Metals, hydroperoxide oxidations

Metal-Catalyzed Oxidation. Trace quantities of transition metal ions catalyze the decomposition of hydroperoxides to radical species and greatiy accelerate the rate of oxidation. Most effective are those metal ions that undergo one-electron transfer reactions, eg, copper, iron, cobalt, and manganese ions (9). The metal catalyst is an active hydroperoxide decomposer in both its higher and its lower oxidation states. In the overall reaction, two molecules of hydroperoxide decompose to peroxy and alkoxy radicals (eq. 5). 

Retard efficiently oxidation of polymers catalysed by metal impurities. Function by chelation. Effective metal deactivators are complexing agents which have the ability to co-ordinate the vacant orbitals of transition metal ions to their maximum co-ordination number and thus inhibit co-ordination of hydroperoxides to metal ions. Main use of stabilisation against metal-catalysed oxidation is in wire and cable applications where hydrocarbon materials are in contact with metallic compounds, e.g. copper. 

Similarly, the metal-catalyzed oxidation of aryl alkyl sulfides by t-butyl hydroperoxide carried out in a chiral alcohol gives rise to optically active sulfoxides of low optical purity (e.e., 0.6-9.8%) (57). 

Pinene hydroperoxide (PHP) when compared with r-butyl hydroperoxide has been proposed as an excellent mechanistic probe in metal-catalysed oxidations. " If inter-molecular oxygen transfer from a peroxometal species to the substrate is rate limiting, the bulky PHP is unreactive, but for reaction of an oxometal species as the rate-limiting step, little or no difference is observed and only small differences in reactivity are observed when re-oxidation of the catalyst by ROOH to an active oxometal species is the rate-limiting step. 

The detailed mechanism for these Co AlPO-18- and Mn ALPO-18-cata-lyzed oxidations are unknown, but as previously pointed out vide supra) and by analogy to other metal-mediated oxidations a free-radical chain auto-oxidation (a type IIaRH reaction) is anticipated [63], This speculation is supported by several experimental observations that include (1) an induction period for product formation in the oxidation of n-hexane in CoAlPO-36, (2) the reduction of the induction period by the addition of free-radical initiators, (3) the ability to inhibit the reaction with addition of free-radical scavengers, and (4) the direct observation of cyclohexyl hydroperoxide in the oxidation of cyclohexane [62],... 

Several different organonitrogen compounds readily undergo metal-catalyzed oxidation using alkyl hydroperoxide or hydrogen peroxide as oxygen transfer agents. In 1961,... 

In the earlier volume of this book, the chapter dedicated to transition metal peroxides, written by Mimoun , gave a detailed description of the features of the identified peroxo species and a survey of their reactivity toward hydrocarbons. Here we begin from the point where Mimoun ended, thus we shall analyze the achievements made in the field in the last 20 years. In the first part of our chapter we shall review the newest species identified and characterized as an example we shall discuss in detail an important breakthrough, made more than ten years ago by Herrmann and coworkers who identified mono- and di-peroxo derivatives of methyl-trioxorhenium. With this catalyst, as we shall see in detail later on in the chapter, several remarkable oxidative processes have been developed. Attention will be paid to peroxy and hydroperoxide derivatives, very nnconunon species in 1982. Interesting aspects of the speciation of peroxo and peroxy complexes in solntion, made with the aid of spectroscopic and spectrometric techniqnes, will be also considered. The mechanistic aspects of the metal catalyzed oxidations with peroxides will be only shortly reviewed, with particular attention to some achievements obtained mainly with theoretical calculations. Indeed, for quite a long time there was an active debate in the literature regarding the possible mechanisms operating in particular with nucleophilic substrates. This central theme has been already very well described and discussed, so interested readers are referred to published reviews and book chapters . 

The intermediate formation of alkyl peroxide complexes has been postulated, and in several cases observed with spectroscopic and spectrometric techniques in several selective procedures based on metal catalyzed oxidation with hydroperoxides, Ti and V ions being among the transition metals most widely used for this purpose. However, to date the few examples of alkyl peroxide complexes isolated and characterized in the solid state refer to (dipic)V0(00Bu-f)(H20) 8, synthesized by Mimoun and coworkers in 1983, and to a dimeric Ti complex [((/7 -OOBu-f)titanatrane)2(CH2Cl2)3] 9, synthesized by Boche and coworkers. ... 

