Research ArticlesNo Access

THEORETICAL STUDIES ON THE FORMATION MECHANISM AND STRUCTURE OF PENTAFULVENONE AND AZAFULVENONE

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Search for more papers by this author

XIU-JUAN JIA

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Search for more papers by this author

YING LIU

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Search for more papers by this author

HAO SUN

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Search for more papers by this author

ZHONG-MIN SU

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Search for more papers by this author

, and

RONG-SHUN WANG

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Search for more papers by this author

https://doi.org/10.1142/S021963360800371XCited by:1 (Source: Crossref)

Abstract

The formation mechanisms of pentafulvenone and azafulvenone were extensively investigated at the B3LYP/6-311++G** level and the potential energy surfaces were drawn out. Ketene pentafulvenone (A) and 3-carbonyl-3H-pyrrole (C) can be formed by eliminating N₂ from the diazo ketone via α elimination reaction and ketene 2-carbonyl-2H-pyrrole (B), 4-carbonyl-4H-imidazole (D), and 2-carbonyl-2H-imidazole (E) were formed by the elimination of water or methanol from pyrrole-2-carboxylic acid (rB) and carboxylate (rD and rE) via β elimination reaction. The structures of these monomers were compared and showed some information about the bond changed characters. The structure investigation indicated that the C=C bond is activated when the nitrogen atom locates in the ortho position of the C=C=O part, and therefore ortho-monomers are more facile to react. The difference of the amount and stability of the corresponding dimers are caused by differing the position and number of nitrogen atom and the variety of the ortho-dimer is complicated. In addition, the infrared spectra of the title species were also analyzed including the vibrational frequencies, IR relative intensities, and vibrational mode assignment.

Keywords:

References

S. Hatakeyamaet al., Bull. Chem. Soc. Jpn. 58, 2157 (1985), DOI: 10.1246/bcsj.58.2157. Crossref, Web of Science, Google Scholar
N. Washidaet al., J. Chem. Phys. 78, 4533 (1983), DOI: 10.1063/1.445346. Crossref, Web of Science, Google Scholar
J. W. Hudgenset al., J. Chem. Phys. 87, 4546 (1987), DOI: 10.1063/1.452867. Crossref, Web of Science, Google Scholar
A. C. Brownet al., Chem. Phys. Lett. 161, 491 (1989), DOI: 10.1016/0009-2614(89)87026-5. Crossref, Web of Science, Google Scholar
M. A. Edwards and J. F. Hershberger, Chem. Phys. 234, 231 (1998), DOI: 10.1016/S0301-0104(98)00174-8. Crossref, Web of Science, Google Scholar
X. M. Panet al., Chem. J. Chin. Univ. 28, 700 (2007). Web of Science, Google Scholar
H. Hou, B. S. Wang and Y. S. Gu, J. Phys. Chem. A 104, 320 (2000), DOI: 10.1021/jp992829+. Crossref, Web of Science, Google Scholar
Z. Y. Zhouet al., J. Mol. Struct. (Theochem) 620, 207 (2003), DOI: 10.1016/S0166-1280(02)00601-2. Crossref, Web of Science, Google Scholar
W. C. Zhang and B. N. Du, Int. J. Quan. Chem. 106, 1076 (2006), DOI: 10.1002/qua.20884. Crossref, Web of Science, Google Scholar
H. Houet al., Chem. J. Chin. Univ. 6, 1131 (2002). Google Scholar
X. L. Chenget al., J. Mol. Struct. (Theochem) 638, 27 (2003), DOI: 10.1016/S0166-1280(03)00416-0. Crossref, Web of Science, Google Scholar
W. C. Zhang and B. N. Du, J. Mol. Struct. (Theochem) 760, 131 (2006), DOI: 10.1016/j.theochem.2005.12.004. Crossref, Web of Science, Google Scholar
Y. Morio, K. Yoshio and A. Toyonobu, Chem. Lett. 1015 (1974). Google Scholar
G. G. Qiaoet al., J. Am. Chem. Soc. 118, 3852 (1996), DOI: 10.1021/ja954226r. Crossref, Web of Science, Google Scholar
G. Gross and C. Wentrup, J. Chem. Soc. Chem. Commun. 360 (1982), DOI: 10.1039/c39820000360. Google Scholar
G. G. Qiao, M. W. Wong and C. Wentrup, J. Org. Chem. 61, 8125 (1996), DOI: 10.1021/jo9609438. Crossref, Web of Science, Google Scholar
A. Maquestiauet al., J. Org. Chem. 51, 306 (1986), DOI: 10.1021/jo00353a006. Crossref, Web of Science, Google Scholar
J. Andraos and C. Wentrup, J. Am. Chem. Soc. 118, 5634 (1996). Web of Science, Google Scholar
Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Zakrzewski V. G., Montgomery J. A. J., Stratmann R. E., Burant J. C., Dapprich S., Millam M. J., Daniels A. D., Kudin K. N., Strain M. C., Farkas O., Tomasi J., Barone V., Cossi M., Cammi R., Mennucci B., Pomelli C., Adamo C., Clifford S., Ochterski J., Petersson G. A., Ayala P. Y., Cui Q., Morokuma K., Malick D. K., Rabuck D. A., Raghavachari K., Foresman J. B., Cioslowski J., Ortiz J. V., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Komaromi I., Gomperts R., Martin R. L., Fox D. J., Keith T., Al-Laham M. A., Peng C. Y., Nanayakkara A., Gonzalez C., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Andres J. L., Gonzalez C., Head-Gordon M., Replogle E. S., Pople J. A., Gaussian 98, Revision A.6; Gaussian, Inc., Pittsburgh, PA, 1998 . Google Scholar
Y. Liuet al., Theor. Chem. Acc. 118, 869 (2007), DOI: 10.1007/s00214-007-0370-y. Crossref, Web of Science, Google Scholar
M. T. Nguyenet al., J. Am. Chem. Soc. 114, 4387 (1992), DOI: 10.1021/ja00037a054. Crossref, Web of Science, Google Scholar
M. T. Nguyen, M. R. Hajnal and L. G. Vanquickenborne, J. Chem. Soc. Perkin Trans. 2 169, 169 (1994). Google Scholar
N. Akaiet al., J. Photochem. Photobiol. A Chem. 146, 49 (2001), DOI: 10.1016/S1010-6030(01)00555-X. Crossref, Web of Science, Google Scholar
M. S. Bairdet al., J. Am. Chem. Soc. 103, 5190 (1981), DOI: 10.1021/ja00407a040. Crossref, Web of Science, Google Scholar