Flowing afterglow study of the gas phase nucleophilic reactions of some formyl, acetyl and cyclic esters

Abstract

A variety of nucleophiles have been investigated for their reactions with formyl and acetyl esters in the gas phase in our flowing afterglow. The reactions that are permitted in the gas phase are more varied than those seen in the condensed phase. The rates of reactions of methyl and ethyl esters as well as various lactones have been undertaken with various nucleophiles: H₂N^–, HO^–, CH₃O^–, NCCH₂^–, F^–, CH₃C([double bond, length half m-dash]O)CH₂^–, CH₃S^– and O₂NCH₂^– . For example, the reaction rate of NCCH₂^– + HCO₂CH₂CH₃ has been found to be (1.3 ± 0.2) × 10^–10 cm³ molecule^–1 s^–1 and the only product is HC(O^–)[double bond, length half m-dash]CHCN which results from nucleophilic acyl substitution (B_AC2) followed by a proton transfer within the ion–molecule complex. Other reaction mechanisms that have been observed include β-elimination (E2), bimolecular nucleophilic substitution at the alkyl group (B_AL2), and the Riveros reaction (elimination of CO). A mechanism for the F^– + HCO₂CH₃ reaction has been determined at the B3LYP/6-31+G(d) level. Most notably, channels were determined computationally (B_AL2 and Riveros), and these channels are also observed experimentally. Furthermore, the B_AC2 pathway which proceeds via nucleophilic attack on the carbonyl group also leads to the Riveros products, F^–(CH₃OH) and CO.

