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Photolyses of phenyl esters


Meyer, James Wilfred (1971) Photolyses of phenyl esters. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/S1DE-KS63.


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The photochemical reactions of phenyl esters have been studied in both solution and gas phases. The irradiation of phenyl esters in the gas phase with ultraviolet light results in their photolyses. The photolysis of phenyl acetate in the vapor phase produces mainly phenol with lesser amounts of [...] and [...]-cresols and [...] and [...]-hydroxy dipheny1 ethers. In addition to these compounds, [...]-benzoquinone was also isolated, however it is believed to be formed from the secondary photolysis of ga-hydroxydiphenyl ether. These products are explained with a mechanism involving the photolysis of phenyl acetate into phenoxy and aryl radicals followed by decarbonylation of the acy1 radical to give carbon monoxide and methyl radicals. The reactions of methyl and phenoxy radicals produce the observed products. Although attempts at scavenging the acyl radical failed, the detection of products from the decomposition of butyry1 radicals in the irradiations of phenyl [...]-butYrate indicates a simi1ar mechanism is operating in solution. These results are taken to indicate that the photo-Fries Rearrangement results from the cage recombination of phenoxy and acyl radicals rather than by means of a molecular rearrangement. The quantum yields of phenyl benzoate were measured in ether: [...]. The emission spectra of several different phenyl esters were recorded and discussed in terms of the excited state leading to reaction.

The irradiations of 1-butanethio1 in solution and [...]-hYdroxYacetophenone in the vapor phase were brieflY studied. 1-Butanethio1 gives hydrogen sulfide, butyldisulfide and dibutyl sulfide. Irradiations of [...]-hydroxyacetophenone appears to give phenol at low pressures and salicy1aidehyde at about 1000 mmHg.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Hammond, George Simms
Thesis Committee:
  • Unknown, Unknown
Defense Date:6 August 1970
Record Number:CaltechETD:etd-02102009-081424
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:597
Deposited By: Imported from ETD-db
Deposited On:11 Feb 2009
Last Modified:21 Dec 2019 04:42

Thesis Files

PDF (Meyer_jw_1971.pdf) - Final Version
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