Transesterification reactions of parabens (alkyl 4-hydroxybenzoates) with polyols in aqueous solution.
Accelerated stability tests of aqueous solutions containing parabens and polyols were performed using concentrations similar to pharmaceutical and cosmetic formulations. Reaction products were detected in these solutions by HPLC and identified by chromatographic and spectroscopic means. Using xylitol and methylparaben as model reactants, three unknown peaks having the relation 1:2:4 were obtained together with the hydrolysis product 4-hydroxybenzoic acid. Diode array detection gave identical UV spectra for each peak with a maximum at 255 nm. The structures of the isomeric 1-, 2-, and 3-xylityl 4-hydroxybenzoic acid esters were proved by means of LC-MS, GC-MS, and NMR and correlated to the peaks in the HPLC chromatograms. The rate of the transesterification was shown to be highest in strongly alkaline medium (ph 10-11), whereas equilibration of the reaction was optimally balanced at pH 8-9. An increase of polyol concentration enhanced the formation of the esters. The reactivity of different substituted parabens was higher in the case of parabens with a short alkyl ester function. Similar reaction profiles were observed with C3-C6 polyols, but no transesterification took place when aldoses were used.
Hensel
A
A
ASTA Medica AG, Frankfurt, Germany.
Leisenheimer
S
S
Müller
A
A
Busker
E
E
Wolf-Heuss
E
E
Engel
J
J
D002851:Chromatography, High Pressure Liquid; D004952:Esters / Q000138:chemical synthesis; D008401:Gas Chromatography-Mass Spectrometry; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010226:Parabens / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry
D004952:Esters; D010226:Parabens; D011108:Polymers; C024617:polyol; D014867:Water