Structural Chemistry

, Volume 4, Issue 5, pp 333–337 | Cite as

Molecular structure of cyclobutanones resulting from cycloaddition of Moore's ketene to styrene, 1-vinylnaphthalene andp-methoxystyrene

  • S. V. Sereda
  • K. M. Turdibekov
  • Yurii T. Struchkov
  • Mircea D. Gheorghiu
  • Marina Mihai
  • Luminitza Parvulescu
Article
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Abstract

Styrene or 1-vinylnaphthalene react with Moore's ketene (t-butylcyanoketene) to give cyclobutanones1a and1b, respectively, withcis configuration of the vicinal bulkyt-butyl and aryl groups. Steric crowding is reduced by (i) nonplanarity distortion of the cyclobutanone ring (ca. 20°), (ii) elongation to ca. 1.6 Å of the C2-C3 bond (which is flanked by the bulky groups), (iii) deviation of the vicinal bulky groups by ca. 22° from the eclipsed conformation, and (iv) increased bond angles of thet-Bu-C2-C3 and Ar-C3-C2 groups.p-Methoxystyrene reacts with Moore's ketene to give cyclobutanone2a with the vicinal bulkyt-butyl and aryl groups in thetrans configuration. In contrast to1a and1b, (i) the cyclobutanone ring is planar, (ii) the C2-C3 bond is shorter (1.59 Å), and the bond angles (iii) and (iv) are each reduced by 12.5°. It is concluded that in the case of styrene and 1-vinylnaphthalene the cycloaddition reaction is seemingly concerted and occurs according to a2πs+2πa reaction mode, whereasp-methoxystyrene reacts stepwise with Moore's ketene, giving the thermodynamically more stable cyclobutanone isomer.

Key words

2+2 cycloaddition Moore's ketene X-ray crystallography 
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Copyright information

© Plenum Publishing Corporation 1993

Authors and Affiliations

  • S. V. Sereda
    • 1
  • K. M. Turdibekov
    • 1
  • Yurii T. Struchkov
    • 1
  • Mircea D. Gheorghiu
    • 2
  • Marina Mihai
    • 2
  • Luminitza Parvulescu
    • 2
  1. 1.Institute of Organoelement Compounds of the USSR Academy of SciencesMoscowUSSR
  2. 2.Department of Organic ChemistryPolytechnic InstituteBucharestRomania

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