Oxidation sorbitol

Supported gold nanoparticles have been used in sorbitol oxidation and compared with analogous Pd and Pt catalysts [41]. The catalytic data for the monometallic catalysts are reported in Table 13.8. Using carbon as a support, the reaction took... 

Polysorha.tes. Polyoxyethylene sorbitan esters [9005-63-4] are formed from the reaction of sorbitol esters with ethylene oxide. These emulsifiers are almost always employed in combination with sorbitan esters and are used in the same appHcations (36). 

Cychc carbonates result from polyols by transesterification using organic carbonates (115). Thus sorbitol and diphenylcarbonate in the presence of dibutyl tin oxide at 140—150°C form sorbitol tricarbonate in quantitative yield (116). 

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). 

The structure of these products is uncertain and probably depends on pH and concentrations in solution. The hydroxyl or carboxyl or both are bonded to the titanium. It is likely that most, if not all, of these products are oligomeric in nature, containing Ti—O—Ti titanoxane bonds (81). Thek aqueous solutions are stable at acidic or neutral pH. However, at pH ranges above 9.0, the solutions readily hydroly2e to form insoluble hydrated oxides of titanium. The alkaline stabiUty of these complexes can be improved by the addition of a polyol such as glycerol or sorbitol (83). These solutions are useful in the textile, leather (qv), and cosmetics (qv) industries (see Textiles). 

Most current industrial vitamin C production is based on the efficient second synthesis developed by Reichstein and Grbssner in 1934 (15). Various attempts to develop a superior, more economical L-ascorbic acid process have been reported since 1934. These approaches, which have met with htde success, ate summarized in Crawford s comprehensive review (46). Currently, all chemical syntheses of vitamin C involve modifications of the Reichstein and Grbssner approach (Fig. 5). In the first step, D-glucose (4) is catalytically (Ni-catalyst) hydrogenated to D-sorbitol (20). Oxidation to L-sotbose (21) occurs microhiologicaRy with The isolated L-sotbose is reacted with acetone and sulfuric acid to yield 2,3 4,6 diacetone-L-sorbose,... 

Sterile aqueous D-sorbitol solutions are fermented with y cetobacter subo >gichns in the presence of large amounts of air to complete the microbiological oxidation. The L-sorbose is isolated by crystallisation, filtration, and drying. Various methods for the fermentation of D-sorbitol have been reviewed (60). A.cetobacter suboyydans is the organism of choice as it gives L-sorbose in >90% yield (61). Large-scale fermentations can be carried out in either batch or continuous modes. In either case, stefihty is important to prevent contamination, with subsequent loss of product. 

A series of sorbitol-based nonionic surfactants are used ia foods as water-ia-oil emulsifiers and defoamers. They are produced by reaction of fatty acids with sorbitol. During reaction, cycHc dehydration as well as esterification (primary hydroxyl group) occurs so that the hydrophilic portion is not only sorbitol but also its mono- and dianhydride. The product known as sorbitan monostearate [1338-41 -6] for example, is a mixture of partial stearic and palmitic acid esters (sorbitan monopalmitate [26266-57-9]) of sorbitol, 1,5-anhydro-D-glucitol [154-58-8] 1,4-sorbitan [27299-12-3] and isosorbide [652-67-5]. Sorbitan esters, such as the foregoing and also sorbitan monolaurate [1338-39-2] and sorbitan monooleate [1338-43-8], can be further modified by reaction with ethylene oxide to produce ethoxylated sorbitan esters, also nonionic detergents FDA approved for food use. 

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. 

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). 

Hydrogenation reactions, particularly for the manufacture of fine chemicals, prevail in the research of three-phase processes. Examples are hydrogenation of citral (selectivity > 80% [86-88]) and 2-butyne-l,4-diol (conversion > 80% and selectivity > 97% [89]). Eor Pt/ACE the yield to n-sorbitol in hydrogenation of D-glucose exceeded 99.5% [90]. Water denitrification via hydrogenation of nitrites and nitrates was extensively studied using fiber-based catalysts [91-95]. An attempt to use fiber-structured catalysts for wet air oxidation of organics (4-nitrophenol as a model compound) in water was successful. TOC removal up to 90% was achieved [96]. 

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