Photochemical transformations. 30. Photosolvolysis of benzyl chlorides in tert-butyl alcohol. 2. Nature of excited states

Journal Article · Wed Dec 02 04:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00414a041· OSTI ID:5735368

Cristol, S J; Bindel, T H

The photosolvolysis of a number of benzyl chlorides in tert-butyl alcohol, both as a result of direct irradiation and ketone triplet sensitization, has been studied. A variety of sensitization and quenching techniques have been used. The results obtained are rationalized by the assumption that there are two triplet states of the benzyl chlorides accessible in these experiments-one a short-lived upper state, which leads to solvolysis product, and another a long-lived (lower energy) state, which reverts to ground-state reactant. Consistent with this idea, m-methoxybenzyl chloride is shown to quench the photoreactions of benzophenone with benzhydrol without the formation of a significant amount of reactive species. The effects of wavelength on the reactions of p-acetobenzyl chloride are measured and discussed in terms of the two-triplet concept.

• Research Organization: Univ. of Colorado, Boulder
• DOE Contract Number: AC02-79ER10366
• OSTI ID: 5735368
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:24; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALCOHOLS
BENZOPHENONE
BUTANOLS
CHEMICAL REACTIONS
DECOMPOSITION
HYDROXY COMPOUNDS
KETONES
MULTIPLETS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
SCINTILLATION QUENCHING
SOLVOLYSIS
TRIPLETS