Polyhydric alcohols, oxidation

FenCon s reagent An aqueous solution of FeSO4 0rotherFe saltandhydrogen peroxide used for oxidizing polyhydric alcohols. 

Ethylene oxide, Polyhydric alcohol See Ethylene oxide Polyhydric alcohol, etc. 

Isotope effects have also been observed in whole cells. Acetobacter suboxydans selectively oxidizes polyhydric alcohols having a specific pattern of hydroxyl groups. It oxidizes D-mannitol at C-2 and C-5. When D-mannitol-I-t, D-mannitol-2-t, and D-mannitol-3-t are oxidized to D-ffuctose, the unlabeled half of the molecule is oxidized the more rapidly. This result was attributed188 to a primary isotope-effect at C-3, and a secondary isotope-effect at C-2. 

ETHYLENE OXIDE - PROPYLENE OXIDE - POLYHYDRIC ALCOHOL AND ETHYLENE OXIDE - PROPYLENE OXIDE AMINE CONDENSATES... 

Polyhydric alcohol mercaptoalkanoate esters are prepared by reaction of the appropriate alcohols and thioester using -toluenesulfonic acid catalyst under nitrogen and subsequent heating (16,17). Organotin mercapto esters are similarly produced by reaction of the esters with dibutyltin oxide (18). Pentaerythritol can be oxidized to 2,2-bis(hydroxymethyl)hydracryhc acid [2831-90-5] C H qO, ... 

Sulfation andSulfamation. Sulfamic acid can be regarded as an ammonia—SO. complex and has been used thus commercially, always in anhydrous systems. Sulfation of mono-, ie, primary and secondary, alcohols polyhydric alcohols unsaturated alcohols phenols and phenolethylene oxide condensation products has been performed with sulfamic acid (see Sulfonation and sulfation). The best-known appHcation of sulfamic acid for sulfamation is the preparation of sodium cyclohexylsulfamate [139-05-9] which is a synthetic sweetener (see Sweeteners). 

Esterification is one of the most important reactions of fatty acids (25). Several types of esters are produced including those resulting from reaction with monohydric alcohols, polyhydric alcohols, ethylene or propylene oxide, and acetjiene or vinyl acetate. The principal monohydric alcohols used are methyl, ethyl, propyl, isopropyl, butyl, and isobutyl alcohols (26) (see Esterification Esters, organic). 

Polyhydric Alcohols. (Polyols). An alcohol with three or more hydroxyl groups, each attached to a different carbon atom. They are w-sol and of sweetish taste, which tends to intensify with increasing hydroxyl content. Examples of polyols of ordn interest are listed below. Polyvinyl alcohol is considered in a separate entry as a polymer although it is defined as a polyhydric alcohol. Polyols, when nitrated, make excellent expls, proplnt binders, plasticizers, etc. Prepn can follow the procedure of Lenth DuPuis (Ref 3) which uses a methanol suspension of either sucrose or dextrose and a special Cu-Al oxide catalyst to yield 60-65% distillable polyols at 240° and 1500psi Refs 1) Beil — refs found under individual compds 2) CA, under Alcohols, Polyhydric for compds of current ordn interest 3) C.W. Lenth R.N. DuPuis, "Polyhydric Alcohol Production by Hydrogenolysis of Sugars in the Presence of Copper-Aluminum Oxide , IEC 37, 152-57 (1945) CA 39, 1391 (1945)... 

Hawley, Glossary of Chemical Terms , Van-Nostrand-Reinhold,NY (1976), 217 Addnl Refs 1) K.S. Warren, Study Nitrates of Polyhydric Alcohols as Explosives , PATR 1103 (1941) la) D.B. Bright et al, Development of Polyol Prepolymers Containing High Energy Oxidizing Groups , Report No S-13843, Contract AF 04(611>5690, Shed Devel Co, Emeryville (1961) (limited distribution) 2) A.D. McElroy, Basic Approach to Incorporation of NP Propellants , Rept No RPL TDR 6448, Contract AF 04(611)-9059, Callery Chem Co, Phlla (1964) 3)... 

Hamelin A, Ho Y, Chang SC, Gao X, Weaver MJ. 1992. Surface crystallographic dependence of voltammetric oxidation of polyhydric alcohols and related systems at monocrystaUine gold-acidic aqueous interfaces. Langmuir 8 975-981. 

A polyether-alcohol, prepared by co-condensation of ethylene oxide and propylene oxide with a polyhydric alcohol, was stored at above 100°C and exposed to air via a vent line. After 10-15 h, violent decomposition occurred, rupturing the vessel. It was subsequently found that exothermic oxidation of the product occurred above 100°C, and that at 300°C a rapid exothermic reaction set in, accompanied by vigorous gas evolution. 

In contrast to the oxidation of acyclic polyhydric alcohols in benzene,508 treatment of 1,2-O-isopropylidene-a-D-glucofuranose with silver carbonate-on-Celite in boiling methanol led to selective oxidation of the primary hydroxyl group, with the formation of the al-duronic acid derivative in 68% yield.517... 

W15. Williams-Ashman, H. G., Banks, J., and Wolfson, S. K., Jr., Oxidation of polyhydric alcohols by the prostate gland and seminal vesicle. Arch. Biochem. Biophys. 72, 485-494 (1957). 

Fuels cells are of interest both from energetic and environmental considerations. When methanol is fed directly to an anode, as in Direct Methanol Fuel Cells , electric power is generated, making the devices suitable for small and lightweight uses [53], Alternative fuels such as polyhydric alcohols like ethylene glycol and glycerol are much less volatile and toxic, on the one hand, and electrochemically oxidizable on the other [54]. Therefore, the electrochemical oxidation of various polyhydric alcohols has been investigated in acidic as well as in alkaline conditions. 

The electrochemical oxidation of polyhydric alcohols, viz. ethylene glycol, glycerol, meso-erythritol, xilitol, on a platinum electrode show high reactivity in alkaline solutions of KOH and K2C03 [53]. This electro-oxidation shows structural effects, Pt(lll) being the most active orientation. This results from different adsorption interactions of glycerol with the crystal planes [59]. 

Prominent co-catalysts for the Pt-on-carbon anode catalyst in the oxidation of polyhydric alcohols are Ru or Ce02 [54, 60]. Their increased resistance to poisoning with mainly CO during operation is associated with the existence of a bifunctional mechanism (Scheme 11.6). 

Hercules Method D90-3e (Ref 17, pll). Nitroglycerin by Periodic Acid Oxidation. NG and some other nitrate nitrogen esters which may be present in expl oils can be quantitatively denitrated to their, respective alcohols by action of methanol and coned HCl. On oxidizing the residue of polyhydric alcohols with periodic acid, H5I06, the secondary carbon and alcohol group in glycerin are oxidized to formic acid,... 

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