The reaction of benzoyl chloride (PhCOCl) and sodium dicarboxylate (R(COONa)2) catalyzed by an inverse-phase-transfer catalyst (IPTC) in the two-phase medium H2O/CH2Cl2 was investigated. Pyridine 1-oxide (PNO) was used as the inverse-phase-transfer catalyst. Ten dicarboxylates, namely oxalate, malonate, maleate, succinate, adipate, nonanedioate, fumarate, phthalate, isophthalate, and terephthalate, were selected for study. In general, the observed mixed products included mono- and bis(benzoyloxycarbonyl) compounds, benzoic anhydride and benzoic acid, depending on the molecular structure of the dicarboxylate ion. Dicarboxylates of four types were classified according to distribution of products. The reaction rate is strongly affected by PhCOCl and R(COONa)2 due to their influence on the distribution of PNO in the organic phase. A mechanistic interpretation of the experimental data is presented.

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The reaction of benzoyl chloride (PhCOCl) and butanoate ion (PrCOO−) catalyzed by pyridine 1-oxide (PNO) in the medium H2O/CH2Cl2 leads to equilibrium with butanoyl chloride (PrCOCl) and benzoate ion (PhCOO−) and vice versa. The rate-determining step takes place in the organic phase and PrCOCl is much more reactive than PhCOCl. The effects of chloride ion, hydroxide ion, pyridine 1-oxide, reactants and temperature on the reaction rate and the equilibrium conversion of acyl chloride (RCOCl) were investigated. Satisfactory detailed mechanistic interpretations of the kinetic results are given.

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The reactions of benzoyl chloride (PhCOCl) and sodium salts of five α-amino acids ((R'NH)CHRCOOH) in a two-phase H 2 O/CH 2 C1 2 medium under inverse phase-transfer catalysis (IPTC) were investigated. Pyridine (Py), Pyridine 1-oxide (PNO) and 4-dimethylaminopyridine (DMAP) were used as the inverse phase-transfer catalysts. A high yield (85-100%) of the main product PhCO(NR')RCOOH was generally obtained. The order of reactivities of amino acids toward reaction with PhCOCl is (N-methylglycine, L-proline)»glycine»DL-α-alanine>β-methylalanine»acetic acid. The characteristics of the PNO-catalyzed reaction of PhCOCl and sodium salts of β-methylalanine are similar to those of the PNO-catalyzed reaction of PhCOCl and sodium benzoate. The PNO-catalyzed reaction of benzoyl chloride and sodium salts of β-methylalanine follows a pseudo-first order kinetics. The observed rate coefficient is a linear function of the concentration of pyridine 1-oxide (PNO). The order of reactivities of catalysts in catalyzing the two-phase reaction of PhCOCl and /3-methylalanine is DMAP>PNO>Py. The experimental results are rationalized.