Abstract
Ion-molecule reactions of the mass-selected distonic radical cation +CH2-O-CH ·2 (1) with several heterocyclic compounds have been investigated by multiple stage mass spectro- metric experiments performed in a pentaquadrupole mass spectrometer. Reactions with pyridine, 2-, 3-, and 4-ethyl, 2-methoxy, and 2-n-propyl pyridine occur mainly by transfer of CH +·2 to the nitrogen, which yields distonic N-methylene-pyridinium radical cations. The MS3 spectra of these products display very characteristic collision-induced dissociation chemistry, which is greatly affected by the position of the substituent in the pyridine ring. Ortho isomers undergo a δ-cleavage cyclization process induced by the free-radical character of the N-methylene group that yields bicyclic pyridinium cations. On the other hand, extensive CH +·2 transfer followed by rapid hydrogen atom loss, that is, a net CH+ transfer, occurs not to the heteroatoms, but to the aromatic ring of furan, thiophene, pyrrole, and N-methyl pyrrole. The reaction proceeds through five- to six-membered ring expansion, which yields the pyrilium, thiapyrilium, N-protonated, and N-methylated pyridine cations, respectively, as indicated by MS3 scans. Ion 1 fails to transfer CH +·2 to tetrahydrofuran, whereas a new α-distonic sulfur ion is formed in reactions with tetrahydrothiophene. Unstable N-methylene distonic ions, likely formed by transfer of CH +·2 to the nitrogen of piperidine and pyrrolidine, undergo rapid fragmentation by loss of the α-NH hydrogen to yield closed-shell immonium cations. The most thermodynamically favorable products are formed in these reactions, as estimated by ab initio calculations at the MP2/6-31G(d,p)//6-31G(d,p) + ZPE level of theory.
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Yates, B. F.; Bouma, W. J.; Radom, L. J. Am. Chem. Soc. 1984, 106, 5805.
Yates, B. F.; Bouma, W. J. Radom, L. Tetrahedron 1986, 42, 6225.
Hammerum, S. Mass Spectrom. Rev. 1988, 7, 123.
Bouchoux, G. Mass Spectrom. Rev. 1988, 7, 203.
Stirk, K. M.; Kiminkinen, M.; Kenttämaa, H. I. Chem. Rev. 1992, 92, 1649.
Kenttämaa, H. I. Org. Mass Spectrom., in press;
Bouma, W. J.; MacLeod, J. K.; Radom, L. J. Am. Chem. Soc. 1980, 102, 2246.
Terlouw, J. K.; Heerma, W.; Dijkstra, G. Org. Mass Spectrom. 1981, 16, 326.
Bouma, W. J.; Nobes, R. H. Radom, L. J. Am. Chem. Soc. 1983, 105, 1743.
Radom, L.; Bouma, W. J.; Nobes, R. H.; Yates, B. F. Pure Appl. Chem. 1984, 56, 1831.
Yates, B. F.; Bouma, W. J.; Radom, L. J. Am. Chem. Soc. 1984, 106, 5805.
Yates, B. F.; Bouma, W. J.; Radom, L. Tetrahedron 1986, 22, 6225.
Bouchoux, G. Mass Spectrom. Rev. 1988, 7, 203.
Bush, K. L.; Glish, G. L.; McLuckey, S. A. Mass Spectrometry / Mass Spectrometry: Techniques and Applications of Tandem Mass Spectrometry; VHC Publishers; New York 1989.
Staley, R. H.; Cordeman, R. R.; Foster, M. S.; Beauchamp, J. L. J. Am. Chem. Soc. 1974, 96, 1260.
Corderman, R. R.; Lebreton, P. R.; Buttrill, S. E.; Williamson, A. D.; Beauchamp, J. L. J. Chem. Phys. 1976, 65, 4929.
Bouma, W. J. ; MacLeod, J. K. ; Radom, L. J. Chem. Soc. Chem. Commun. 1978, 724
Bouma, W. J.; MacLeod, J. K.; Radom L. Adv. Mass. Spectrom. 1979, 8A, 178.
de Koster C. G.; van Houte J. J.; Shadid, J. B., van Thuijl J. Rapid Commun. Mass Spectrom. 1988, 2, 97.
de Koster, C. G.; van Houte, J. J.; van Thuijl, J. Int. J. Mass Spectrom. Ion Processes 1990, 98, 235.
Rusli, R. D.; Schwarz, H. Chem. Ber. 1990, 123, 535.
Stirk, K. M.; Orlowski, J. C.; Leeck, D. T.; Kenttämaa, H. I. J. Am. Chem. Soc. 1992, 114, 8604.
Smith, R. L.; Franklin, R. L.; Stirk, K. M.; Kenttämaa, H. I. J. Am. Chem. Soc. 1993, 115, 10348.
Yu, S. J.; Gross, M. L.; Fountain, K. R. J. Am. Soc. Mass Spectrom. 1993, 4, 117.
Baumann, B. C.; MacLeod, J. K. J. Am. Chem. Soc. 1981, 103, 6223.
