Radical additions peroxidation, manganese

Fig. 50 Manganese(III)-catalyzed radical addition/peroxidation reactions...

Unsymmetrical dialkyl peroxides are obtained by the reaction of alkyl hydroperoxides with a substrate, ie, R H, from which a hydrogen can be abstracted readily in the presence of certain cobalt, copper, or manganese salts (eq. 30). However, this process is not efficient since two moles of the hydroperoxide are consumed per mole of dialkyl peroxide produced. In addition, side reactions involving free radicals produce undesired by-products (44,66). 

The additional protection given to nylon by antioxidants has already been mentioned. Since the need is to protect against oxidation by free radicals, antioxidants are essentially of two types peroxide decomposers and radical scavengers. Reviews of these products are available [409,410,413] these should be consulted for details of the mechanisms involved. Peroxide decomposer types include compounds of manganese (II) or copper(I) and copper(II) complexes, such as azomethine bridge derivatives of the type represented by 10.160, of which numerous water-soluble or water-insoluble variants are possible [409]. These products have a catalytic action and are therefore used in very small amounts. 

Without additives, radical formation is the main reaction in the manganese-catalyzed oxidation of alkenes and epoxide yields are poor. The heterolytic peroxide-bond-cleavage and therefore epoxide formation can be favored by using nitrogen heterocycles as cocatalysts (imidazoles, pyridines , tertiary amine Af-oxides ) acting as bases or as axial ligands on the metal catalyst. With the Mn-salen complex Mn-[AI,AI -ethylenebis(5,5 -dinitrosalicylideneaminato)], and in the presence of imidazole as cocatalyst and TBHP as oxidant, various alkenes could be epoxidized with yields between 6% and 90% (in some cases ionol was employed as additive), whereby the yields based on the amount of TBHP consumed were low (10-15%). Sterically hindered additives like 2,6-di-f-butylpyridine did not promote the epoxidation. 

Olefins react with manganese(III) acetate to give 7-lactones.824 The mechanism is probably free-radical, involving addition of CH2COOH to the double bond. Lactone formation has also been accomplished by treatment of olefins with lead tetraacetate,825 with a-bromo carboxylic acids in the presence of benzoyl peroxide as catalyst,826 and with dialkyl malonates and iron(III) perchlorate Fe(C104)3-9H20.827 Olefins can also be converted to 7-lactones by indirect routes.828 OS VII, 400. 

Alkoxy radicals for ring expansion can be generated from alcohols by oxidative methods such as hypohalite thermolysis/photolysis [19a] and lead tetraacetate oxidation [19b], or peroxide reduction [19c]. The recent development of the hyper-valent organoiodine reagent (diacetoxyiodo)benzene (DIB) provides another way for efficient generation of alkoxy radicals (Scheme 11) [19d]. Additional oxidative methods to prepare cyclopropyloxy radicals include reaction of tertiary cyclopropanols or their silyl ether derivatives with various reagents such as manganese(III) tris(pyridine-2-carboxylate) [Mn(pic)3] [20a], Fe(III) salts [20b], and vanadyl ace-tylacetate [20c] (Scheme 12). 

Commercial poly(butadiene), which is mainly the 1,4 isomer, is also used to improve the impact resistance of polystyrene (Chapter 1). Polydienes also increase the rate of physical disintegration of polyblend containing them. The addition of a styrene-butadiene block copolymer e.g. SBS, page 9 et seq.) to polyethylene also accelerates the peroxidation of the latter. However, this system also requires a polymer-soluble transition metal ion catalyst e.g. an iron or manganese carboxylate) to increase the rate of photooxidation in the environment by the reactions shown in Scheme 5.3. The products formed by breakdown of alkoxyl radicals (PO ) (Scheme 3.4) are then rapidly biodegradable in compost (page 107 et seq.). 

Mn(III)TMPyP is a manganese porphyrin that acts as a superoxide dismutase (SOD) mimetic and peroxynitrite decomposition catalyst (Han et al., 2001). SOD mimetics described to date are unstable and are capable of catalyzing undesired side reactions in addition to the dismutation of the superoxide radical. Mn(III)TMPyP is an SOD mimetic with increased stability to pH and hydrogen peroxide. The rate constants for superoxide dismutation and peroxynitrite decomposition are 3.9 X 10 M s and... 

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