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Journal of the American Chemical Society,, 1977, 6119-6124

Mechanism of Carbanion Addition to Carbonyl Compounds. Equilibria and Kinetics of Substituted Cyanohydrin Cleavage and Formation in Aqueous Solution. Substituted Cyanohydrin Proton Dissociation Constants. Journal of the American Chemical Society,, 1977, 6119-6124.

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Journal of the American Chemical Society,, 1977, 6119-6124

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  1. Mechanism of Carbanion Addition to Carbonyl Compounds. Equilibria and Kinetics of Substituted Cyanohydrin Cleavage and Formation in Aqueous Solution. Substituted Cyanohydrin Proton Dissociation Constants Journal of the American Chemical Society,, 1977, 6119-6124

  2. Evidence for the Conservation of the Aldehydic Hydrogen Atom during Cyanohydrin Formation

  3. Lifetime of an Aliphatic Iminium Ion in Aqueous Solution J. Am. Chem. SOC. 1995,117, 6631-6632

  4. Loss of resonance stabilization in the transition state for hydration of the aromatic iminium ions may involve structural rearrangement that provides an additional barrier to hydration of the ions.

  5. The Strecker reaction: kinetic and equilibrium studies of cyanideaddition to iminium ions Org. Biomol. Chem., 2004, 2, 2567-2571

  6. first-order ! KCN 1: 0 2: 0.001 mol dm−3 3: 0.002 mol dm−3 4: 0.004 mol dm−3 5: 0.008 mol dm−3 6: 0.016 mol dm−3 7: 0.020 mol dm−3 4 : 250nm => strong absorption 6 : 220 nm => no strong absorption 7 : 250 nm => less strong absorption cyanide↓, absorbance ↑ => benzaldehyde formation

  7. KCN 1: 0 2: 0.001 mol dm−3 3: 0.002 mol dm−3 4: 0.004 mol dm−3 5: 0.008 mol dm−3 6: 0.016 mol dm−3 7: 0.020 mol dm−3 4 : 250nm => strong absorption 6 : 220 nm => no strong absorption 7 : 250 nm => less strong absorption Cyanohydrin : 250 nm => no absorption Benzaldehyde  equilibrium  cyanohydrin

  8. 5 The ‘low’ reactivity charge delocalisation. (stabilised both by amino groups and by a benzene ring.) Strongly electron withdrawing nitro group  enhances its reactivity relative to 5

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