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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 24, 1994 - Issue 3
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Original Articles

N-Benzylidenebenzenesulfonamide as a Benzaldehyde Equivalent in the Knoevenagel Reaction

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Pages 427-432 | Received 24 May 1993, Published online: 23 Sep 2006

References

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  • We and others (ref 5a) have observed that sterically crowded amines and hydroxylamines may require more forcing conditions, if they react at all. We have found that the reaction of 2 equivalents of 1 with 2,3-diamino-2,3-dimethylbutane results in the formation of the mono imine instead of the diimine which is readily available from the reaction of diamine with 2 equivalents of benzaldehyde. This result is believed to arise due steric considerations with the large size of the N-sulfonylimino group of 1, relative to the oxygen of benzaldehyde, inhibiting the reaction of the second equivalent of 1 with the more sterically encumbered amino group of the mono imine. This observation suggests that 1 may be a selective benzylideneating agent when a molecule possesses two sterically differentiable amine or hydroxylamine functions
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  • March , J. 1992 . “Advanced Organic Chemistry; Reactions, Mechanisms and Structure” , 945 – 951 . New York : John Wiley amp Sons . For a discussion of the Knoevenagel reaction. See:
  • Reference 3c reports the addition of the anion of dimethyl malonate to N-benzylidene-p-toluenesulfonamide
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  • The addition products obtained in this study were contaminated with small amounts of benzenesulfonamide. Analytically pure samples were difficult to obtain as either chromatography or recrystallization resulted in some decomposition. However the 1H and 13C NMR spectra are fully consistent with the structure proposed in reference8
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  • 1993 . Aldrich Chemical Co., , Edition I. Vol. 2 , 1507B The Aldrich Library of 13C and 1H FT NMR Spectra
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  • Barchiesi , E. , Bradamante , S. , Ferraccioli , R. and Pagani , G. A. 1990 . J. Chem. Soc. Perkin Trans. , 2 : 375

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