Reaction of 4-benzylidene-2-methyl-5-oxazolone with amines, Part 2: Influence of substituents in para-position in the phenyl ring and a substituent on amine nitrogen atom on the reaction kinetics

Abstract

An influence of a structure of the amine (benzylamine, N-methyl-benzylamine, N-isopropyl-benzylamine, N-methyl-butylamine, N-ethyl-butylamine, sec-butylamine, and tert-butylamine) on a rate constant of the ring-opening reaction of 4-benzylidene-2-methyl-5-oxazolone (Ox) was studied. The good correlation between logarithm of the rate constants and Charton's steric substituent constant ν as well as good correlation with a form of the simple branching equation indicate that there is a steric effect because of substitution at C1 carbon atom of nucleophile which decreases the reaction rate. Additionally, an influence of a structure of the benzylidene moiety of Ox on a rate of the oxazolone ring-opening reaction was studied. The substituents (OH, OCH3, N(CH3)2, Cl, NO2) in para-position of the phenyl ring of Ox substantially modified the rate of the reaction with benzylamine in acetonitrile. The rate of the Ox ring-opening reaction decreased with increase of the electron-donating properties of the substituent. A good correlation between the rate constants of the reaction of 4-(4′-substituted-benzylidene)-2-methyl-5-oxazolones with benzylamine and the electron density at the reaction center (carbon C5 of the oxazolone ring), calculated using ab initio method, and the Hammett substituent constants, and CR equation were established. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 148–155, 2002; DOI 10.1002/kin.10039