Abstract
Though 2- and 3-hydroxypyridines, structurally resemble imidazole, 2-hydroxypyridine seems to function as a nucleophile in the hydrolysis ofp-nitrophenylbenzoate as it can acquire a pyridine form (Mosher 1959) while the latter cannot. The bifunctional activity of benzamidine has also been enhanced by anionic micelles of sodium laurylsulphate. The anionic micelle formed by sodium laurylsulphate retards the rate of hydroxylaminolysis ofp-nitrophenylbenzoate, while the cationic micelle formed from cetyltrimethylammonium bromide enhances the rate in H2NOH−H2NOH·HCl buffer at pH=6·14. Such behaviour is in favour of the anion, H2NO−, acting as a nucleophile to some extent. On the contrary, hydroxylaminolysis ofp-nitrophenylphenylmethane sulphonate (PMS) proceeds at a slower rate and imidazole catalysis is observed as these esters at pH=6·14 possibly prefer aB Ac 2 mechanism, which is absent at pH=9·2 as the same reactions proceed by aE 1 cB path.
Similar content being viewed by others
References
Alburn T C and Grant N H 1965J. Am. Chem. Soc. 87 4174
Balasubramanian D, Ganesh K N and Mitra P 1982J. Phys. Chem. 86 4291
Bender M L and Turnquest B W 1957J. Am. Chem. Soc. 79 1652, 1656
Brown J M and Bunton C A 1974J. Am. Chem. Soc. 96 960
Bruice T C and Schmir G L 1957J. Am. Chem. Soc. 79 1663
Bruice T C and Fedor L 1964J. Am. Chem. Soc. 86 738
Davy M B, Douglas K T, Loran J S, Steltner A and Williams A 1977J. Am. Chem. Soc. 99 1196
Fendler J H and Fendler E J 1975Catalysis in micellar and macro-molecular systems (New York: Academic Press)
Geneste R, Durand R, Finiels A and Schlick B 1976Tetrahedron Lett. 431
Jencks W P 1969Catalysis in chemistry and enzymology (New York: McGraw-Hill)
Menger F M 1966J. Am. Chem. Soc. 88 3081
Menger F M and Portnoy C E 1968J. Am. Chem. Soc. 90 1875
Mosher H S 1959Heterocyclic compounds (ed.) R C Elderfield (New York: John Wiley and Sons) vol. 1, chap. 8
Moss R A, Nahas R C, Ramaswamy S and Sanders W J 1975Tetrahedron Lett. 3379
Piskiewicz D 1977J. Am. Chem. Soc. 99 1550
Swain C G and Brown J F 1952J. Am. Chem. Soc. 74 2538
Tagaki W, Fukushima D, Eiki T and Yano Y 1979J. Org. Chem. 44 555
Vogel A I 1978A text book of practical organic chemistry 4th ed. (London: Longman ELBS)
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Raghavan, P.S., Srinivasan, V.S. Influence of imidazole and bifunctional nucleophiles on the micellar catalysed hydrolysis and hydroxylaminolysis of esters. Proc. Indian Acad. Sci. (Chem. Sci.) 95, 375–380 (1985). https://doi.org/10.1007/BF02867351
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF02867351