WOLFF Rearrangement, Flash Light Photolysis, Kinetic Measurements, 9,10-Diazophenantlirone, Diphenylene Ketene 9,10-Diazophenanthrone undergoes WOLFF rearrangement in alcoholic solvents and yields esters of 9-fluorene carboxylic acid. By flash light photolysis four intermediates could be detected. Kinetic measurements showed that the ketene formed by photolysis reacts with the solvent to give a cyclopentadienylic carbanion, which is protonated. A carbene or an oxirene intermediate could not be found.
In a photochemical decomposition reaction of the a-Diazoketone 1 in the presence of toluene ring-opening of the adjacent furanoyl substituent occurs as well as conversion of a norcaradiene intermediate thus forming the acetylenic olefinic aldehyde 4 and the dihydrobenzofuran 3. Reaction pathways are derived from the corresponding ketocarbeneoxirene equilibrium in which surprisingly the secondary ketocarbene B-1 gives rise to the formation of the aldehyde 4! No Wolff rearrangement product could be detected.
Abstract There are numerous simple chemical reactions in which reaction products arise, which compared with the materials at the outset, possess a considerably greater surface area. A significant example is the reaction of aluminium alcoholates with water. Reactions of this kind can, to a certain extent, be used as auxiliary reactions, in order to distribute other materials homogenously. In the chosen example, a material dissolved beforehand in the alcoholate, e.g. a solution of a metal salt, would be transferred in the course of the distributing reaction into the newly-developing structure of the reaction product. In this publication the application of some catalysts thus prepared to some classical organic chemical reactions is described by way of example
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.