Kinetics and mechanism of alkaline hydrolysis of aryl carbazates

Abstract

Hydrolysis of aryl carbazates (H₂NNHCO₂Ar with Ar = phenyl, 3- or 4-chlorophenyl, 3- or 4-nitrophenyl, 4-methylphenyl and 4-methoxyphenyl) and/or their 2- or 3-methyl derivatives in aqueous buffers or sodium hydroxide solutions gives phenolate and sodium carbazate. The kinetics and acidity constants and thermodynamic parameters are given. By analysing the pH profiles, the activation entropy, and effects of the substituent on the aromatic ring it was found that aryl carbazates containing a methyl group in the 2 position are hydrolysed by a B_Ac2 mechanism and the others by an E1cB mechanism. The pH profiles of nitrophenyl carbazates show a maximum. The rate of decarboxylation of carbazic acid decreases with increasing pH value.

References

1. T. Takematsu, S. Aman and M. Fujiwara, JPN 2295962, 1990.
2. K. Hemmi, M. Neya and H. Marusawa, EP 300189, 1989.
3. J. M. Cassal, A. Edenhofer and Z. H. Ramu, EP 189 094, 1986.
4. A. Safraoui, M. Calmon and J. P. Calmon, J. Chem. Soc., Perkin Trans. 2, 1991, 1349.
5. J. Mindl and V. Štěrba, Collect. Czech., Chem. Commun., 1983, 48, 900.
6. R. L. Blakeley and B. Zerner, Chem. Ind. (London), 1973, 133.
7. P. Vlasák, P. Pařík and J. Mindl, Collect Czech., Chem. Commun., in the press.
8. G. Yagil, J. Phys. Chem., 1967, 71, 1034.