IR spectrophotometry, 661, 662 TEARS assay, 667 hydroperoxide oxidation, 692 Upid hydroperoxides, 977-8 decomposition, 669 DNA adducts, 978-84 protein adducts, 984-5 ozone adducts, 734 ozonide reduction, 726 ozonization characterization, 737, 739 peroxydisulfate reactions, 1013, 1018 Alkali metal ozonides, 735-7 Alkaline peroxide process, pulp and paper bleaching, 623... 

C-H bond unreactive to insertion, 1160 flavonoid, 548-9, 550 hydroperoxide oxidation, 692 a-hydroxylation, 519-21, 522-3 IR spectrophotometry, 662 oxidation of alkenes, 521-5 Baeyer-VilUger, 784-7 transition metal peroxides, 1108-14 a,/S-unsaturated, 199-202, 246-7, 285,... 

The method of photosensitized oxygenation was successfully applied in the preparation of alcohols 265-270 from sylvestrene (264),207 and seems to be the most simple and successful method for the preparation of optically active rose oxides (272,273) from (+)- or (—)-citronellol C271).177 It may also be used for the preparation of certain organo-metallic hydroperoxides. Thus, the triphenyl-tin derivative of tri-methylethylene (274) undergoes a photosensitized oxygenation reaction with a rate similar to that of tetramethylethylene, giving rise to the hydroperoxides 275 and 276 219... 

It is clear from a recent review of the mechanisms of metal-catalyzed oxidations of hydrocarbons (89) that by far the most extensive studies have been on the oxidation of alkenes and aromatic compounds relatively little work on alkane oxidation is to be found. The studies on these reactions show that, if the reactivity is enhanced by a hard metal, it is often because the metal becomes involved in the free-radical reactions and generates further free radicals by the chain decomposition of hydroperoxides (39) ... 

While there are differences in mechanistic detail, studies by others (13, 25) substantiate the existence of allylic hydroperoxides as intermediates in the homogeneous, transition-metal promoted oxidation of cyclohexene. 

We studied the oxidation of cyclohexene at 70°C in the presence of cyclopentadienylcarbonyl complexes of several transition metals. As with the acetylacetonates, the metal center was the determining factor in the product distribution. The decomposition of cyclohexenyl hydroperoxide by the metal complexes in cyclohexene gave insight into the nature of the reaction. With iron and molybdenum complexes the product profile from hydroperoxide decomposition paralleled that observed in olefin oxidation. When vanadium complexes were used, this was not the case. Variance in product distribution between the cyclopentadienylcarbonyl metal-promoted oxidations as a function of the metal center were more pronounced than with the acetylacetonates. Results are summarized in Table V. 

Alkylperoxo species are extremely important reactive intermediates in the metal-catalyzed oxidation of hydrocarbons by alkyl hydroperoxides. 

In this metal hydroperoxide (or an equivalent such as Cu==0), molecular oxygen activates Cu to raise its oxidation potential to the required extent, but Cu also activates the oxygen in a manner quite... 

Aggarwal and co-workers have used Jackson s metal peroxide oxidants for the epoxidation of ketene thioacetals. This resulted in highly diastereoselective epoxide formation (>20 1 selectivity).136 Carmen Carreiio and colleagues showed that epoxidation of (S)-(2-p-tolylsulfonyl)-2-cyclohexan-1 -ol and its OAc and OMOM derivatives, with lithium tert-butyl hydroperoxide, proceeds with high stereoselectivity to give the syn epoxy alcohols.137... 

Because two or more radicals, R, are produced by the reaction of one initial polymer molecule, PH, the reaction speeds up as the reaction proceeds, as shown in Figure 15.8. (Note PH = A in this figure.) Autocatalytic oxidation kinetics are often prevalent with hydroperoxide and metal catalyzed oxidation of polymers. 

DOT CLASSIFICATION 8 Label Corrosive SAFETY PROFILE Poison by inhalation. A corrosive irritant to the eyes, skin, and mucous membranes. With the appropriate conditions it undergoes hazardous reactions with formic acid, hydrogen fluoride, inorganic bases, iodides, metals, methyl hydroperoxide, oxidants (e.g., bromine, pentafluoride, chlorine trifluoride, perchloric acid, oxygen difluoride, hydrogen peroxide), 3-propynol, water. When heated to decomposition it emits toxic fumes of POx. 

Because protein oxidation may occur at any stage of the manufacture of the product, it is necessary to assess the susceptibility of the protein to oxidation through several mechanisms. Hydrogen peroxide, tert-butyl hydroperoxide (TBHP), and light are often used to promote oxidation in protein samples. Metal ions such as Cu and Fe have been added to protein formulations to purposefully assess whether a protein is susceptible to metal-catalyzed oxidation. 

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