3240-24-2Relevant academic research and scientific papers
Nucleophilic addition to 4-acetyl-1-methylpyridinium iodide studied by 1H nmr
Tan, Liang K.,Cocivera, Michael
, p. 1929 - 1938 (2007/10/02)
The 1H nuclear magnetic resonance spectra obtained during the addition of amines to 4-acetyl-1-methylpyridinium iodide in aqueous solution provide data for the kinetic parameters associated with:(1) the rapid equilibrium of the addition step to form the carbinolamine intermediate; (2) the rate determining dehydration step to form the syn and anti imines; and (3) the anti to syn isomerization.Depending on the amine used, (1) can result in methyl proton exchange that is either fast or slow relative to the chemical shift between the acetyl-CH3 resonance of 4-acetyl-1-methylpyridinium iodide and the corresponding one due to carbinolamine.The line width data and the equilibrium constant Kn, which is determined by flow uv, provide values for the rate constants (kn and k-n) of the forward and reverse steps of the equilibrium.The logarithm of kn does not correlate with log Kn or pKa of the amines.In addition, the enthalpy change ΔH for the equilibrium step is found not to depend significantly on the nature of the amine.It remains relatively constant at about -11 kcal M-1.The dehydration step is subject to general acid and base catalysis with the effect decreasing in the order hydrazine, hydroxylamine, semicarbazide, and methoxyamine.For hydrazine and hydroxylamine, the syn/anti ratios are pH dependent.For hydrazine and semicarbazide the anti to syn imine conversion depends on pH.The occurence of anti to syn isomerism indicates that the dehydration of carbinolamine gives the anti imine as the product of kinetic control.
