An effective, practical, large-scale adaptable procedure has been developed to selectively dehydrate the fructose portion of isomaltulose (glucosyl-a( 1-+6)-fructose] (6): heating in DMSO in the presence of a strongly acidic ion-exchange resin generates a-D-glucosyloxymethylfurfural ("a-GMF" , 3), isolable in yields up to 70%. A variety of ensuing reactions have been exploited concerning the generation of products with industrial application profiles such as aldol-type additions to the dicyanovinyl (16), nitrovinyl (20), and benzoylvinyl (21) derivatives, or to the polymerizable unsubstituted vinyl compound (25) and the GMF-acrylic acid (22). Oxidation to GMF-carboxylic acid (1 1) and reductive amination to GMF-amine 8 can be carried out without affecting the hydroxyl groups in the glucosyl portion; esterification of 11 with long-chain alcohols and N-acylation of 8 with fatty acid chlorides provide novel surfactants in which hydrophilic and hydrophobic parts of the molecule are separated by a heteroaromatic spacer.5-Hydroxymethylfurfural (HMF, l), readily generated from fructose by acid-induced dehydrationL21, has been designated as one of the few "petrochemicals" accessible from regrowing and a key substance between carbohydrate chemistry and mineral oil-based industrial organic Despite the fact, however, that the technology for its pilot plant-size manufacture has been elaborated[2,4,51, it is not produced on an industrial scale for several obvious reasons: its chemistry is not fully developed with respect to products with industrial application profiles, and, more aggravatingly, raw materials from petrochemical sources are still more economical.Glycosylated hydroxymethylfurfurals of type 2-5, if accessible economically on a large scale, would substantially broaden the scope of HMF applications: carbonyl olefination and polymerization yield hydrophilic polymers, attachmet of long-chain alkyl residues via the respective furoic acid, for example, leads to novel APGs (alkylpolyglycosides), i.e. biodegradable surfactants in which the hydrophilic sugar moiety and hydrophobic alkyl portion of the molecule are separated by a heteroaromatic spacer.
The utilization of inexpensive, bulk‐scale accessible, renewable disaccharides as organic raw materials necessitates their practice‐oriented conversion into products with different functional groups and, hence, broader application profiles. The backlog for the development of practical reaction channels to versatile building blocks from disaccharides being particularly obvious. Correspondingly, this account describes a series of examples by which the reaction potential inherent in disaccharides such as sucrose, lactose, maltose and isomaltulose is utilized towards the acquisition of versatile building blocks without cleaving the intersaccharidic linkage. ‐ The glucose portion of sucrose, e.g. can be converted into dihydropyranones with the carbonyl function at C‐2 or C‐4, the reducing glucose parts of maltose and lactose may be transformed into enediolone, enelactone, or enollactone structures, whilst the fructose moiety of isomaltulose elaborates a furan ring by threefold, acid‐induced elimination of water to yield the terminally O‐glucosylated HMF, i.e. glucosyloxymethyl‐furan‐2‐carboxaldehyde. ‐ All reaction sequences comply with criteria of practicallity and therefore being transformable to large scale without major changes. Another novel entry reaction into O‐functionalized disaccharide derivatives, the cathodic deprotonation and subsequent trapping of the mono‐anion with suitable reagents according to Hamann, was evaluated in terms of understanding the regioselectivity attainable through computer simulations of relevant conformers of sucrose in solution, and the corresponding molecular electrostatic potential (MEP) profiles.
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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
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