Manganese active, oxidations with

A highly active gamma-Mn02 can be produced by treating manganese(III) oxide with hot sulfuric acid ... 

These batteries are new systems which use a lithium-manganese composite oxide for the active material of the positive electrode a lithium-titanium oxide with a spinel... 

Ordinary alkenes (without an allylic OH group) have been enantioselectively epoxidized with sodium hypochlorite (commercial bleach) and an optically active manganese-complex catalyst. Variations of this oxidation use a manganese-salen complex with various oxidizing agents, in what is called the Jacobsen-Katsuki... 

Some years later, Miller and others (1996) described a modified TEAC assay that is able to determine the antioxidant activity of carotenoids. In the improved version, ABTS,+, the oxidant, is generated by oxidation of 2,2 -azinobis(3-ethylbenzothiazoline-6-sulfonic acid)(ABTS2 ) with manganese dioxide. A similar approach was described by Re and others (1999) in which ABTS was oxidized with potassium persulfate (Fig. 10.2), this version of the TEAC assay is applicable to both water soluble and lipophilic antioxidants (Re and others 1999 Pellegrini and others 1999). 

Some oxide-type minerals have been found to luminesce when irradiated. A simple example is ruby (aluminium oxide with chromium activator), which emits bright-red light. The phosphors are incorporated into colour television screens to emit the colours blue (silver-activated zinc sulphide), green (manganese-activated zinc orthosilicate), and red (europium-activated yttrium vanadate). 

Figure 1.1 XRD patterns for different manganese oxides before and after pretreatment in H2 at 420°C [17]. The top three traces correspond to the original Mn02, Mn2Os, and Mn304 solids used in these experiments, while the bottom three were obtained after H2 treatment. It can be seen here that the catalysts are all reduced to the same MnO phase regardless of the nature of the starting material. It was inferred that MnO is the actual working catalyst in all cases, hence the similarity in methyl benzoate hydrogenation activity obtained with all these MnO solids. (Reproduced with permission from Elsevier.)...

Also, other metal oxide coatings are possible, for example, electrochemically deposited manganese dioxide. Moreover, further electrocatalytically active oxides are research objectives, for example, oxides with spinel structure such as CoMu204 [36]. 

The total synthesis of the carbazomycins emphasizes the utility of the iron-mediated synthesis for the construction of highly substituted carbazole derivatives. The reaction of the complex salts 6a and 6b with the arylamine 20 leads to the iron complexes 21, which prior to oxidative cyclization have to be protected by chemoselective 0-acetylation to 22 (Scheme 13). Oxidation with very active manganese dioxide followed by ester cleavage provides carbazomycin B 23a [93] and carbazomycin C 23b [94]. The regioselectivity of the cyclization of complex 22b to a 6-methoxycarbazole is rationalized by previous results from deuterium labeling studies [87] and the regiodirecting effect of the 2-methoxy substituent of the intermediate tricarbonyliron-coordinated cyclo-hexadienylium ion [79c, 79d]. Starting from the appropriate arylamine, the same sequence of reactions has been applied to the total synthesis of carbazomycin E (carbazomycinal) [95]. 

The modified cephalosporin ceftobiprole (31-8), yet another compound that contains a double bond at the ring carbon, though in this case with a rather complex extended side chain, has shown activity in the clinic against some strains of multidrug resistant bacteria. The synthesis starts with the weU-precedented acylation of the cephalosporin (31-2), available in several steps from the commercially available 7-acetoxy cephalosporanic acid, with the activated thiadiazole carboxylic acid (31-1). The hydroxyl group in the product (31-3) is then oxidized with manganese dioxide to afford the corresponding aldehyde (31-4). This product is then condensed with the fcw-pyrrolidyl phosphonium salt (31-5), itself protected with the... 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

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