Abstract
Competitive reactions of dimethyl ether ions are used to probe the steric and substituent effects of substituted phenols and anisoles in a quadrupole ion trap. The relative percentages of protonation and methylene substitution from the reactions of dimethyl ether ions show a correlation with size, location, and number of subsrituents on the aromatic ring. Although gas-phase basicity measurements of the phenols show no discernible correlation with the percentages of competitive reactions, semiempirical calculations show a good correlation between the trend in heats of formation and the trend in methylene substitution percentage. Reactions with deuterated compounds show that the methylene substitution reaction occurs on the ring.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Isaacs, N. S. Physical Organic Chemistry Longman Group: Essex, England, 1987, pp 135–144, 282–329.
Jasinski, J. M.; Brauman, J. I. J. Am. Chem. Soc. 1980, 102, 2906–2913.
Meot-Ner (Mautner), M.; Sieck, L. W. J. Am. Chem. Soc. 1983, 105, 2956–2961.
Meot-Ner (Mautner), M.; Smith, S. C. J. Am. Chem. Soc. 1991, 123, 862–869.
Attinà, M.; Cacace, F. Int. J. Mass Spectrom. Ion Processes 1992, 109, 95–104.
Houriet, R.; Rolli, E. New J. Chem. 1987, 11, 221–224.
Büker, H.; Grützmacher, H. Int. J. Mass Spectrom. Ion Processes 1991, 109, 95–104.
Benezra, S. A.; Bursey, M. M. J. Am. Chem. Soc. 1972, 94, 1024.
Kadentsev, V. I.; Krokhin, A. V.; Chizov, O. S.; Ershov, V. V. Izv. Akad. Nauk SSSR, Ser. Khim. 1978, 11, 2532–2538.
Brodbelt, J. S.; Liou, C.; Donovan, T. Anal. Chem. 1991, 63, 1205–1209.
Wood, K. V.; Burinsky, D. J.; Cameron, D.; Cooks, R. G. J. Org. Chem. 1983, 48, 5236–5242.
Stafford, G. C., Jr.; Kelley, P. E.; Syka, J. E. P.; Reynolds, W. E.; Todd, J. F. J. J. Int. J. Mass Spectrom. Ion Processes 1984, 60, 85–98.
Weber-Brabau, M.; Kelley, P. E.; Syka, J. E. P.; Bradshaw, S. C.; Brodbelt, J. S. Proceedings of the 35th Annual Conference of the American Society for Mass Spectrometry, 1987; p 1114.
Brauman, J. I.; Blair, L. K. J. Am. Chem. Soc. 1970, 92, 5986–5992.
Stewart, J. P. Quantum Chemistry Program Exchange 455, Indiana University, Bloomington, IN.
Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902–3909.
Donovan, T.; Liou, C.; Brodbelt, J. J. Am. Soc. Mass Spectrom. 1992, 3, 39–46.
Hopkins, H., Jr.; Jahagirdar, D.; Moulik, P.; Aue, D.; Webb, H.; Davidson, W.; Pedley, M. J. Am. Chem. Soc. 1984, 106, 4341–4348.
Solomons, T. W. G. Organic Chemistry; John Wiley: New York, 1988; pp 648–663.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Bauerle, G.F., Brodbelt, J.S. Evaluation of steric and substituent effects in phenols by competitive reactions of dimethyl ether ions in a quadrupole ion trap. J Am Soc Mass Spectrom 6, 627–633 (1995). https://doi.org/10.1016/1044-0305(95)00229-7
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/1044-0305(95)00229-7