Mannitol, oxidation

Reduction with) ascorbic acid, hydrazine, or NH2OH HC1, CN-, EDTA, F-, H202, mannitol, oxidation to vanadate, triethanolamine, tiron Citrate, F-, H202, hydrazine, Na5P3O10, NH2OH HC1, oxalate, SCN-, tartrate, tiron, triphosphate, oxidation to tungstate(VI)... 

Fic. 8. NAD polyol dehydrogenase in sera of CCl4-poisoned mice sorbitol, ribitol, and mannitol oxidation (pH 9.6 polyols as substrates). 

Reaction of olefin oxides (epoxides) to produce poly(oxyalkylene) ether derivatives is the etherification of polyols of greatest commercial importance. Epoxides used include ethylene oxide, propylene oxide, and epichl orohydrin. The products of oxyalkylation have the same number of hydroxyl groups per mole as the starting polyol. Examples include the poly(oxypropylene) ethers of sorbitol (130) and lactitol (131), usually formed in the presence of an alkaline catalyst such as potassium hydroxide. Reaction of epichl orohydrin and isosorbide leads to the bisglycidyl ether (132). A polysubstituted carboxyethyl ether of mannitol has been obtained by the interaction of mannitol with acrylonitrile followed by hydrolysis of the intermediate cyanoethyl ether (133). 

Absorption of mannitol (209), sorbitol (210), and xyfltol (4) from the intestinal tract is relatively slow, compared to that of glucose. In humans, approximately 65% of orally adrninistered mannitol is absorbed in the dose range of 40—100 g. About one-third of the absorbed mannitol is excreted in the urine. The remainder is oxidized to carbon dioxide (211). 

For the most part boric acid esters are quantitated by hydrolysis in hot water followed by determination of the amount of boron by the mannitol titration (see Boron compounds, boric oxide, boric acid and borates). Separation of and measuring mixtures of borate esters can be difficult. Any water present causes hydrolysis and in mixtures, as a result of transesterification, it is possible to have a number of borate esters present. For some borate esters, such as triethanolamine borate, hydrolysis is sufftciendy slow that quantitation by hydrolysis and titration cannot be done. In these cases, a sodium carbonate fusion is necessary. 

Nonionic Surface-Active Agents. Approximately 14% of the ethyleae oxide consumed ia the United States is used in the manufacture of nonionic surfactants. These are derived by addition of ethylene oxide to fatty alcohols, alkylphenols (qv), tall oil, alkyl mercaptans, and various polyols such as poly(propylene glycol), sorbitol, mannitol, and cellulose. They are used in household detergent formulations, industrial surfactant appHcations, in emulsion polymeri2ation, textiles, paper manufacturing and recycling, and for many other appHcations (281). 

Specific Volume of Gases Formed on Explosion. 723ml/g (NG 712ml) (Ref 46) Stabilization. Chromatographically pure Mannitol Hexanitrate was mixed with varying percentages of 22 stabilizers and the mixts tested for stability in the 100° heat test best results were obtained with a mixt of 96% MHN, 2% Amm oxalate, and 2% dicyandiamide (4.07% wt loss after 48 hours, 5.74% after 96 hours) (Ref 56). The use of ethylene oxide as a stabilizer is reported in Ref 27 Thermal Decomposition. Slow heating causes decompn at 150° with evolution of red fumes (Ref 20, p 249)... 

Oxidation of PI with chromium trioxide. Fraction PI was twice acetylated as described above. The peracetylated polysaccharide (75 mg), together with 20 mg of mannitol hexacetate as internal standard was dissolved in 1.5 mL of HCCI3, and treated with 1.89 mL of glacial acetic acid and 189 mg of chromium trioxide, at 50°C. Aliquots were removed at zero, 30, 60 and 120 min, water then added, and the material recovered by extraction with chloroform, hydrolyzed and analysed by GLC of derived alditol acetates. 

Another procedure for preparing 4-hydroxy-4,5-dihydroisoxazole 2-oxides derivatives in 86-100% yield, and published by the same group [27], is based on an oxidative cleavage of D-mannitol-derivatives furnishing 2 equiv. of identical enantiopure (2R)-2-methanesulfonyloxyaldehydes which can react with a-nitroacetate in the usual manner. 

An amount of 16 g. of the glycol (m. p. 18°) dissolved in 250 ml. of water was oxidized with 18 g. of silver chlorate and 0.3 g. of osmic acid. The reaction mixture yielded 3 g. of allitol and no D,L-mannitol. We may therefore assign the meso configuration to the divinylglycol melting at 18°, since on hydroxylation it yielded allitol, but not D,L-mannitol. 

In the course of work on the potentiometric titration of some oxidizing acids, Malaprade1 found the existing method for determination of periodic acid in periodic-iodic acid mixtures too inaccurate for estimation of small proportions of one component. He discovered that mannitol will reduce only the periodic acid and, furthermore, that it only reduces the acid to iodic acid.2 The following general reaction appeared to take place. 

The rate law of Eq. (15) holds at all pHs, despite the fact that is strongly pH dependent (see below). Free radical oxidation chemistry (60) appears not to be involved in these Fem-TAML catalyzed oxidations to any detectable degree. The efficient hydroxyl radical scavenger, mannitol (61,62), when added over the concentration range (0.5-2.0) x 10 3 M has no effect on the rate. This peroxide oxidation catalyzed by 1 does not proceed extensively via the hydroxyl free radical serving as the reactive intermediate. 

In 1977, Kellogg and Fridovich [28] showed that superoxide produced by the XO-acetaldehyde system initiated the oxidation of liposomes and hemolysis of erythrocytes. Lipid peroxidation was inhibited by SOD and catalase but not the hydroxyl radical scavenger mannitol. Gutteridge et al. [29] showed that the superoxide-generating system (aldehyde-XO) oxidized lipid micelles and decomposed deoxyribose. Superoxide and iron ions are apparently involved in the NADPH-dependent lipid peroxidation in human placental mitochondria [30], Ohyashiki and Nunomura [31] have found that the ferric ion-dependent lipid peroxidation of phospholipid liposomes was enhanced under acidic conditions (from pH 7.4 to 5.5). This reaction was inhibited by SOD, catalase, and hydroxyl radical scavengers. Ohyashiki and Nunomura suggested that superoxide, hydrogen peroxide, and hydroxyl radicals participate in the initiation of liposome oxidation. It has also been shown [32] that SOD inhibited the chain oxidation of methyl linoleate (but not methyl oleate) in phosphate buffer. 

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