Accession Number : AD0647430

Title :   PHOTO-INDUCED REDOX REACTIONS.

Descriptive Note : Biennial rept., 1 Jan 63-1 Dec 66,

Corporate Author : CASE INST OF TECH CLEVELAND OHIO

Personal Author(s) : Kochi,Jay K. ; Bethea,Tristram W. , III ; Hay,Nelson E.

Report Date : 01 DEC 1966

Pagination or Media Count : 65

Abstract : Despite the ease of formation of silver ion complexes of olefins, photolysis of a variety of these complexes in several solvents afforded no apparent photoreaction but the cuprous chloride-1,5-cyclooctadiene complex structure of which has been determined has been shown to undergo photoreaction in ether solution at 2537A to produce tricyclo (3.3.0.0) octane. In the decarboxylation of cyclohexane carboxylic acid, the same products were obtained in the thermal reaction and in all of the photolytic ones. The esters and alkylbenzenes show the most pronounced differences in the two methods of decarboxylation; the combined yields of these components in the thermal reaction are over twice those obtained by any photolytic method. The decarboxylation of 2,2-dimethylbutyric acid, a tertiary acid, showed a more obvious difference. In the thermal reaction no 2-methylbutane was produced; in the photolytic reactions, however, this product was found. In the photolysis of primary carboxylic acids, shorter wavelength irradiation, 2537A, produces greater amounts of alkene and dimer than does the 3500A reaction. (Author)

Descriptors :   (*OXIDATION REDUCTION REACTIONS, *PHOTOLYSIS), (*COMPLEX COMPOUNDS, PHOTOLYSIS), ALKENES, SILVER COMPOUNDS, SALTS, ACETATES, CARBOXYLIC ACIDS, CYCLOHEXANES, LEAD COMPOUNDS, THALLIUM COMPOUNDS, METALS, ELECTRON PARAMAGNETIC RESONANCE, CERIUM COMPOUNDS

Subject Categories : Physical Chemistry
      Radiation and Nuclear Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE