Abstract
The hydrolytic rate constants of thep-nitrophenyl esters of acetic, octanoic, dodecanoic and hexadecanoic acids in six aquiorgano binary mixtures of graded compositions at various initial substrate concentrations were measured and discussed in terms of the hydrophobic-lipophilic interactions between the substrate molecules, and the organic cosolvents which were MeOH, Me2SO, 1, 4-dioxane, 1,2-dimethoxyethane,n-propanol andt-butanol. The accelerating or retarding effects of the organic cosolvents on the rate constants of hydrolysis were found to be directly related to the lipophilicities of the solvents which were changed either by changing the content (ϕ) or the nature of the organic cosolvent. The classification or ordering of the six solvents on the basis of their solvent effects were found to conform to the lipophilicity order derived from Rekker's Σf values. The results support the proposition that lipophilic interactions can play an important role in solvent effects of aqueous binaries.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Ben-Naim A 1980Hydrophobic interactions (New York: Plenum Press) chap. 1
Blyth C A and Knowles J R 1971J. Am. Chem. Soc. 93 3021
Diederich F, Dick K and Griebe D 1986J. Am. Chem. Soc. 108 2273
Elsemongy M M, Amira M F and Ahmed A M 1981Indian J. Chem. A20 802, and their earlier work
Engberts J B F N 1982Pure Appl. Chem. 54 1797
Fan Wei-Qiang and Jiang **-Kui 1985J. Am. Chem. Soc. 107 7680
Fan Wei-Qiang, Jiang **-Kui, Hui Yong-Zheng and Li Mei-Zheng 1985Acta Chim. Sin. 43 839
Franks F 1975 inWater, a comprehensive treatise (ed.) F Franks (New York: Plenum Press) vol.4, chap. 1
Guthrie J P 1973Can. J. Chem. 51 3494
Gutmann 1978The donor-acceptor approach to molecular interactions (New York: Plenum Press) pp. 27–33
Holterman H A J and Engberts J B F N, 1983J. Org. Chem. 48 4025
Jiang **-Kui, Fan Wei-Qiang and Hui Yong-Zheng 1984aJ. Am. Chem. Soc. 106 7202
Jiang **-Kui, Gu Jian-Huia, Cheng **an-En and Hui Yong-Zheng 1987Acta Chim. Sin. 45 159
Jiang **-Kui, Hui Yong-Zheng and Fan Wei-Qiang 1984bActa Chim. Sin. 42 1276
Jiang **-Kui, Hui Yong-Zheng and Fan Wei-Qiang 1984cJ. Am. Chem. Soc. 106 3839
Jiang **-Kui, Hui Yong-Zheng and Fan Wei-Qiang 1985Acta Chim. Sin 43 57
Lowry J H 1982Mechanism and theory in organic chemistry 2nd edn. p. 266 (New York: Harper and Row)
Menger F M and Portnoy C E 1968J. Am. Chem. Soc. 90 1875
Menger F F and Venkataram U V 1986J. Am. Chem. Soc. 108 2980
Murakami Y, Aoyama Y and Kida M 1977J. Chem. Soc. Perkin II 1947
Murakami Y, Sunamoto J and Kano K 1974Bull. Chem. Soc. Jpn. 47 1238
Oakenfull D 1973J. Chem. Soc. Perkin II 1006
Oakenfull D and Fenwick D E 1974Aust. J. Chem. 27 2149
Oakenfull D and Fenwick D E 1977Aust. J. Chem. 30 741
Oakenfull D and Fenwick D E 1979J. Chem. Soc. Faraday I 635
Parker A J 1969Chem. Rev. 69 1
Perrin D D 1980Purification of laboratory chemicals 2nd edn. (Oxford: Pergamon)
Reichardt C 1979Solvent effects in organic chemistry (Weinheim: Verlag Chemie) pp. 19 and 26
Rekker R F 1977.The hydrophobic fragmental constants (Amsterdam: Elsevier) vol. 1
Rekker R F and de Kort H M 1979Eur. J. Med. Chem. 14 479
Shapiro E and Ohki S 1974 JColloid Interface Sci. 47 38
Singh L, Singh R T and Jha R C 1981J. Indian Chem. Soc. 58 966
Shobha J and Balasubramanian D 1986J. Phys. Chem. 90 2800
Tanford C 1980The hydrophobic effect: Formation of micelles and biological membrane (New York: Wiley Interscience) 2nd edn. p. 3
Yang Y C and Fagley T F 1981J. Am. Chem. Soc. 103 5849
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Jiang, XK., Li, XY. & Huang, BZ. The effect of hydrophobic-lipophilic interactions on chemical reactivity. 9. Putting the spotlight on lipophilic forces in solvent-effect studies. Proc. Indian Acad. Sci. (Chem. Sci.) 98, 409–421 (1987). https://doi.org/10.1007/BF02861537
Issue Date:
DOI: https://doi.org/10.1007/BF02861537