This Thesis aims to examine the effects of substituents on the adjacent proton accepting phenyl ring with respect to a new type of excited state intramolecular proton transfer (ESIPT) process discovered by Wan and co-workers. Therefore, a number of 2-phenylphenols 23-28 were synthesized with electron-donor and electron-acceptor substituents such as methyl, methoxy, and ketone moieties on the adjacent proton accepting phenyl ring.
The results obtained from examination of photochemical deuterium exchange showed that all derivatives except for ketone 27 underwent deuterium exchange (Фex = 0.019 - 0.079), primarily at the 2’-position on photolysis in D2O-CH3CN. In general, compounds with methoxy moiety (ies) on the adjacent proton accepting ring showed higher deuterium exchange yields.
Diol 28 has the potential to undergo photosolvolysis as well as ESIPT process since it has both a benzyl alcohol and a phenol chromophore on the same molecule. Irradiation of 28 in 1:1 H2O-CH3OH gave the corresponding methyl ether product in high yield. Photolysis of 28 in 1:1 D2O-CH3OH also showed that ESIPT competes very well with photosolvolysis. Thus, this work has established that ESIPT can compete efficiently with photosolvolysis.
Semi-empirical AM1 (examination of HOMOs and LUMOs) calculations show a large degree of charge transfer in the electronic excited state (except 27), from the phenol ring to the attached phenyl ring of the studied compounds. The AM1 calculation for ketone 27 showed that the carbonyl oxygen is more basic than the carbon atoms of the benzene ring, which explains the lack of deuterium exchange observed for 27.
| Identifer | oai:union.ndltd.org:uvic.ca/oai:dspace.library.uvic.ca:1828/2944 |
| Date | 12 August 2010 |
| Creators | Behin Aein, Niloufar |
| Contributors | Wan, Peter |
| Source Sets | University of Victoria |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Rights | Available to the World Wide Web |
Page generated in 0.0025 seconds