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Original Articles

CONFORMATIONAL PREFERENCES OF MONOCYCLIC PENTAOXYPHOSPHORANES VARYING IN RING SIZE

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Pages 23-50 | Received 06 Nov 1989, Published online: 24 Sep 2006

References

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  • This work represents in part a portion of the Ph.D. Thesis of Sarah D. Burton Amherst , MA : University of Massachusetts .
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  • The extra intensity of the signal at ∼2.09 ppm in the spectrum at –70 °C is due to a multiplet for toluenc-d 8. This is apparent in Figure 9 where the methyl signals undergo small shifts at higher temperatures (cf. at –30 °C) and the peak at 2.09 ppm splits into separate signals, one for CH3 protons and one for toulene-d 8. The latter is present due to incomplete substitution, C6D5CD2H.
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  • . For 2, these values are for the configuration having the lowest R w
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  • The CH2OH and OH groups in the diol used to synthesize 7 were cis to each other
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  • The van der Waals' sum for an aromatic ring and a methyl group is 1.7 + 2.0 = 3.7 Å. The van der Waals' sum for two methyl groups is 2.0 + 2.0 = 4.0.
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  • Buono , G. and Linas , J. R. 1981 . J. Am. Chem. Soc. , 103 : 4532 See also Errors in ΔG 2 using this method are indicated to be less than ± 0.5 kcal/mol when compared to line-shape analysis. See ref 36 in the paper by Buono and Llinas cited here
  • Litvinov , I. A. , Yufit , D. S. , Struchkov , Y. T. , Arbuzov , B. A. , Gurrarii , L. I. and Mukmenev , E. T. 1982 . Dokl. Akad. Nauk SSSR , 265 : 884
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  • Reference 18 discusses NMR behavior of F and F, depicted in the Introduction, and concludes that steric inhibition of pseudorotation exists due to the presence of the ring tert-butyl groups. Howver, activation energies for E (R = t-Bu) of 14.6 kcal/mol and for F (R = R' = CH2CF3) of 15.4 and (R = CH2CF3, R' = Et) 15.7 kcal/mol refer to ground-state TBP's with diequatorial rings which are postulated to exchange via a–e sites.
  • Yu , J. H. and Bentrude , W. G. 1988 . J. Am. Chem. Soc. , 110 : 7897
  • 1989 . Tetrahedron Lett. , 30 : 2195 Ibid.
  • Holmes , R. R. , Swamy Kumara , K. C. , Holmes , J. M. and Day , R. O. submitted for publication

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