosphorinanes. Journal of the American Chemical Society. 1981 Jan 1;103(15):4432–45.
Maryanoff, B. E., et al. “Phosphorus-Containing Cyclohexanes. Nuclear Magnetic Resonance Studies and Conformational Analysis of 1,3,2-Dithiaphosphorinanes.” Journal of the American Chemical Society, vol. 103, no. 15, Jan. 1981, pp. 4432–45. Scopus, doi:10.1021/ja00405a025.
Maryanoff BE, McPhail AT, Hutchins RO. Phosphorus-Containing Cyclohexanes. Nuclear Magnetic Resonance Studies and Conformational Analysis of 1,3,2-Dithiaphosphorinanes. Journal of the American Chemical Society. 1981 Jan 1;103(15):4432–4445.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

January 1, 1981

Volume

103

Issue

15

Start / End Page

4432 / 4445

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences