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Rearrangements of organic peroxides and related processes

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ABSTRACT

This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

No MeSH data available.


Mechanisms of Schenck and Smith rearrangements.
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C123: Mechanisms of Schenck and Smith rearrangements.

Mentions: The Smith rearrangement is a free-radical chain reaction in which atmospheric oxygen may play a greater role than in the Schenck rearrangement. Apparently, the Smith rearrangement proceeds through a dissociation to the allylic radical and 3O2. Presumably, the distance between these active species is large enough to allow an exchange with atmospheric oxygen (Scheme 123). The Schenck and Smith rearrangements are both a consequence of the reversibility of the reaction of allyl radicals with triplet dioxygen and differ mechanistically in the degree of separation of these two components [186]. There are only a few examples of the Smith rearrangement known and some of them are collected in Table 19.


Rearrangements of organic peroxides and related processes
Mechanisms of Schenck and Smith rearrangements.
© Copyright Policy - Beilstein
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC4979652&req=5

C123: Mechanisms of Schenck and Smith rearrangements.
Mentions: The Smith rearrangement is a free-radical chain reaction in which atmospheric oxygen may play a greater role than in the Schenck rearrangement. Apparently, the Smith rearrangement proceeds through a dissociation to the allylic radical and 3O2. Presumably, the distance between these active species is large enough to allow an exchange with atmospheric oxygen (Scheme 123). The Schenck and Smith rearrangements are both a consequence of the reversibility of the reaction of allyl radicals with triplet dioxygen and differ mechanistically in the degree of separation of these two components [186]. There are only a few examples of the Smith rearrangement known and some of them are collected in Table 19.

View Article: PubMed Central - HTML - PubMed

ABSTRACT

This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

No MeSH data available.