Sucrose oxidation

S. Brochette-Lemoine, S. Trombotto, D. Joannard, G. Descotes, A. Bouchu, and Y. Queneau, Ultrasound in carbohydrate chemistry Sonophysical glucose oligomerisation and sonocatalysed sucrose oxidation, Ultrason. Sonochem., 7 (2000) 157-161. 

Because of the wide availability of sucrose, oxidation of this disaccharide seems to be industrially attractive. However, aside from serving as a substrate for fermentation, very little sucrose is used as an industrial raw material. Nevertheless a wide range of products may be expected, as shown in Figure 21.11. 

Leupold, E.I, Schoenwaelder, K.H., Fritsche-Lang, W., Schlingmann Linkies, M.A, Heinz, G., Werner, D., and Franz, J. (1990) Preparation of sucrose oxidation product containing tricarboxy derivative for use in detergents. Patent DE 3900677. 

Photosystem Il-enriched particles from A. nidulans to be used for EPR were obtained by extraction of membranes with sulfobetaine detergents as described in (4) and suspended in 16 mM Mes, pH 6.0 containing 20Z (v/v) glycerol, 0.4 M mannitol, 10 mM CaClz, 8 mM MgCla and 1.6 mM KbHPOa. Photosystem II membranes from spinach were prepared as in (5) and suspended in 20 mM Mes, pH 6.3, 15 mM NaCl, 5 mM MgClz and 400 mM sucrose. Oxidation of the PS II acceptor side was accomplished with 5 mM ferricyanide (1) or by the quinone method (2) with 2 mM phenyl-p-benzoquinone (PPBQ). Bicarbonate depletion was done by incubation with Na-formate in the dark for 30 minutes (6). EPR spectra were recorded with the equipment described in (7). 

Sucrose (C,2H220], table sugar) is oxidized in the body by O2 via a complex set of reactions that produces C02(g) and H20(g) and releases 5.64X 10 kJ/mol of sucrose, (a) Write a balanced thermochemicai equation for the overall process, (b) How much heat is released per gram of sucrose oxidized ... 

Hickey D, Giroud F, Schmidke D, Glatzhofer D, Minteer SD. Enzyme cascade for catalyzing sucrose oxidation. 4C5 Catal, 2013 3(12) 2729-2737. 

C (decomp.) It is made by the oxidation of toluene-o-sulphonamide with alkaline permanganate. Saccharin has about 550 times the sweetening power of sucrose, and is used extensively as a sweetening agent, usually in the form of the sodium salt. The use of saccharin is restricted in the U.S. 

The apparent viscosity, defined as du/dj) drops with increased rate of strain. Dilatant fluids foUow a constitutive relation similar to that for pseudoplastics except that the viscosities increase with increased rate of strain, ie, n > 1 in equation 22. Dilatancy is observed in highly concentrated suspensions of very small particles such as titanium oxide in a sucrose solution. Bingham fluids display a linear stress—strain curve similar to Newtonian fluids, but have a nonzero intercept termed the yield stress (eq. 23) ... 

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. 

Catalytic oxidation ia the presence of metals is claimed as both nonspecific and specific for the 6-hydoxyl depending on the metals used and the conditions employed for the oxidation. Nonspecific oxidation is achieved with silver or copper and oxygen (243), and noble metals with bismuth and oxygen (244). Specific oxidation is claimed with platinum at pH 6—10 ia water ia the presence of oxygen (245). Related patents to water-soluble carboxylated derivatives of starch are Hoechst s on the oxidation of ethoxylated starch and another on the oxidation of sucrose to a tricarboxyhc acid. AH the oxidations are specific to primary hydroxyls and are with a platinum catalyst at pH near neutraUty ia the presence of oxygen (246,247). Polysaccharides as raw materials ia the detergent iadustry have been reviewed (248). 

Oxidation of Sucrose. Sucrose can be oxidized by HNO, KMnO, and peroxide. Under selected conditions using oxygen with palladium or platinum, the 6- or 6 -hydroxyls can be oxidized to form sucronic acid derivatives (29). 

To date (ca 1996) many potentially usefiil sucrose derivatives have been synthesized. However, the economics and complexities of sucrochemical syntheses and the avadabiLity of cheaper substitutes have limited their acceptance hence, only a few of them are in commercial use. A change in the price and availability of petroleum feedstocks could reverse this trend. Additional impetus may come from regioselective, site-specific modifications of sucrose to produce derivatives to facilitate and improve the economics of sucrochemical syntheses. For example, the microbe yigwbacterium tumifaciens selectively oxidizes sucrose to a three-keto derivative, a precursor of alkylated sucroses for detergent use (50). Similarly, enzymes have been used for selective synthesis of specific sucrose derivatives (21). 

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. 

Acetylsucrose [63648-81-7] has been prepared in 40% yield by direct acetylation of sucrose using acetic anhydride in pyridine at 40° C (36). The 6-ester has subsequently been obtained in greater than 90% yield, by way of 4,6-cycHc orthoacetate. Other selective methods for the 6-acylated derivatives include the use of alkyl tin reagents such as dibutyl tin oxide (37) and of dibutyl stannolane derivatives (38). Selective acetylation of sucrose by an enzymic process has also been described. Treatment of sucrose with isopropenyl acetate in pyridine in the presence of Lipase P Amano gave, after chromatography, 6-0-acetylsucrose (33%) and 4/6-di-O-acetylsucrose (8%). The latter compound has been obtained in 47% yield by the prolonged treatment (39). 

Sorbitol is the most important higher polyol used in direct esterification of fatty acids. Esters of sorbitans and sorbitans modified with ethylene oxide are extensively used as surface-active agents. Interesteritication of fatty acid methyl esters with sucrose yields biodegradable detergents, and with starch yields thermoplastic polymers (36). 

Surface-Active Agents. Polyol (eg, glycerol, sorbitol, sucrose, and propylene glycol) or poly(ethylene oxide) esters of long-chain fatty acids are nonionic surfactants (qv) used in foods, pharmaceuticals, cosmetics, textiles, cleaning compounds, and many other appHcations (103,104). Those that are most widely used are included in Table 3. 

Corundum (AljOj) Vegetable oil mists (except castor cashew nut, or similar irritant oils) Sucrose, Tin Oxide, Titanium Dioxide Silicoh Carbide... 

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)... 

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