Influence of solvents on the kinetics of the reaction of benzyl chloride with methacrylic acid in the presence of tertiary amines
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The direction of the reaction of benzyl chloride with methacrylic acid in the presence of tertiary amines depends on the basicity of the amine. In the presence of highly basic amines, benzyl methacrylate is formed. Weakly basic amines are alkylated by benzyl chloride.
Aprotonic polar solvents accelerate the formation of the ester. The reaction rate constant correlates with the dielectric constant ɛ of the solvent according to the Kirkwood and Amis equations for the reaction of two dipoles.
An hypothesis of a push-pull SN2 mechanism in media with a low or moderate value of ɛ and replacement of this mechanism by an SN1 mechanism in media with a high value of ɛ has been advanced.
KeywordsChloride Ester Dielectric Constant Methacrylate Benzyl
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- 1.M. A. Bulatov, K. A. Charushnikov, L. G. Surovtsev, and S. S. Spasskii, Plastmassy,1975, No. 1, 11.Google Scholar
- 2.K. A. Charushnikov, M. A. Bulatov, and S. S. Spasskii, Inventor's Certificate No. 366,185 (1972); Byull. Izobr., No. 7 (1973).Google Scholar
- 3.Chemist's Handbook [in Russian], Vol. 3 (1964).Google Scholar
- 4.K. Nakanishi, Infrared Absorption Spectroscopy. Practical, Holden-Day, San Francisco (1962).Google Scholar
- 5.G. V. Gusakova, G. S. Denisov, and A. L. Smolyanskii, Zh. Prikl. Spektrosk.,17, 666 (1972).Google Scholar
- 6.I. Gyenes, Titration in Nonaqueous Media, Van-Nostrand-Reinhold (1968).Google Scholar
- 7.C. Larsson, Z. Phys. Chem.,A159, 316, 319 (1932).Google Scholar
- 8.T. I. Temnikova, in: Reactivity and Mechanism of Reactions of Organic Compounds [in Russian], Izd. Leningr. Univ. (1971), p. 26; L. D. Parker, Usp. Khim.,40, 2209 (1971);34, 1227 (1965).Google Scholar
- 9.Chemist's Handbook [in Russian], Vol. 1 (1966).Google Scholar
- 10.S. W. Benson, The Foundations of Chemical Kinetics, McGraw-Hill, New York (1960).Google Scholar
- 11.E. S. Amis, Solvent Effects on Reaction Rates, Academic Press, New York (1964).Google Scholar
- 12.V. A. Savelova, L. M. Litvinenko, Reakts. Sposobn. Org. Soedin.,5, 838, 862 (1968).Google Scholar
- 13.O. A. Osipov, V. I. Minkin, and A. D. Granovskii, Handbook of Dipole Moments [in Russian], Vysshaya Shkola (1971), p. 203.Google Scholar
- 14.O. A. Reutov, Theoretical Principles of Organic Chemistry [in Russian], Khimiya (1968), p. 275.Google Scholar
- 15.A. Weissberger, E. Proskauer, J. Riddick, and E. Toops, Jr., Organic Solvents-Physical Properties and Methods of Purification, Wiley-Interscience (1955).Google Scholar
- 16.K. J. Laidler, Reaction Kinetics, Pergamon, Oxford-New York (1963).Google Scholar