KINETIC AND THEORETICAL-STUDIES ON THE REACTION OF PHENACYL BROMIDE WITH 4DMAP IN THE PRESENCE OF CERTAIN PHENOLS

Authors
PILLAY MK JEYARAMAN R NALLU M VENUVANALINGAM P RAMALINGAM M
Citation
Mk. Pillay et al., KINETIC AND THEORETICAL-STUDIES ON THE REACTION OF PHENACYL BROMIDE WITH 4DMAP IN THE PRESENCE OF CERTAIN PHENOLS, Indian journal of chemistry. Sect. A: Inorganic, physical, theoretical & analytical, 36(5), 1997, pp. 414-417
Citations number
14
Categorie Soggetti
Chemistry
Journal title
Indian journal of chemistry. Sect. A: Inorganic, physical, theoretical & analytical → ACNP
ISSN journal
03764710
Volume
36
Issue
5
Year of publication
1997
Pages
414 - 417
Database
ISI
SICI code
0376-4710(1997)36:5<414:KATOTR>2.0.ZU;2-T
Abstract
The quaternization reaction between phenacyl bromide and 4-(dimethylam ino)pyridine (4DMAP) has been studied at 25, 30 and 35 degrees C in ac etone. Added phenols with pK(a) > 7.0 retard the rate of quaternizatio n and there is no ether formation. This has been confirmed through pro duct analysis by HPLC using paired ion chromatography (PIC) reagent-A. The reaction has been followed conductometrically using Guggenheim's method. Theoretical calculations (PM3) confirm the formation of H-bond ed complex between the phenol(s) and 4DMAP, that could retard the rate of quaternization. Relative proton affinity (PA) values of various ph enolates computed here explain the preferential formation of quaternar y salt over ether in the reaction.