Hydroperoxides, rearrangement

Bugg, T. D. H., and Lin, G., Solving the Riddle of the Intradiol and Extradiol Catechol Dioxygenases How Do Enzymes Control Hydroperoxide Rearrangements. J. Chem.Soc. Chem. Commun., 2001. pp. 941-952. 

The stable chromanyl hydroperoxide 52 is formed through a hydroperoxide rearrangement of the 1-methylindanol in 65% yield . 

Bisphenol A is manufactured by a reaction between phenol and acetone, the two products from the cumene hydroperoxide rearrangement. The temperature of the reaction is maintained at 50 °C for about 8-12 hr. A sluny... 

Finally, a series of novel hydroperoxy-l,2-dioxanes 233a, b (Scheme 65) were synthesized by hydroperoxide rearrangement and ozonolysis <2006EJ02174> all the products showed weak antimalarial acitivity. Also the epoxy-endoperoxides 234a,b were designed which proved to have inhibitory acitivity against Candida albicans (Scheme 65) <2007BMC36>. 

The most common current method of phenol production is from the cumene hydroperoxide rearrangement process. In this process, benzene reacts with propylene to produce cumene. Cumene is oxidized to cumene hydroperoxide. When cumene hydroperoxide is treated with dilute sulfuric acid, it rearranges and splits into phenol and acetone. Because the reactants are inexpensive and the process is simple, the acidic oxidation of cumene is used to produce more than 95% of the worlds supply of phenol. 

It is difficult to tell from patent literature at what scale processes have been operated, but a recent presentation indicated that the hydroperoxide rearrangement shown in Scheme 11.14 has been used to make -1.2 tonnes at 28 kg day product [32]. Other very attractive features of the continuous processes shown in Schemes 11.13 and 11.14 are the reduction in organic solvent use and the minimization of cryogenic cooling [30-32]. 

Two-carbon ring expansion. Some year. ago Criegee- reported that the benzoate (1) of 9-decalyl hydroperoxide rearranges on standing by way of l-benzoyloxy-1,6-epox-ycyclodecane (2) to the hydroxycyclodecanone L... 

The migration terminus is an oxygen atom. The unstable hemiketal intermediate readily hydrolyses to give the final products. This, not surprisingly, is called the hydroperoxide rearrangement. 

In the hydroperoxide rearrangement, a hydroperoxide, R3C-0-0-H, fragments under acidic conditions to give a ketone and an alcohol. 

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