62055-72-5Relevant academic research and scientific papers
Mechanism of Nucleophilic Attack at Carbon-Nitrogen Double Bonds. The Solovolysis of Substituted Benzohydrazonoyl Halides in Aqueous Binary Mixtures
Rowe, Jeffrey E.
, p. 463 - 468 (2007/10/02)
Rate data for the solvolysis of a series of substituted benzohydrazonoyl halides in aqueous dioxan at 329 K and in aqueous ethanol and methanol at 303 K are presented.The products in the aqueous alcohols were measured by h.p.l.c., and the selectivities determined.The data are used to support proposals about the mechanism of the reaction.
Kinetic and Stereochemical Study on Bimolecular Substitution Reactions of Hydrazonates, Thiohydrazonates, and Hydrazonoyl Chlorides with Methoxide Ion
Rowe, Jeffrey E.,Hegarty, Anthony F.
, p. 3083 - 3087 (2007/10/02)
Reaction of the (Z)-hydrazonoyl chlorides 2 with methoxide ion in methanol, under conditions where kinetic results show the reaction is bimolecular, leads to stereospecific formation of the (Z)-methyl hydrazonates 5.Less than 2percent of the product with the "inverted" configuration at carbon (6) is formed.When a poorer leaving group than Cl(-) is involved, then mixtures of E and Z products result.Thus the aryl thiohydrazonates (3) which have the Z configuration give 84-90percent of the (Z)-methyl hydrazonate on reaction with methoxide ion.The (E)-aryl hydrazonates undergo reaction ca. 12-fold more slowly and isomer ratios of the (Z)- and (E)-methyl hydrazonates which result are closer to 1:1.The product methyl hydrazonates 5 and 6 undergo MeO(-)-catalysed interconversion to an equilibrium mixture which favors 6, but at a slower rate than the formation of either 5 or 6.The stereochemical outcome of these displacements at the C=N bond is rationalized in terms of stereoelectronic control of the addition and elimination steps.
