5628-60-4Relevant articles and documents
Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide
Camelio, Andrew M.,Liang, Yong,Eliasen, Anders M.,Johnson, Trevor C.,Yuan, Changxia,Schuppe, Alex W.,Houk,Siegel, Dionicio
, p. 8084 - 8095 (2015/09/01)
The oxidation of arenes by the reagent phthaloyl peroxide provides a new method for the synthesis of phenols. A new, more reactive arene oxidizing reagent, 4,5-dichlorophthaloyl peroxide, computationally predicted and experimentally determined to possess enhanced reactivity, has expanded the scope of the reaction while maintaining a high level of tolerance for diverse functional groups. The reaction proceeds through a novel "reverse-rebound" mechanism with diradical intermediates. Mechanistic insight was achieved through isolation and characterization of minor byproducts, determination of linear free energy correlations, and computational analysis of substituent effects of arenes, each of which provided additional support for the reaction proceeding through the diradical pathway.
Photorearrangements of Carbomethoxy-Substituted Cyclohexadienones in Neutral Media
Broka, Chris A.
, p. 575 - 583 (2007/10/02)
The photochemistry of several 2-carbomethoxy-3-keto-Δ1,4-hexahydronaphthalenes has been investigated.Unlike analogous bicyclic cyclohexadienones lacking a 2-carbomethoxy substituent, these systems do not undergo normal type-A photorearrangements upon irradiation in nonprotonating solvents.Instead, they afford exocyclic hydroazulenone olefins resulting from proton loss from their angular substituents as well as hydroxy ketones and decarbomethoxylated ethers which have been shown to arise from their derived Zimmerman-Schuster zwitterions by way of intramolecular processes involving attack of the carbomethoxy group upon the electrophilic C-9 center.The behavior of these systems is contrasted with that of a 4-carbomethoxy-substituted dienone and a monocyclic, 2-carbomethoxy-substituted dienone, both of which were found to undergo the expected type-A photorearrangements under neutral conditions.