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Synthesis and Conformational Properties of 3,8-Phosphonanedione 1-Oxides

Publication ,  Journal Article
Quin, LD; Middlemas, ED; Rao, NS; Miller, RW; McPhail, AT
Published in: Journal of the American Chemical Society
January 1, 1982

Ozonolysis at −78 °C of 3-phospholene derivatives with cyclohexane or substituted cyclohexanes fused at the double bond provides a useful route to derivatives of the 3,8-phosphonanedione 1-oxide system. Synthesized were the 1-methyl, 1-phenyl, 1-hydroxy, 1-phenyl-cis-5,6-dimethyl, 1-phenyl-trans-5,6-dibromo, and 1-phenyl-5,6-epoxy derivatives. Opening of the 9,10 bond of a phenanthrene fused to a 3-phospholene provided a dibenzo[d,f]phosphonanedione derivative. 1-Methyl-3,8-phosphonanedione 1-oxide, shown by X-ray analysis to exist in a twist chair-chair form in the solid state, undergoes rapid interconversion of conformers at room temperature, giving an averaged 13C NMR spectrum. The interconversion is halted at −97 °C, where signals for two conformers are obtained (Tc = −84 °C, approximate ΔG‡ = 9.6 kcal/mol). 1-Phenyl-5,6-dibromo-3,8-phosphonanedione 1-oxide, which X-ray analysis also showed to be in a twist chair-chair form in the solid state, however, showed nonequivalence of comparable ring carbons, implying the existence of a strongly biased equilibrium or a high barrier to ring inversion. The dibenzo[d,f]phosphonanedione derivative has marked rigidity, and the 13C NMR spectrum reveals that comparable ring carbons are non-equivalent at room-temperature. The other phosphonanedione derivatives gave 13C NMR spectra showing equivalence of comparable ring carbons, through either conformational interconversion or adoption of a symmetrical conformation. © 1982, American Chemical Society. All rights reserved.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

January 1, 1982

Volume

104

Issue

7

Start / End Page

1893 / 1900

Related Subject Headings

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

Citation

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Quin, L. D., Middlemas, E. D., Rao, N. S., Miller, R. W., & McPhail, A. T. (1982). Synthesis and Conformational Properties of 3,8-Phosphonanedione 1-Oxides. Journal of the American Chemical Society, 104(7), 1893–1900. https://doi.org/10.1021/ja00371a018
Quin, L. D., E. D. Middlemas, N. S. Rao, R. W. Miller, and A. T. McPhail. “Synthesis and Conformational Properties of 3,8-Phosphonanedione 1-Oxides.” Journal of the American Chemical Society 104, no. 7 (January 1, 1982): 1893–1900. https://doi.org/10.1021/ja00371a018.
Quin LD, Middlemas ED, Rao NS, Miller RW, McPhail AT. Synthesis and Conformational Properties of 3,8-Phosphonanedione 1-Oxides. Journal of the American Chemical Society. 1982 Jan 1;104(7):1893–900.
Quin, L. D., et al. “Synthesis and Conformational Properties of 3,8-Phosphonanedione 1-Oxides.” Journal of the American Chemical Society, vol. 104, no. 7, Jan. 1982, pp. 1893–900. Scopus, doi:10.1021/ja00371a018.
Quin LD, Middlemas ED, Rao NS, Miller RW, McPhail AT. Synthesis and Conformational Properties of 3,8-Phosphonanedione 1-Oxides. Journal of the American Chemical Society. 1982 Jan 1;104(7):1893–1900.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

January 1, 1982

Volume

104

Issue

7

Start / End Page

1893 / 1900

Related Subject Headings

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