Model reactions of pyridinecarboxylic acids with glycidyl phenyl ether

Abstract

The reactions of 3-pyridinecarboxylic acid (nicotinic acid, NA) and Cpyridinecarboxylic acid (isonicotinic acid, ISNA) with 2,3-epoxypropyl phenyl ether (glycidyl phenyl ether, GPE) were studied by means of high performance liquid chromatography (HPLC). It is found that both reactions involve two-step mechanisms and have induction periods. 'Wo products, pyridinium salt and ester, are obtained in each study. The formation of pyridinium salt is the cause of the occurrence of the induction period. After the induction period, the kinetics of the reaction is second order. Pyridinium ions do not form complexes with carboxylate ions of pyridinecarboxylates but form activated complexes with the hydrogen-bonded complexes of pyridinecarboxylic acids and GPE to activate the esterification reactions. The mechanisms of the reactions are discussed in detail.there is no data in the literature on the reaction between N-containing model acids (e. g. PCA) and epoxide. The kinetics and mechanisms of the reaction between PCA and epoxide are quite different from those of the carboxyl-epoxide reaction which had been discussed previously lo-12, 15-22). Experimental partMaterials: GPE was dried over calcium hydride and distilled at reduced pressure. Anisole and 1-butanol were distilled and stored over molecular sieves. NA and ISNA were purified by recrystallization from a mixture of ethanol and diethyl ether. Instruments:Bruker AM-300WB FT-NMR or JEOL 100 MHz FT-NMR, JASCO FT/IR-3 and JEOL JMS-300 GC/MS were used to obtain NMR, IR and mass spectra.Kinetic euperiments: These were carried out under nitrogen in a thermostatted flask fitted with a constant speed stirrer, an inert gas inlet, a sampling device, a thermometer and a condenser. The reaction flask containing PCA (NA or ISNA) and solvent was heated to a desired temperature (100 0 1990, Htithig & Wepf Verlag, Basel CCC 0025-1 16X/90/$03.00

Study of heterocyclic polymers, 3. Synthesis and properties of the ampholytic heteroccylic polyelectrolyte poly[n‐(2‐hydroxy‐3‐methacryloyloxypropyl)‐pyridinium‐3‐carboxylate]

“…N-(2-Hydroxy-3-methacryloyloxypropyl)pyridinium-3-carboxylate (NHMPPC) (1) is a zwitterionic heterocyclic monomer which was synthesized by the reaction of 2,3-epoxypropyl methacrylate (EPMA) with nicotinic acid (NA) following the reaction model described before I, 31). The homopolymer, poly(NHMPPC) (2), and copolymers, poly(NHMPPC-co-AM), containing various fractions of AM (acrylamide) were synthesized in our laboratory.…”