Catalysis of Trans-esterification Reactions in Model Ester Mixtures

V.A. Vasnev1, G.D. Markova1, B.A. Uvarov1, W.Yu. Voytekunas2 and M.J.M. Abadie2

1A.N. Nesmeyanov Institute of Organo-Element Compounds - INEOS, Russian Academy of Science, 28 Vavilov str., Moscow, 117813, Russia

2Laboratory of Polymer Science & Advanced Organic Materials – LEMP/MAO – Université Montpellier 2, Sciences et Techniques du Languedoc, Place Bataillon, 34095 Montpellier Cedex 05 – France

Abstract

Model trans-esterification reaction of n-butylbenzoate with phenyl-p-chlorobenzoate in the molar ratio of 20:1 has been studied.

In order to evaluate catalysts based on lanthanide system the activity of nyodymium compounds – neodymium acetate, neodymium acetylacetonate and nitrate complex with benzo-12-crown-4 (neodymium nitrate coronate) – has been studied in the model trans-esterification reaction of n-butylbenzoate with phenyl-p-chlorobenzoate.

The effect of the electronic structure of the metal on the catalytic activity of the coronates of lanthanum, cerium, praseodymium, neodymium, samarium, terbium and erbium nitrates has been studied.

In order to estimate the optimum concentration of the catalysts, a study of the dependence of the transesterification reaction on concentration of neodymium nitrate coronate was carried out. An asymptotic nature of the concentration dependence on the catalytic activity of lanthanide compounds has been observed.

In order to look for new classes of inhibitors of trans-esterefication reaction, the model trans-esterificatiom reaction of n-butylbenzoate with phenyl-p-chlorbenzoate has been studied in the presence of some carborane derivatives: cesium salts of bis-1,2-(dicarbollyl) complexes of iron, cobalt and nickel(3+) and bis-1,2(dicarbollyl)nickel(4+) [(C2B9H11)2Me]. Some of these compounds were found to be effective inhibitors.

The dependence of the constant rate of the model trans-esterification reaction of n-butylbenzoate with phenyl-p-chlorobenzoate on the concentration of cerium salt of bis-1,2-(dicarbollyl) complex of nickel has been studied to determine the optimum concentration of inhibitors.

The influence of the ester chemical structure on the activity of ester groups in the trans-esterification activity has been determined in the reaction of di-n-butylterephthalate with different p-substituted derivatives of phenylbenzoate (phenyl-p-methoxybenzoate, phenyl-p-methylbenzoate, phenylbenzoate, phenyl-p-chlorobenzoate, phenyl-p-nitrobenzoate, p-methoxyphenylbenzoate, p-methylphenylbenzoate, p-chlorophenylbenzoate, p-nitrophenylbenzoate, n-butylbenzoate, di-n-butylterephthalate) in presence of the samarium nitrate coronate.