References

1. (a) The Chemistry of the Carbonyl Group, S. Patai, Ed., Interscience, New York, 1966; (b) J. Falbe, in Methoden der Organische Chemie (Houben-Weyl), G. Thieme Verlag, Stuttgart, 1983, Vol. E3; E. Muller, in Methoden der Organische Chemie (Houben-Weyl), G. Thieme Verlag, Stuttgart, 1973, Vol. 7/7; (c) M. L. Bender, J. Am. Chem. Soc., 1951, 73, 1626; (d) M. L. Bender, Chem. Rev., 1960, 60, 53; (e) W. P. Jencks, Prog. Phys. Org. Chem., 1964, 2, 63; (f) A. J. Parker, Chem. Rev., 1969, 69, 1; (g) E. H. Cordes and H. G. Bull, Chem. Rev., 1974, 74, 581; (h) W. P. Jencks, Acc. Chem. Res., 1980, 13, 161.
2. (a) K. B. Wiberg, C. M. Hadad, P. R. Rablen and J. Cioslowski, J. Am. Chem. Soc., 1992, 114, 8644; (b) K. B. Wiberg and P. R. Rablen, J. Am. Chem. Soc., 1995, 117, 2201; (c) C. M. Hadad, P. R. Rablen and K. B. Wiberg, J. Org. Chem., 1998, 63, 8668.
3. (a) G. D. Paderas, P. Metivier and W. L. Jorgensen, J. Org. Chem., 1991, 56, 4718; (b) R. A. J. O'Hair, G. E. Davico, J. Hacaloglu, T. T. Dang, C. H. DePuy and V. M. Bierbaum, J. Am. Chem. Soc., 1994, 116, 3609; (c) S. T. Arnold, R. A. Morris and A. A. Viggiano, J. Chem Phys., 1995, 103, 9242; (d) J. V. Seeley, R. A. Morris and A. A. Viggiano, J. Phys. Chem., 1996, 100, 15821; (e) S. T. Arnold, R. A. Morris, A. A. Viggiano and M. A. Johnson, J. Phys. Chem., 1996, 100, 2900.
4. (a) O. I. Asubiojo, L. K. Blair and J. I. Brauman, J. Am. Chem. Soc., 1975, 97, 6685; (b) O. I. Asubiojo and J. I. Brauman, J. Am. Chem. Soc., 1979, 101, 3715; (c) J. L. Wilbur and J. I. Brauman, J. Am. Chem. Soc., 1994, 116, 5839; (d) J. L. Wilbur and J. I. Brauman, J. Am. Chem. Soc., 1994, 116, 9216.
5. (a) J. M. Riveros, S. M. Jose and K. Takashima, Adv. Phys. Org. Chem., 1985, 21, 197; (b) J. M. Riveros, J. Chem. Soc., Chem. Commun., 1990, 773.
6. (a) J. D. Baldeschweiler and S. S. Woodgate, Acc. Chem. Res., 1971, 4, 114; (b) M. Comisarow, Can. J. Chem., 1977, 55, 171; (c) C. H. DePuy, J. J. Grabowski, V. M. Bierbaum, S. Ingemann and N. M. M. Nibbering, J. Am. Chem. Soc., 1985, 107, 1093; (d) N. M. M. Nibbering, Acc. Chem. Res., 1990, 23, 279; (e) C. F. Bernasconi, M. W. Stronach, C. H. DePuy and S. Gronert, J. Am. Chem. Soc., 1990, 112, 9044.
7. (a) E. E. Ferguson, F. C. Fehsenfeld and A. L. Schmeltekopf, Adv. At. Mol. Phys., 1969, 5, 1; (b) C. H. DePuy and V. M. Bierbaum, Acc. Chem. Res., 1981, 14, 146.
8. (a) N. G. Adams and D. Smith, Int. J. Mass Spectrom. Ion Phys., 1976, 21, 349; (b) J. M. Van Doren, S. E. Barlow, C. H. DePuy and V. M. Bierbaum, Int. J. Mass Spectrom. Ion Proc., 1987, 81, 85.
9. S. T. Graul and R. R. Squires, J. Am. Chem. Soc., 1990, 112, 2517.
10. M. McFarland, D. L. Albritton, F. C. Fehsenfeld, E. E. Ferguson and A. L. Schmeltekopf, J. Chem. Phys., 1973, 59, 6610.
11. (a) D. B. Dunkin, F. C. Fehsenfeld, A. L. Schmeltekopf and E. E. Ferguson, J. Chem. Phys., 1968, 49, 1365; (b) S. R. Kass, H. Guo and G. D. Dahlke, J. Am. Soc. Mass Spectrom., 1990, 1, 366; (c) B. T. Frink, PhD Thesis, The Ohio State University, 1999.
12. S. T. Graul and R. R. Squires, Mass Spectrom. Rev., 1988, 7, 263.
13. (a) J. F. G. Faigle, P. C. Isolani and J. M. Riveros, J. Am. Chem. Soc., 1976, 98, 2049; (b) K. Takashima and J. M. Riveros, J. Am. Chem. Soc., 1978, 100, 6128.
14. J. E. Bartmess, R. L. Hays and G. Caldwell, J. Am. Chem. Soc., 1981, 103, 1338.
15. (a) J. D. Madura and W. L. Jorgensen, J. Am. Chem. Soc., 1986, 108, 2517; (b) J. F. Blake and W. L. Jorgensen, J. Am. Chem. Soc., 1987, 109, 3856.
16. R. E. Rosenberg, J. Am. Chem. Soc., 1995, 117, 10358.
17. M. Zhong and J. I. Brauman, J. Am. Chem. Soc., 1999, 121, 2508.
18. I. Lee, D. Lee and C. K. Kim, J. Phys. Chem. A, 1997, 101, 879.
19. J. J. Grabowski and L. Zhang, J. Am. Chem. Soc., 1989, 111, 1193.
20. GAUSSIAN94, Revision D.3: 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. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1995.
21. (a) T. Ziegler, Chem. Rev., 1991, 91, 651; (b) Density Functional Methods in Chemistry, J. Labanowski and J. Andzelm, Eds., Springer-Verlag, New York, 1991; (c) R. G. Parr and W. Yang, Density-Functional Theory of Atoms and Molecules, Oxford University Press, New York, 1989; (d) A. D. Becke, J. Chem. Phys., 1993, 98, 5648; (e) C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785; (f) P. J. Stephens, F. J. Devlin and M. J. Frisch, J. Phys. Chem., 1994, 98, 11623; (g) B. G. Johnson, P. M. W. Gill and J. A. Pople, J. Chem. Phys., 1993, 98, 5612; (h) W. Hehre, L. Radom, P. v. R. Schleyer and J. A. Pople, Ab initio Molecular Orbital Theory, John Wiley & Sons, New York, 1986.
22. (a) C. Gonzalez and H. B. Schlegel, J. Chem. Phys., 1989, 90, 2154; (b) C. Gonzalez and H. B. Schlegel, J. Phys. Chem., 1990, 94, 5523.
23. T. Su and M. T. Bowers, Int. J. Mass Spectrom. Ion Phys., 1973, 12, 347.
24. C. H. DePuy, S. Gronert, A. Mullin and V. M. Bierbaum, J. Am. Chem. Soc., 1990, 112, 8650 and references therein.
25. (a) C. H. DePuy and V. M. Bierbaum, J. Am. Chem. Soc., 1981, 103, 5034; (b) C. H. DePuy, E. C. Beedle and V. M. Bierbaum, J. Am. Chem. Soc., 1982, 104, 6483; (c) V. M. Bierbaum, J. Filley, C. H. DePuy, M. F. Jarrold and M. T. Bowers, J. Am. Chem. Soc., 1985, 107, 2818; (d) S. Gronert, C. H. DePuy and V. M. Bierbaum, J. Am. Chem. Soc., 1991, 113, 4009.
26. B. T. Frink, C. M. Geise and C. M. Hadad, unpublished results.
27. S. M. José and J. M. Riveros, Nouv. J. Chim., 1977, 1, 113.
28. J. Mulzer and T. Kerkmann, J. Am. Chem. Soc., 1980, 102, 3620.