Photochemistry of di-tert-butyl ketone and structural effects on the rate and efficiency of intersystem crossing of aliphatic ketones
01 Nov 1970-Journal of the American Chemical Society (American Chemical Society)-Vol. 92, Iss: 23, pp 6974-6976
About: This article is published in Journal of the American Chemical Society.The article was published on 1970-11-01. It has received 81 citations till now. The article focuses on the topics: Intersystem crossing & Ketone.
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TL;DR: In this paper, transient alkyl radicals and triplet-state molecules are generated simultaneously in solution by laser flash irradiation, and chemically induced electron polarization (CIDEP) of the radicals is studied by time-resolved ESR spectroscopy.
220 citations
TL;DR: The advanced chemistry of the CIEEL-type dioxetanes as highly efficient chemiluminescent substrates is described, focusing on their molecular design and synthesis.
Abstract: A class of high-energy molecules, the 1,2-dioxetanes, have received a great deal of attention because of their unique ability to decompose thermally into electronically excited carbonyl products. Their chemistry originates from studies on molecular mechanisms of bioluminescence and has a history of over 30 years. However, the luminescent efficiency of the dioxetanes could hardly be compared with that for bioluminescence until a dioxetane bearing an easily oxidized aryl group was found to afford efficient chemiluminescence by the intramolecular chemically initiated electron exchange luminescence (CIEEL) mechanism. Nowadays, the CIEEL-type dioxetanes are being applied to modern biochemical and biomedical analyses. In this review, the advanced chemistry of the CIEEL-type dioxetanes as highly efficient chemiluminescent substrates is described, focusing on their molecular design and synthesis. Singlet chemiexcitation processes for the intramolecular CIEEL decay of dioxetanes and triplet chemiexcitation processes for the thermolysis of dioxetanes are also discussed.
173 citations
TL;DR: In this article, electron spin resonance was used to detect and identify alkyl and acyl radicals during UV-irradiation of dialkyl aryl ketones in liquid solutions and the results were discussed with respect to the photochemical behaviour of the ketones.
Abstract: Transient alkyl and acyl radicals are detected and identified by electron spin resonance during UV.-Irradiation of dialkyl and alkyl aryl ketones in liquid solutions. They are formed by the primary processes of α-cleavage, intermolecular photoreduction or α-chloro elimination. For several ketones a temperature dependent competition between α-cleavage and photo-reduction is observed indicating a higher energy of activation for the cleavage than for the reduction process. The results are discussed with respect to the photochemical behaviour of the ketones.
Electron spin resonance parameters are reported for a variety of radicals. In particular 13C coupling constants support a sigma type structure of acyl radicals and require a nearly planar radical center of t-butyl and isopropyl radicals.
148 citations
TL;DR: The fossil record of the Ketones family can be traced back to the 6th Century AD, although the precise date is still poorly known.
Abstract: e-Cleavage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 A. Aeyelic Al iphat ie Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 B. Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 C. Cyclic Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 D. Phenyl Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
147 citations