Three classes of new photoreactions were discovered and their reaction
mechanisms investigated. These reactions are related in that the same critical o-quinonemethide
intermediate is involved in the mechanism of each reaction.
The first reaction is the photocyclization of 2-(2’-hydroxyphenyl)benzyl
alcohol (1) and derivatives to 6H-dibenzo[b,d]pyrans (e.g., 7 from 1), with
excellent chemical (>95%) and quantum yields (Φp = 0.50 for 7 from 1 in basic
solution). Results from investigations of structure-reactivity, pH-effects and
fluorescence data suggest that, in neutral solution, the primary photochemical step
involves ionization of the phenol moiety to phenolate ion in S1, which is probably
concerted with twisting of the phenyl rings, to give a more planar species in S,.
The subsequent dehydroxylation step of the benzyl alcohol moiety, to give o-quinonemethide
20, is initiated by a charge transfer from phenolate to the adjacent
phenyl ring. The thermal ring closure of 20 competes with nucleophilic solvent
(e.g., H20 or MeOH) capture, to give observed pyran 7 and alcohol 1 (by H20) and
5 (by MeOH), respectively. In moderately strong acidic media, acid-catalyzed
photosolvolysis occurs, to give carbocation 21 which can also cyclize to afford
pyran 7.
The second photoreaction is the photocyclization reaction of 2-
phenoxybenzyl alcohols 22 and 23 to give dibenzo[b,d]pyrans 7 and 29,
respectively, in aqueous solution. The primary photochemical step is believed to
involve initial aryl-O bond homolysis followed by rearrangement to give alcohol
1, which cyclizes to observed pyran 7 upon secondary photolysis. The meta-substituted isomer 24 did not produce cyclized photoproducts, but instead gave
isomeric hydroxybiphenyls which are also derived from initial aryl-O bond
homolysis followed by simple radical recombination. The photocyclization appears
to be general for the ortho-phenoxybenzyl alcohol system, in which an appropriate
assembly of phenoxy and hydroxymethyl (CH2OH) functional groups is a necessary
requirement. In acidic solution, a competing proton-assisted photosolvolysis
reaction, via heterolysis of the benzylic C-OH bond, takes place for all these
compounds, to give carbocation intermediates which were subsequently trapped by the solvent.
The last reaction is the photoisomerization of xanthene (26) to pyran 7
(~70% yield and Φp ~ 0.0035 in aqueous solution). In addition to 7, 2-
benzylphenol (40) (Φ = 0.001), 9,9’-bixanthyl (41) (Φ < 0.001) and alcohol 1 (Φ
< 0.001) were also observed as minor products in the reaction. The
photoisomerization is again initiated by aryl-O bond homolysis in S1, to give a
singlet phenyl/phenoxy biradical 48 which undergoes a radical ipso-attack on the
adjacent phenyl ring, followed by rearrangement to afford o-quinonemethide 20,
which cyclizes to form pyran 7 in competition with nucleophilic solvent capture to
give 5 (by MeOH). Xanthene derivative 42 also photoisomerizes to the
corresponding pyran derivative 29, which was obtained in much lower yield due
to secondary photochemistry of 29. / Graduate
| Identifer | oai:union.ndltd.org:uvic.ca/oai:dspace.library.uvic.ca:1828/9519 |
| Date | 26 June 2018 |
| Creators | Huang, Cai-Gu |
| Contributors | Wan, Peter |
| Source Sets | University of Victoria |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Format | application/pdf |
| Rights | Available to the World Wide Web |
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