2408-01-7Relevant articles and documents
Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water
Rozhko, Elena,Solmi, Stefania,Cavani, Fabrizio,Albini, Angelo,Righi, Paolo,Ravelli, Davide
, p. 6425 - 6431 (2015)
The mechanism of the oxidation of cyclohexanone with an aqueous solution of hydrogen peroxide has been investigated. Experiments revealed the preliminary formation of an intermediate, identified as cyclohexylidene dioxirane, in equilibrium with the ketone, followed by formation of 1-hydroperoxycyclohexanol (Criegee adduct). Computational analysis with explicit inclusion of up to two water molecules rationalized the formation of the dioxirane intermediate via addition of the hydroperoxide anion to the ketone and revealed that this species is not involved in the formation of the Criegee adduct. The direct addition of hydrogen peroxide to the ketone is predicted to be favored over hydrolysis of the dioxirane, the latter in competition with ring opening to carbonyl oxide followed by hydration. However, dioxirane may account for the formation of the bis-hydroperoxide derivative.
Hydrogen peroxide and arenediazonium salts as reagents for a radical beckmann-type rearrangement
Prechter, Agnes,Heinrich, Markus R.
experimental part, p. 1515 - 1525 (2011/06/24)
The reductive ring-opening of hydroperoxides derived from cyclic ketones leads to alkyl radicals which can effectively be trapped by arenediazonium salts. This synthetic transformation yielding azo carboxylic acids or lactams, after a reductive step, can be classified as a radical version of the well-known Beckmann rearrangement. In this article, we present results on the scope, the limitations and possible applications of this new reaction type. Georg Thieme Verlag Stuttgart · New York.
Preparation of 2-(6-carboxyhexyl)- and 2-(6-methoxycarbonylhexyl)cyclopent-2-en-1-one using free radical reactions
Ogibin,Starostin,Aleksandrov,Pivnitsky,Nikishin
, p. 901 - 903 (2007/10/02)
Two short and simple synthetic routes to the prostaglandin synthons 2-(6-carboxyhexyl)- and 2-(6-methoxycarbonylhexyl)cyclopent-2-en-1-one have been developed. The first is based on a cyclohexanone oxidative transformation with hydrogen peroxide and di-tert-butyl peroxide, the second on the free radical addition reaction of methyl 9-oxononanoate to acrylaldehyde diacylal.
