Compounds dimerization, oxidative

The compound is oxidized by air to orange-red crystals, which are possibly 0=Ti(acac)2 or an oligomer. If, however, the mixture is refluxed in the absence of ammonia, a red dimer is formed (mp 214°C), to which the doubly bridged stmcture,... 

Oxaziranes are rapidly decomposed by the further action of peracids. As shpwn by Emmons and Krimm the oxazirane is converted into a carbonyl compound and a nitroso compound dimer. The reaction can be formulated via an oxazirane A -oxide intermediate [Eq. (30)]. 

Phenols (p-cresol, guaiacol, pyrogallol, catechol) and aromatic amines (aniline, p-tolidine, o-phenyldiamine, o-dianisidine) are typical substrates for peroxidases [90 -109]. These compounds are oxidized by hydrogen peroxide or hydroperoxides under peroxidase catalysis to generate radicals, which after diffusion from the active center of the enzyme react with further aromatic substrates to form dimeric, oligomeric or polymeric products. 

Azo compounds may be considered to have the carbon-nitrogen framework of dimeric nitroso compounds. The oxidation of one of the nitrogen atoms of an azo compound to an azoxy compound has been discussed in Chapter 15. The oxidation of the second nitrogen would give rise to one of the resonance forms of a nitroso dimer. Indeed, on oxidation of 4-methylcinnoline with hydrogen... 

Pyridinium cations are reduced electrochemically or by metals to neutral radicals of considerable stability, especially when merostabilization by an a- or y-substituent occurs thus (381) has been isolated. Bispyridinium compounds are particularly readily reduced to radical cations, such as (383). Radical (383 R = Me) is the active species of the herbicide paraquat. Pyridyl radicals without such stabilization dimerize and form bispyridinium compounds by oxidation. 

The pyridazine dioxide derivative (108) was made by intramolecular nitroso compound dimerization as shown (Scheme 23). 1,2-Oxathiin 2,2-dioxides are obtained by the addition of sulfuric acid to a,(3-unsaturated ketones, e.g. (109) — (110) (66HC(21-2)774). 1,2-Dithiins are synthesized from conjugated diynes using benzyl thiol reductive debenzylation of intermediate (111) by sodium in liquid ammonia at - 70°C gives, after aerial oxidation, the 1,2-dithiin (112) (67AG(E)698). 

Oxidation of chromans has been extensively studied, especially of those which resemble the tocopherols which act as antioxidants in nature and in food. The behaviour of a-tocopherol (vitamin E, 547) and many simpler model compounds under oxidizing conditions varies with the oxidizing agent. Among the many products formed are the o- and p-quinones (609) and (610), the spiran (611) and dimer (612). A detailed account is available (81HC(36)59). 

The most common oxidation states and corresponding electronic configurations of rhodium are +1 (tf8), which is usually square planar although some five coordinate complexes are known, and +3 (T) which is usually octahedral. Dimeric rhodium carboxylates are +2 (oxidation states —1 (industrial applications include rhodium-catalyzed carbonylation of methanol to acetic acid and acetic anhydride, and hydroformylation of propene to tf-butyraldehyde. Enantioselective catalytic reduction has also been demonstrated. 

The addition of nitrosyl chloride to alkenes is a well-known reaction1 3, nevertheless the mechanistic and stereochemical aspects are still not properly understood. The course of the reaction depends on the nature of the alkene and the experimental conditions. After the initial addition step, which gives a blue or sometimes green 1 1 adduct, three competitive pathways may be followed 1) dimerization of the nitroso group to give a white crystalline compound 2) oxidation of the nitroso group to a nitro group (see Section 7.2.1.8) 3) isomerization to a-chloro oximes. 

Naphthol can successfully be dimerized oxidatively, selectively through the o-site to give (22) using copper(II)-amine complexes (70%) or manganese(III) acetylacetonate (69%), and o-o coupling is the major paAway (90%) on ferricyanide oxidation of the trisubstituted phenol (23) to the orthodiphenoqui-none (24). In this context it is of interest that a compound obtained (74%) on ferricyanide oxidation of... 

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