Van Velzen, P. N. T.; Van der Hart, W. J. Chem. Phys. Lett. 1981, 83, 56.
Bally, T.; Nitsche, S.; Haselbach, E. Helv. Chim. Acta 1984, 67, 86.
Qin, X. Z.; Snow, L. D.; Williams F. J. Am. Chem. Soc. 1985, 107, 3366.
Bouma, W. J.; Poppinger, D.; Saebo, S.; MacLeod, J. K.; Radom L. Chem. Phys. Lett. 1984, 104, 198.
Mabud, Md. A.; Ast, T.; Verma, S.; Jiang, Y. -X.; Cooks, R. G. J. Am. Chem. Soc. 1987, 109, 7597.
Wesdemiotis, C.; Leyh, B.; Fura, A.; McLafferty, F. W. J. Am. Chem. Soc. 1990, 112, 8655.
Eberlin, M. N. Proceedings of the 41st ASMS Conference on Mass Spectrometry and Allied Topics, 1993; p 975
Gozzo, F. C. ; Eberlin, M. N. , to appear.
Shay, B. J.; Eberlin, M. N.; Cooks, R. G.; Wesdemiotis C. J. Am. Soc. Mass Spectrom. 1992, 3, 518.
Kotiaho, T.; Shay, B. J.; Cooks, R. G.; Eberlin, M. N. J. Am. Chem. Soc. 1993, 115, 1004.
Eberlin, M. N.; Majumdar, T. K.; Cooks R. G. J. Am. Chem. Soc. 1992, 114, 2884.
Eberlin, M. N.; Cooks, R. G. J. Am. Chem. Soc. 1993, 115, 9226.
Eberlin, M. N.; Cooks, R. G. Org. Mass Spectrom. 1993, 28, 679.
Eberlin, M. N.; Kotiaho, T.; Shay, B.; Yang, S. S. Cooks, R. G. J. Am. Chem. Soc. 1994, 116, 2457.
Bortolini, O.; Yang, S. S.; Cooks, R. G. Org. Mass Spectrom. 1993, 28, 1313.
Eberlin, M. N.; Mor-gon, N. H.; Yang, S. S.; Shay, B. J.; Cooks, R. G. J. Am. Soc. Mass Spectrom. 1995, 6, 1.
Schwartz, J. C.; Schey, K. L.; Cooks RG. Int. J. Mass Spectrom. Ion Processes 1990, 101, 1.
Juliano, V. F. ; Kascheres, C. ; Eberlin, M. N. ; Lago, C. L. , to appear.
Hanús, V.; Cermáck, V. Collect. Czech. Chem. Commun. 1959, 24, 1602.
Spilker, R.; Grutzmacher, H. F. Org. Mass Spectrom. 1986, 21, 459.
Gaussian92, revision C, Frisch, M. J. ; Trucks, G. W. ; Head- Gordon, M. ; Gill, P. M. W. ; Wong, M. W. ; Foresman, J. B. ; Johnson, B. G. ; Schlegel, H. B. ; Robb, M. A. ; Replogle, E. S. ; Gomperts, R. ; Andres, J. L. ; Raghavachari, K. ; Binkley, J. S. ; Gonzales, C. ; Martin, R. L. ; Fox, D. J. ; Defrees, D. J. ; Baker, J. ; Stewart, J. J. P. ; Pople, J. A. ; Gaussian, Inc. , Pittsburgh PA, 1992.
Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
Hariharan, P. C.; Pople, J. A. Theor. Chem. Acta 1973, 72, 650.
Gordon, M. S. Chem. Phys. Lett. 1980, 76, 163.
Frisch, M. J.; Pople, J. A.; Binkley, J. S. J. Chem. Phys. 1984, 80, 3265.
Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618.
Xmol, version 1. 3. 1, Minnesota Supercomputer Center, Inc. , Minneapolis, MN, 1993.
Yu, S. J.; Holliman, C. L.; Rempel, D. L.; Gross, M. L. J. Am. Chem. Soc. 1993, 115, 9676.
Cooks, R. G.; McDonald, R. N.; Cranor, P. T.; Petty, H. E.; Wolfe, N. L. J. Org. Chem. 1973, 38, 1114.
Porter, A. E. Adv. Heterocyclic Chem. 1989, 45, 151.
Brumlik, G. C.; Kosak, A. L.; Pitcher R. J. Am. Chem. Soc. 1964, 86, 5360.
Health, T. G.; Allison, J.; Watson, J. T. J. Am. Chem. Soc. 1991, 2, 270.
Smith, R. L.; Chyall, L. J.; Stirk, K. M.; Kenttämaa, H. I. Org. Mass Spectrom. 1993, 28, 1623.
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Gozzo, F.C., Eberlin, M.N. The ionized methylene transfer from the distonic radical cation +CH2-O-CH2 to heterocyclic compounds. A pentaquadrupole mass spectrometric study. J Am Soc Mass Spectrom 6, 554–563 (1995). https://doi.org/10.1016/1044-0305(95)00246-A
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DOI: https://doi.org/10.1016/1044-0305(95)00246-A