Sugars carbohydrate oxidation

Levulinic acid is formed by the treatment of six-carbon sugar carbohydrates from starch or lignocellulosics with acids, or by add treatment plus a reductive step of five-carbon sugars derived from hemicellulose. Levulinic add can serve as a building block for the synthesis of many derivatives of interest may be the selective oxidation to succinic and acrylic add. [i-Acetylacrylic add could be used in the production of new acrylate polymers. 

One of the most useful methods for shortening the carbon chain of a sugar involves oxidation of a soluble salt of the aldonic acid with hydrogen peroxide in the presence of ferric acetate 184), Prior to the development of this method by Ruff, H. J. H. Fenton had shown that tartaric acid is oxidized by hydrogen peroxide in the presence of ferrous salts, but apparently no oxidative cleavage of carbon-carbon bonds was noted. The ferrous ion-catalyzed oxidation was extended to many carbohydrates by associates of Fenton (Chapter VI) and by other workers 185), The ferric ions used as the catalyst in the Ruff method permit the oxidation of aldonic acids but are inactive with respect to sugars. Ferrous ions are much less selective. 

Other non-carbohydrate starting materials have been converted into amino-sugars. Addition-oxidative elimination of a phenyl-selenium reagent has been used to convert the racemic dihydropyran (43) into the 2,3-unsaturated glycoside (44), which yielded g-lyxo, and a- and g-rlbo-epoxldes in the ratio 61 26 13 the minor epoxide was converted into methyl DL-desosamlnlde (45)... 

Certain aliphatic compounds are oxidised by concentrated nitric acid, the carbon atoms being split off in pairs, with the formation of oxalic acid. This disruptive oxidation is shown by many carbohydrates, e.g., cane sugar, where the chains of secondary alcohol groups, -CH(OH)-CH(OH)-CH(OH)CH(OH)-, present in the molecule break down particularly readily to give oxalic acid. 

The formation of a red precipitate of copper(I) oxide by reduction of Cu(II) is taken as a positive test for an aldehyde Carbohydrates that give positive tests with Benedict s reagent are termed reducing sugars... 

Reducing sugar (Section 25 19) A carbohydrate that can be oxidized with substances such as Benedict s reagent In general a carbohydrate with a free hydroxyl group at the anomenc position... 

Phosphorus. Eighty-five percent of the phosphoms, the second most abundant element in the human body, is located in bones and teeth (24,35). Whereas there is constant exchange of calcium and phosphoms between bones and blood, there is very Httle turnover in teeth (25). The Ca P ratio in bones is constant at about 2 1. Every tissue and cell contains phosphoms, generally as a salt or ester of mono-, di-, or tribasic phosphoric acid, as phosphoHpids, or as phosphorylated sugars (24). Phosphoms is involved in a large number and wide variety of metaboHc functions. Examples are carbohydrate metaboHsm (36,37), adenosine triphosphate (ATP) from fatty acid metaboHsm (38), and oxidative phosphorylation (36,39). Common food sources rich in phosphoms are Hsted in Table 5 (see also Phosphorus compounds). 

Oxidation of Carbohydrates. Oxahc acid is prepared by the oxidation of carbohydrates (7—9), such as glucose, sucrose, starch, dextrin, molasses, etc, with nitric acid (qv). The choice of the carbohydrate raw material depends on availabihty, economics, and process operating characteristics. Among the various raw materials considered, com starch (or starch in general) and sugar are the most commonly available. Eor example, tapioka starch is the Brazihan raw material, and sugar is used in India. 

The oxidation of carbohydrates is the oldest method for oxahc acid manufacture. The reaction was discovered by Scheele in 1776, but was not successfully developed as a commercial process until the second quarter of the twentieth century. Technical advances in the manufacture of nitric acid, particularly in the recovery of nitrogen oxides in a form suitable for recycle, enabled its successful development. Thus 150 t of oxahc acid per month was produced from sugar by I. G. Earben (Germany) by the end of World War II. 

Colorimetric Methods. Numerous colorimetric methods exist for the quantitative determination of carbohydrates as a group (8). Among the most popular of these is the phenol—sulfuric acid method of Dubois (9), which rehes on the color formed when a carbohydrate reacts with phenol in the presence of hot sulfuric acid. The test is sensitive for virtually all classes of carbohydrates. Colorimetric methods are usually employed when a very small concentration of carbohydrate is present, and are often used in clinical situations. The Somogyi method, of which there are many variations, rehes on the reduction of cupric sulfate to cuprous oxide and is appHcable to reducing sugars. 

Oxidation to Sugar Acids and Lactones. When the aldehyde group of an aldose is oxidized, the resulting compound is an aldonic acid (salt form = aldonate) (11)4. Some aldonic acids are products of carbohydrate metaboHsm. 

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