Sucrose oxidation products

Barry and Mitchell were the first to oxidize sucrose with periodic acid, separating the product as a phenylhydrazone. On finding that, after oxidation, each of the two monosaccharides of the sucrose reacted with only one molar proportion of phenyhydrazine, these workers attributed to the oxidized sucrose not a dialdehyde, but the following hemialdal [bis(hemi-acetal) hydrate] structure. 

The conversion 3deld at the end of the electrolysis was very low (5%). However, these first results allowed us to identify the oxidation products of sucrose on a smooth platinum electrode. Particularly, it was important to confirm that it is possible to oxidize sucrose without breaking the acetalic bond. 

Ofner Method. This method is for the determination of invert sugar in products with up to 10% invert in the presence of sucrose and is a copper-reduction method that uses Ofner s solution instead of Fehling s. The reduced cuprous oxide is treated with excess standardized iodine, which is black-titrated with thiosulfate using starch indicator. 

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)... 

The hexoses that are the initial products of acid hydrolysis of sucrose (1) react at el vated temperature under the influence of acids to yield furfural derivatives (2). Thed condense, for example, with the phenols to yield triarylmethanes (3), these react furthei by oxidizing to yield colored quinoid derivatives (2, 4). Polyhydric phenols, e. g. resorj cinol, on the other hand, yield condensation products of Types 5 and 6 [2],... 

Hora et al. [3.19] described the complexity of protein stabilization by the example of recombinant, human Interleukin-2 (rhIL-2). Formulations with amino acids and mannitol/ sucrose are sensitive to mechanical stress e. g. by pumping. Hydroxypropyl-beta-cyclodextrin (HPcD) provides stability, but increases the sensitivity to oxygen. Polysor-bate 80 forms a mechanically stable product, but results in oxidation. In both cases contamination in the HPcD or traces of H202 in the Polysorbate may have been the starter for the oxidation. Brewster [3.20] reports, that HPcD stabilizes interleukin without forming aggregations and this results in 100 % biopotency. 

Oxidation Products of Sucrose. The essentially regiospecific oxidation by Agrobacterium tumefaciens, whose dehydrogenase exclusively generates 3 -ketosucrose, is the prototype of an entry reaction into modified sucroses. This ready access opened the way to manifold modifications at the 3 -carbonyl function (Scheme 2.16)." Chemical oxidation proceeds less uniformly, for... 

The only large-scale application of sucrose ethers appears to be to use poly-(9-(hydroxylpropyl) ethers, generated by alkoxylation with propylene oxide, as the polyol component for rigid polyurethanes —sucrose itself gives only brittle ones—which are used primarily in cushioning applications. The structures of these products, that is, the positions at which sucrose is alkoxylated and then carbamoylated with diisocyanates, and the type(s) of cross-linking involved, are not well defined though. 

Several products were also detected in base-degraded D-fructose solution acetoin (3-hydroxy-2-butanone 62), l-hydroxy-2-butanone, and 4-hydroxy-2-butanone. Three benzoquinones were found in the product mixture after sucrose had been heated at 110° in 5% NaOH these were 2-methylbenzoquinone, 2,3,5-trimethylbenzoquinone, and 2,5-dimethyl-benzoquinone (2,5-dimethyl-2,5-cyclohexadiene-l,4-dione 61). Compound 62 is of considerable interest, as 62 and butanedione (biacetyl 60) are involved in the formation of 61 and 2,5-dimethyl-l,4-benzenediol (63) by a reduction-oxidation pathway. This mechanism, shown in Scheme 10, will be discussed in a following section, as it has been proposed from results obtained from cellulose. 

No oxidation products of sucrose other than those produced by degradation have been described. Oxidation of sucrose with periodic acid has been carried out, but neither the method nor the products need to be considered for the present purpose. 

Although many workers have been interested in the production of oxalic acid from sucrose, it is probably true that sucrose cannot compete with other raw materials as a source of this acid. For example, sawdust has been found to be an excellent source of oxalic acid. It is possible, however, to arrest the oxidation of sucrose before the oxalic acid stage is reached and the much more valuable tartaric acid has been obtained in this way. Tartaric acid, at the moment manufactured from waste... 

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