34577-24-7

Upstream product

• 1944-83-8 2-methyl-1-phenyl-2-propylhydroperoxide 
• 292-64-8 Cyclooctan 
• 100-86-7 2-Methyl-1-phenyl-2-propanol 

Relevant academic research and scientific papers

A putative monooxygenase mimic which functions via well-disguised free radical chemistry

The hydroxylation of cycloalkanes at 25°C by the syringe pump addition of tert-alkyl hydroperoxides (10 and 1 equiv based on catalyst) to deoxygenated acetonitrile containing cycloalkanes (0.64 M) and 0.61 mM of the catalyst, [Fem(III)2O(TPA)2(H2O)2]4+, is demonstrated to be a reaction which involves freely diffusing cycloalkyl radicals, i.e., free alkyl radicals.

Oxygen activation by metal complexes and alkyl hydroperoxides. Applications of mechanistic probes to explore the role of alkoxyl radicals in alkane functionalization

The mechanism of the oxidation of cycloalkanes by tertiary alkyl hydroperoxides catalysed by iron(III) dichlorotris(2-pyridylmethyl)amine IIICl2(TPA)>+ and by the acetate bridged (μ-oxo) di-iron complex III(TPA)2O(OAc)>3+ has been investigated.Product studies do not support oxidation via a high valent iron-oxo intermediate (formally FeV=O), but are consistent with a mechanism involving hydrogen atom abstraction from the alkane by alkoxyl radicals derived from the hydroperoxide.In the presence of a large excess of tert-butyl hydroperoxide, the oxidation of cyclohexane yields cyclohexanone, cyclohexanol and tert-butylcyclohexyl peroxide in more than stoichiometric amounts and, in the case of the mono-iron catalyst, one equivalent of cyclohexyl choride.Replacement of Me3COOH by hydroperoxides, which could yield tert-alkoxyl radicals having much shorter lifetimes than the tert-butoxyl radical prevents oxidation of the cycloalkane.The products obtained with these hydroperoxide mechanistic probes are those derived from the fast unimolecular reactions (generally β-scissions) of the corresponding alkoxyl radicals.The inapplicability of dimethyl sulfide as a mechanistically diagnostic trap for the putative FeV=O intermediate and the value of di-tert-butyl hyponitrite as a non-iron-based source of tert-butoxyl radicals are discussed.

The Role of Alkoxyl Radicals in Gif (GoAggv) Chemistry

The oxidation of cyclooctane using tert-alkyl hydroperoxides under GoAggv conditions has been examined using selected alkyl hydroperoxides as mechanistic probes. The results indicate that the products are formed by alkoxyl radical-induced reactions, there being no need to invoke any chemistry involving high valent iron-oxo species.

Catalysis by Phthalocyanines, XXVI. - Decomposition of Hydroperoxides on Iron and Cobalt Phthalocyanine

The decomposition of 7-cumyl hydroperoxide and tert-butyl hydroperoxide on iron or cobalt phthalocyanine in 1-chloronaphthalene, 1-bromonaphthalene and 3-chlorotoluene proceeds with evolution of oxygen and according to second order kinetics (Figures 2 and 3; Tables 1 - 3 and 7); the yield of oxygen is not quantitative (Figure 1, Tables 1 - 3 and 7).Evolution of oxygen is not observed in 1-methylnaphthalene and decalin. - In the presence of N-(2-naphthyl)aniline the oxygen yield decreases with increasing concentration of the inhibitor (Table 4).The inhibitor efficiency is influenced by substituents in the phenyl group (Table 5), a Hammett relation being fulfilled in the case of 3-Cl and 4-Cl or CH3O (Figure 4). - 2-Benzyl-2-propyl hydroperoxide decomposes without evolution of oxygen.The decomposition rate on cobalt phthalocyanine is influenced by the composition of the solvent systems (1-chloronaphthalene/decalin, 1-chloronaphthalene/3-chlorotoluene, 3-chlorotoluene/decalin) (Table 6). - The mechanism of the decomposition of the hydroperoxides, especially the stabilizing reactions of the radicals, and the attack of the inhibitors is discussed in the light of previous results.