Dynamic Stereochemistry—a Comparator for Electron Impact and Pyrolytic Elimination of Acetic Acid from Acetates

Journal of the American Chemical Society

Volumn 92, Issue 11, 1970, Pages 3491-3492

  Green, Mark M ^a   Moldowan, J Michael ^a   Hart, David J ^a   Krakower, Jeffrey M ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542616568     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00714a057     Document Type: Article

References (12)

1. M. M. Green, J. Amer. Chem. Soc., 90, 3872 (1968).
2. K. Mislow and M. Raban, Top. Stereochem., 1, 1 (1967).
3. C. H. DePuy and R. W. King, Chem. Rev., 60, 431 (1960).
4. P. S. Skell and W. L. Hall, J. Amer. Chem. Soc., 86, 1557 (1964).
5. D. Y. Curtin and D. B. Kellom, J. Amer. Chem. Soc., 75, 6011 (1953).
6. Earlier work on acetates has demonstrated abstraction from various β positions as well as some 1, 3 loss of acetic acid. See: W. Benz and K. Biemann, J. Amer. Chem. Soc., 86, 2375 (1964);
7. W. S. Briggs and C. Djerassi, J. Org. Chem., 33, 1612 (1968).
8. Determined under conditions identical with those for the data in Table I. The compounds were prepared by Grignard reaction of the appropriately deuterated benzyl chloride and benzaldehyde. Mono- deuteriobenzaldehyde was prepared as reported previously: D. See-bach, B. W. Erickson, and G. Singh, J. Org. Chem., 31, 4303 (1966).
9. The invariance of the results on change of beam energy from 70 eV to near threshold (Tables I and II) does not alter this argument since the ions produced near threshold must have low internal energies. The lack of dependence of competitive eliminations on beam energy has precedence in chloride and acetates. See: A. M. Duffield, S. D. Sample, and C. Djerassi, Chem. Commun., 193 (1966); Briggs and Djerassi, ref 8 herein.
10. This follows from the quasi-equilibrium theory and the derived kinetic expression. See: R. G. Cooks, I. Howe, and D. H. Williams, Org. Mass Sped., 2, 137 (1969), and numerous references therein.
11. d leads to trans- or cis-stilbene or even an ion with a stilbene structure at all. See P. F. Donaghue, P. Y. White, J. H. Bowie, B. D. Roney, and H. J. Rodda, Org. Mass Spectrom., 2, 1061 (1969).
12. Measured by varying the accelerating voltages. See: M. Barber and R. M. Elliott, Abstracts of Papers of 12th Annual Conference on Mass Spectrometry, ASTM E-14, Montreal, 1964, p 150.