Mass Spectrometry of Cyclopentadienylideneketene: Differentiation of Isomeric Ion Structures by Means of Ion/Molecule Reactions
Pascal Gerbaux A C and Curt Wentrup B CA Mass Spectrometry Research Group, Interdisciplinary Center for Mass Spectrometry, University of Mons, UMONS, 23 Place du Parc, B-7000 Mons, Belgium.
B School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, Australia.
C Corresponding authors. Email: wentrup@uq.edu.au; Pascal.Gerbaux@umons.ac.be
Australian Journal of Chemistry 65(12) 1655-1661 https://doi.org/10.1071/CH12327
Submitted: 11 July 2012 Accepted: 16 August 2012 Published: 13 September 2012
Abstract
The nature of the m/z 104 ions formed by loss of CO2 or Ph-O-NCO from the molecular ions of phthalic anhydride, N-phenoxyphthalimide, and N-phenoxyisophthalimide was investigated by means of ion/molecule reactions with acetone. This allows a clear-cut differentiation of the so-obtained ions from the isomeric molecular ions of cyclopentadienylideneketene. The different intrinsic chemical reactivities of ionized cyclopentadienylideneketene and its distonoid isomer towards neutral acetone were investigated on a large-scale hybrid mass spectrometer and confirmed by density functional theory calculations.
References
[1] T. Monsandl, G. Macfarlane, R. Flammang, C. Wentrup, Aust. J. Chem. 2010, 63, 1076.| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXosl2hs7Y%3D&md5=495ea2850becb927364a1119760e818fCAS |
[2] (a) M. Winkler, W. Sander, Aust. J. Chem. 2010, 63, 1013.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXosl2hs7c%3D&md5=e4e1d3156d52e5de108d816038a98f95CAS |
(b) T. Sato, H. Niino, Aust. J. Chem. 2010, 63, 1048.
| Crossref | GoogleScholarGoogle Scholar |
(c) R. F. C. Brown, N. R. Browne, K. J. Coulston, L. B. Danen, F. W. Eastwood, M. J. Irvine, A. D. E. Pullin, Tetrahedron Lett. 1986, 27, 1075.
| Crossref | GoogleScholarGoogle Scholar |
(d) R. F. C. Brown, N. R. Browne, K. J. Coulston, F. W. Eastwood, M. J. Irvine, A. D. E. Pullin, U. E. Wiersum, Aust. J. Chem. 1989, 42, 1321.
| Crossref | GoogleScholarGoogle Scholar |
[3] C. Wentrup, R. Blanch, H. Briehl, G. Gross, J. Am. Chem. Soc. 1988, 110, 1874.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXhtlWmtro%3D&md5=bd6cf6784653a2068ed48c69cdba68bcCAS |
[4] P. Gerbaux, J.-Y. Salpin, G. Bouchoux, R. Flammang, Int. J. Mass Spectrom. 2000, 195–196, 239.
| Crossref | GoogleScholarGoogle Scholar |
[5] S. Hammerum, Mass Spectrom. Rev. 1988, 7, 123.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1MXntF2g&md5=54bbda71f9de73ba01329582b8353edfCAS |
[6] L. A. B. Moraes, M. N. Eberlin, J. Am. Chem. Soc. 1998, 120, 11136.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXms1amu7k%3D&md5=74818691239530e009acd114f2b77523CAS |
[7] (a) R. L. Cotter, C. K. Sauers, J. M. Whelan, J. Org. Chem. 1961, 26, 10., : phthalimides rearrange thermally to isophthalimides, if at all.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF3MXhtVGnsLw%3D&md5=d00109bd69f2e38427653f733eccf58dCAS |
(b) R. T. Alpin, J. H. Jones, Chem. Commun. 1967, 261.: thermal isomerization of N-methylphthalimide to isophthalimide is suggested.
(c) R. M. Srivastava, L. Cottier, G. Descotes, Rapid Commun. Mass Spectrom. 2000, 14, 657.
| Crossref | GoogleScholarGoogle Scholar |
[8] (a) C. M. Anderson, R. N. Warrener, C. S. Barnes, Chem. Commun. 1968, 166., : MS of N-phenylisophthalimide almost indistinguishable from the phthalimide. Suggest the rearrangement is by EI, not thermal.
| Crossref | GoogleScholarGoogle Scholar |
(b) C. Cermak, M. Sebranek, Z. Nyvltova, J. Jirman, Collect. Czech. Chem. Commun. 1991, 56, 809. : MS of N-arylphthalimides and isophthalimides almost indistinguishable.
| Crossref | GoogleScholarGoogle Scholar |
(c) J. L. Cotter, R. A. Dine-Hart, Org. Mass Spectrom. 1968, 1, 915.
