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Science in China Series B: Chemistry

, Volume 43, Issue 3, pp 240–246 | Cite as

Mechanism for the addition of carbenoid CH2ClLi to formaldehyde

  • Jihai Li
  • Changjun Sun
  • Shaojie Liu
  • Shengyu Feng
  • Dacheng Feng
Article
  • 34 Downloads

Abstract

Ab initio HF/6-31G calculations have been performed for the addition mechanism of carbenoid CH2ClLi with formaldehyde in tetrahydrofuran. An early complex of formaldehyde with CH2ClLi is first formed with quite exothermic effect. Only a little activation energy of 14.6 kJ/mol is needed for the complex developing into the product through a transition state with coplanar bicyclic structure. In this process, the eletrophilic attack of carbonyl carbon of formaldehyde is more active than the nucleophilic attack of carbon of carbenoid. The exothermal effect of this addition process isupto 216.5kJ/mol.

Keywords

carbenoid transition state reaction pathway ab initio calculation 

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References

  1. 1.
    Villieras, J., Kirschleger, B., Tarhouni, R. et al., Nucleophilic properties of monohalogenated nonfunctionaliged carbenoid, Bull. Soc. Chem. Fr., 1986, 3: 470.Google Scholar
  2. 2.
    Barluenga, J., Fernandez-Simon, J. L., Concellon, J. M. et al, β-oxido funtionaliged organolithium intermediates from ketones: A simple new access, J. Chem. Soc. Chem. Commun., 1987, 12: 915.CrossRefGoogle Scholar
  3. 3.
    Herbete, C. B., Avinash, S. P., Milind, V. R., Ring enlargement of boracyclanes via sequential one-carbon homologation, the first synthesis of boracyclanes, in the strained medium ring range, J. Am. Chem. Soc., 1988, 110: 6263.CrossRefGoogle Scholar
  4. 4.
    Mu Guangzhao, Organic Active Intermediate (in Chinese), Beijing: Science Press, 1988, 227–228.Google Scholar
  5. 5.
    Li Jihai, Feng Shengyu, Liu Wei, Theoretical studies on the structure and reactions of halocarbenoids: (I) Structures and stability of chlorocarbenoid CHCl2Li, Chemical Research in Chinese Universities, 1997, 13(3): 256.Google Scholar
  6. 6.
    Li Jihai, Feng Shengyu, Theoretical studies on the structure and reactions of halocarbenoids: (II) Structure and stability of carbenoid CHClFLi, Chem. J. Chinese Universities, 1998, 19(4): 613.Google Scholar
  7. 7.
    Foreman, J. B., First, A., Exploring Chemistry with Electronic Structure Methods: A Guide to Using Gaussian, Pittsburgh: Gaussian Inc., 1992, 191.Google Scholar
  8. 8.
    Lozach, D., Molle, G., Bauer, P. et al., Organolithiens a structure “cage” reactivite vis-a-vis des cetones non enolisables coexistence D’un complexe evolutif et D’un complexe inerte, Tetrahedron Lett., 1983, 24: 4213.CrossRefGoogle Scholar
  9. 9.
    Del Bene, J. D., Frisch, M. J., Raghavachari, K. et al., A molecular orbital study of some lithium ion complexes, J. Phys. Chem., 1983, 87: 73.CrossRefGoogle Scholar

Copyright information

© Science in China Press 2000

Authors and Affiliations

  • Jihai Li
    • 1
  • Changjun Sun
    • 1
  • Shaojie Liu
    • 1
  • Shengyu Feng
    • 1
  • Dacheng Feng
    • 1
  1. 1.College of ChemistryShandong UniversityJinanChin

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