Cleavages and Rearrangements Involving Oxygen Radicals and Cations.

Leffler, John E.

doi:10.1021/cr60142a001

Cited by 80 publications

(26 citation statements)

References 19 publications

(29 reference statements)

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“…The decomposition of arenesulfonyl azides by thermolysis and photolysis has been studied in a variety of media. 5 The reported reaction products always contain the unrearranged sequence RS02N. When the substrate R'H was attacked at its C-H bonds the major products were RSO2NHR' and RS02NH2.…”

Section: Introductionmentioning

confidence: 97%

Curtius and Lossen Rearrangements. I. The Benzenesulfonyl System¹

Lwowski¹,

Scheiffele²

1965

J. Am. Chem. Soc.

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Benzenesulfonyl azide, when thermolyzed in aprotic solvents, gives products containing the unrearranged sequence ArS02N. Photolysis in alcohols, however, leads to rearrangement and formation of the hitherto unknown phenylsulfamic esters, ArNHS020R.N-ip-Nitrobenzenesulfonoxy)benzenesulfonamide (VII) undergoes base-induced decomposition in alcohols and in aniline to give p-nitrobenzenesulfonate ion and the addition products of the alcohol or aniline to the hypothetical intermediate, sulfurylaniline, ArNS02, in high yields.

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Section: Introductionmentioning

confidence: 97%

Curtius and Lossen Rearrangements. I. The Benzenesulfonyl System¹

Lwowski¹,

Scheiffele²

1965

J. Am. Chem. Soc.

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“…It is important to point out that, in this acidic medium, it is possible to form up to 2 mol of AMS per 1 mol of DCP decomposed by liberating hydrogen peroxide (following the k 2 ′ and k 4 steps). In a detailed report on peroxide chemistry, Leffler mentions the formation of hydrogen peroxide upon the reaction of tert -butyl hydroperoxide with acid . This is analogous to the proposed k 4 step shown in Figure , lending support to this portion of the postulated pathway.…”

Section: Resultsmentioning

confidence: 80%

“…Proposed mechanism of acid-catalyzed decomposition of DCP . After formation of the acid–peroxide complex, there are several possible pathways: (i) reversal to form the starting materials ( k –1 , shown in Figure ); (ii) rearrangement to form CHP and AMS ( k 2 ′); (iii) rearrangement to form CA and an OCC, which proceeds to form phenol and acetone ( k 2 ″).…”

Section: Resultsmentioning

confidence: 99%

Mechanism of Acid-Catalyzed Decomposition of Dicumyl Peroxide in Dodecane: Intermediacy of Cumene Hydroperoxide

Conley¹,

Mohammed²,

Winslow³

et al. 2016

Ind. Eng. Chem. Res.

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Acid-catalyzed decomposition of dicumyl peroxide in dodecane from 60 to 130 °C produces α-methylstyrene and phenol as the major products. Pseudo-first-order rate constants were determined as a function of the temperature for the reaction of DCP with dodecylbenzenesulfonic acid in dodecane and resulted in an Arrhenius plot exhibiting two distinct kinetic regimes with differing activation energies: 76.9 kJ/mol at low temperatures (measured from 60 to 90 °C) and 8.50 kJ/mol at higher temperatures (measured from 90 to 130 °C). With employment of a combination of kinetics, product analysis, and trapping experiments, evidence is presented to show the intermediacy of cumene hydroperoxidea reactive intermediate absent from previous mechanistic descriptions of this process. The yield of cumene hydroperoxide production is discussed, and the mechanistic pathways for formation of the observed products are presented.

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“…The chemistry of peroxide compounds has been reviewed in a number of monographs and reviews (e.g., ref 105,119,141,142,178,186,201,320). Peroxides contain two adjacent oxygen atoms with overlapping lone-pair orbitals.…”

Section: Peroxidesmentioning

confidence: 99%