o-Quinone methide as a common intermediate in the pyrolysis of o-hydroxybenzyl alcohol, chroman and 1,4-benzodioxin

Abstract

The product composition in the very low pressure pyrolysis (550–1210 K) of o-hydroxybenzyl alcohol (HBA), 3,4-dihydro-2H-1-benzopyran (chroman), and 1,4-benzodioxin (BD) indicates that o-quinone methide (o-QM) is the common intermediate in each case. At complete conversion of HBA, o-QM was observed as the only product and the mass spectrum of o-QM could be obtained. At higher temperatures (>950 K), o-QM is subsequently converted into benzene and CO. The thermolysis process for chroman starts with cleavage of the phenoxy–carbon bond and proceeds with ethene elimination, yielding o-QM. The high pressure rate parameters for unimolecular decay have been determined to obey k_chroman /s^–1 = 10^15.3 exp (–269/RT). For BD only the cleavage of the phenyl–vinoxy bond has been observed, and after rearrangement and CO elimination o-QM is formed. The Arrhenius equation for the overall rate of disappearance has been found as k_BD /s^–1 = 10^15.6 exp (–310/RT). Ultimately (1100 K) the thermolysis of BD leads to 1 mole of benzene and 2 moles of CO.

References

1. S. M. Shevchenko and A. G. Apushkinskii, Russ. Chem. Rev., 1992, 61, 105.
2. E. Dorrestijn, R. Pugin, M. V. Ciriano Nogales and P. Mulder, J. Org. Chem., 1997, 62, 4804.
3. V. Eck, A. Schweig and H. Vermeer, Tetrahedron Lett., 1978, 27, 2433.
4. (a) P. D. Gardner, R. H. Sarrafizadeh and R. L. Brandon, J. Am. Chem. Soc., 1959, 81, 5515; (b) S. B. Cavitt, R. H. Sarrafizadeh and P. D. Gardner, J. Org. Chem., 1962, 27, 1211; (c) C. L. McIntosh and O. L. Chapman, Chem. Commun., 1996, 771; (d) Y. L. Mao and V. Boekelheide, Proc. Nat. Acad. Sci. USA, 1980, 77, 1732; (e) M. Letulle, P. Guenot and J. L. Ripoll, Tetrahedron Lett., 1991, 32, 2013.
5. O. L. Chapman and C. L. McIntosh, J. Chem. Soc., Chem. Commun., 1971, 383.
6. B. Guan and P. Wan, J. Photochem. Photobiol. A, 1994, 80, 199.
7. (a) I. W. C. E. Arends, R. Louw and P. Mulder, J. Phys. Chem., 1993, 97, 7914; (b) W. van Scheppingen, E. Dorrestijn, I. Arends, P. Mulder and H. G. Korth, J. Phys. Chem. A, 1997, 101, 5404; (c) G. J. Schraa, I. W. C. E. Arends and P. Mulder, J. Chem. Soc., Perkin Trans. 2, 1994, 189; (d) E. Dorrestijn, L. J. J. Laarhoven, I. W. C. E. Arends and P. Mulder, J. Anal. Appl. Pyrolysis, submitted.
8. O. J. Epema, Ph.D. Thesis, Leiden University, 1996.
9. E. Dorrestijn, M. V. Ciriano Nogales, M. Kranenburg and P. Mulder, to be published.
10. J. de Jonge and B. H. Bibo, Recl. Trav. Chim. Pay-Bas, 1955, 74, 1448.
11. W. Tsang and J. P. Cui, J. Am. Chem. Soc., 1990, 112, 1665.
12. M. A. Grela and A. J. Colussi, J. Phys. Chem., 1986, 90, 434.
13. W. G. Mallard, F. Westley, J. T. Herron and R. G. Hampson, NIST Chemical Kinetics Database version 5.0, Gaithersburg, NIST Standard Reference Data, National Institute of Standards and Technology, 1993.
14. M. M. Suryan, S. A. Kafafi and S. E. Stein, J. Am. Chem. Soc., 1989, 111, 1423.
15. S. E. Stein, J. M. Rukkers and R. L. Brown, NIST Structures and Properties Database version 2.0, Gaithersburg, NIST Standard Reference Data, National Institute of Standards and Technology, 1994.
16. J. Berkowitz, G. Barney Ellison and D. Gutman, J. Phys. Chem., 1994, 98, 2744.
17. O. V. Dorofeeva, Thermochim. Acta, 1992, 200, 121.
18. F. G. Bordwell and X. Zhang, J. Am. Chem. Soc., 1994, 116, 973.
19. F. G. Bordwell, T. Gallagher and X. Zhang, J. Am. Chem. Soc., 1991, 114, 3495.
20. D. M. Golden, G. N. Spokes and S. W. Benson, Angew. Chem., Int. Ed. Engl., 1973, 12, 534; D. A. Robaugh and S. E. Stein, Int. J. Chem. Kinet., 1981, 13, 445; M. Rossi and D. M. Golden, Int. J. Chem. Kinet., 1979, 11, 715.
21. R. G. Gilbert and S. C. Smith, Theory of Unimolecular and Recombination Reactions, Blackwell Scientific Publications, Oxford, 1990.
22. J. A. Walker and W. Tsang, J. Phys. Chem., 1990, 94, 3324.
23. G. Farina and G. Zecchi, Synthesis, 1977, 755.
24. M. L. Poutsma, in Free Radicals, ed. J. K. Kochi, Wiley, New York, 1973, vol. 2, p. 211; J. G. Traynham and Y. S. Lee, J. Am. Chem. Soc., 1974, 96, 3590; W. Offerman and F. J. Vögtle, Org. Chem., 1978, 44, 710.
25. I. C. Calder, R. B. Johns and J. M. Desmarchelier, Org. Mass Spectrom., 1970, 4, 121; K. K. Deb, J. E. Bloor and T. C. Cole, Org. Magn. Res., 1970, 2, 431.
26. Density Functional Methods in Chemistry, ed. J. K. Labanowski and J. Andzelm, Springer, New York, 1991; R. G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules, Oxford University Press, Oxford, 1989; T. Ziegler, Chem. Rev., 1991, 91, 651; R. O. Jones and O. Gunnarsson, Rev. Mod. Phys., 1989, 61, 689; J. M. Seminario and P. Politzer, Modern Density Functional Theory: A Tool for Chemistry, Elsevier, Amsterdam, 1995.
27. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Degrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian 94, Revision D.4, Pittsburgh, Gaussian, 1995.
28. A. P. Scott and L. Radom, J. Phys. Chem., 1996, 100, 16 502.