Reactions with peroxides

Similar procedures have been used to prepare 4-hydroxy-dibenzothiophene (48%) [5], 4-hydroxydibenzofuran (50-60%) [6] and 1-hydroxyphenoxathiin-10,10-dioxide (49%) [4], 

Recently, the oxidation of dioctylmagnesium with dioxygen to give 1-octanol in high yield has been fully described [7], 

The general reaction between an organomagnesium compound and an organic peroxide is represented by the following equation  

Formation of Carbon-Sulfur, Carbon-Selenium and Carbon-Tellurium Bonds via Organomagnesium Compounds 

---

Peroxides 1-Naphthol + N -ethyl-N (2-methanesulfon-amidoethyl)-2-niethyl-1,4-phenylenediamine (peroxide reagent) A quinonimine dyestuff is produced on reaction with peroxides. [3]... 

A quinonimine dyestuff is produced on [3] reaction with peroxides. 

The dismutation (disproportioning) of two free radicals is accompanied by release of a portion of reaction energy as a light quantum. As the quantum yield of such a process is extremely low, the detection of this type of chemiluminescence is technically complicated. Several compounds like lucigenin and luminol have a high quantum yield after reaction with peroxide radicals. Therefore, they are widely used for the detection of these radicals, particularly in the examination of phagocyting cells. 

The comparison of the values of Ee0 for reactions of ketyl radicals with peroxides with those for reactions R1R2C 0H + R2C(0) show that the reaction of the ketyl radical with peroxide occurs with sufficiently higher Ee0 (see Table 6.30). Obviously, this is the result of strong additional repulsion in the nonlinear polyatomic transition state of the ketyl radical reaction with peroxide... 

The alkyl radicals possess reducing activity as well. In the disproportionation reaction, one alkyl radical reacts as an acceptor and another as a donor of the hydrogen atom. This is the reason for the reducing action of alkyl radicals in reactions with peroxides. 

Iron catalysis in oxidation reactions with peroxides, both hydrogen peroxide and alkyl hydroperoxides, is frequently regarded as just a Haber-Weiss-type system where hydroxyl... 

Many different oxidation reactions with peroxides and H202 as the oxidants and titanium silicates as the catalysts have been reported. 

Carbon-carbon bond formation reactions with peroxides are quite limited, in view of the synthetic features. However, the following atom-transfer reaction may be useful. Treatment of iodomethyl phenyl sulfone (45) with benzoyl peroxide generates an electrophilic benzenesulfonylmethyl radical, which adds to electron-rich 1-hexene to give the addition product (46) (eq. 4.18) [49-51]. The same treatment of bromoacetic acid and 1-hexene with benzoyl peroxide affords 7-butyl-7-lactone through the cyclization of the formed 7-bromoctanoic acid. 

The participation by metal catalysts in autoxidations may be divided into four main groups (a) reaction with peroxides (h) reaction with substrate (c) reaction with oxygen (d) reaction with alkoxy and alkylperoxy radicals. The latter (d) leads to inhibition rather than to catalysis. Each of these types of participation will be discussed in the following sections. 

These reactions provide yet another example of the generally observed trend (see Section II.B.3.c) that oxidations in the presence of high concentrations of metal catalysts proceed by different pathways than those in the presence of catalytic amounts. In the former case, direct reaction of the metal oxidant with the substrate is often implicated. At lower concentrations, the metal species produce chain-initiating radicals by reaction with peroxides. 

Hindered amine which formula is presented below is introduced into polymer. As a result of amine reaction with peroxide radicals formed during polymer oxidation process (Scheme 5) stable nitroxyl radicals are formed. Nitroxyl radicals may be formed only at those parts of polymers where there are peroxide radicals, i.e. process of thermo-oxidative (or photo-oxidative) destruction proceeds. Then one determines spatial distribution of nitroxyl radicals through the sample and so, it becomes possible to identify those regions of polymer in which oxidation reaction proceeds. 

---