| Crossref | GoogleScholarGoogle Scholar |
(d) J. L. Cotter, R. A. Dine-Hart, Chem. Commun. 1966, 809.
| Crossref | GoogleScholarGoogle Scholar |
(e) R. A. W. Johnstone, B. J. Millard, D. S. Millington, Chem. Commun. 1966, 600a.
| Crossref | GoogleScholarGoogle Scholar |
(f) T. W. Bentley, R. A. W. Johnstone, J. Chem. Soc. C 1968, 2354.
| Crossref | GoogleScholarGoogle Scholar |
[9] (a) S. Gronert, Chem. Rev. 2001, 101, 329.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXlt1Kgtw%3D%3D&md5=4d4469821abc5983ea2a7279742948d5CAS |
(b) M. Eberlin, Mass Spectrom. Rev. 1997, 16, 113.
| Crossref | GoogleScholarGoogle Scholar |
(c) P. Gerbaux, R. Flammang, M. T. Nguyen, J.-Y. Salpin, G. Bouchoux, J. Phys. Chem. A 1998, 102, 861.
| Crossref | GoogleScholarGoogle Scholar |
(d) P. Gerbaux, R. Flammang, C. Th. Pedersen, M. W. Wong, J. Phys. Chem. A 1999, 103, 3666.
| Crossref | GoogleScholarGoogle Scholar |
[10] K. M. Stirk, L. K. M. Kiminkinen, H. I. Kenttämaa, Chem. Rev. 1992, 92, 1649.For a review on ion/molecule reactions of distonic radical ions, see:
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XmtFWlu74%3D&md5=8f9b7b672a814934f49e96c66e3d5e08CAS |
[11] E. D. Nelson, S. E. Tichy, H. I. Kenttämaa, J. Chem. Soc., Perkin Trans. 2 1999, 2267.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXmvFyktbg%3D&md5=7b8a6592083b6137ddab98005d541e8fCAS |
[12] R. Flammang, Y. Van Haverbeke, P. Gerbaux, M. T. Nguyen, Tetrahedron Lett. 2001, 42, 669.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXosFWnug%3D%3D&md5=d0aea3863f64736aa2d06e3670589f73CAS |
[13] P. Gerbaux, L. Lamote, Y. Van Haverbeke, R. Flammang, J. Brown, Eur. J. Mass Spectrom. (Chichester, Eng.) 2012, 18, 93.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xpt1ersbk%3D&md5=dc2187cacbe95a169ac0e3fefa503b5dCAS |
[14] L. Trupia, N. Dechamps, R. Flammang, G. Bouchoux, M. T. Nguyen, P. Gerbaux, J. Am. Soc. Mass Spectrom. 2008, 19, 126.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXosFKltA%3D%3D&md5=69c769aab03f67ed29a5dafbbd3a5c4eCAS |
[15] D. M. Tomazela, A. A. Sabino, R. Sparrapan, F. C. Gozzo, M. N. Eberlin, J. Am. Soc. Mass Spectrom. 2006, 17, 1014.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XmsVyjt7s%3D&md5=5e43ee6a200360c1e0d67c436f04b2c1CAS |
[16] E. D. Nelson, R. Li, H. E. Kenttämaa, Int. J. Mass Spectrom. 1999, 91, 185.
[17] For the mass spectrum of dimethylphthalide, see NIST database at: http://webbook.nist.gov/ (accessed 4 July 2012).
[18] P. Gerbaux, Y. Van Haverbeke, R. Flammang, J. Mass Spectrom. 1997, 32, 1170.
| Crossref | GoogleScholarGoogle Scholar |
[19] J. Brown, R. Flammang, Y. Govaert, M. Plisnier, C. Wentrup, Y. Van Haverbeke, Rapid Commun. Mass Spectrom. 1992, 6, 249.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XitlCqtro%3D&md5=c36e74ff7aae85171439cf65ea77fc59CAS |
[20] R. J. Armstrong, R. F. C. Brown, F. W. Eastwood, M. E. Romyn, Aust. J. Chem. 1979, 32, 1767.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3cXnsFGlsg%3D%3D&md5=f76ebd42b63dd3558026109aeb466219CAS |
[21] J. I. G. Cadogan, A. G. Rowley, Synth. Commun. 1977, 7, 365.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1cXmsVKj&md5=5f7f58d94944bebafb3b0bcf604d6273CAS |
[22] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuserai, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, B. B. Liu, A. Liashenko, P. Piskorz, A. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, M. W. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Reploge, J. A. Pople, GaussianW 98 1998 (Gaussian, Inc.: Pittsburg, PA).