Glucose with methyl sulfoxide

The 3-epimer sugar derivative was synthesized in a similar manner as the parent compound except that the hydroxyl group at the C-3 position in diacetone-D-glucose was initially epimerized (13) by oxidation with methyl sulfoxide and acetic anhydride followed by reduction with sodium borohydride. 

The reaction of the aldehyde 174, prepared from D-glucose diethyl dithio-acetal by way of compounds 172 and 173, with lithium dimethyl methyl-phosphonate gave the adduct 175. Conversion of 175 into compound 176, followed by oxidation with dimethyl sulfoxide-oxalyl chloride, provided diketone 177. Cyclization of 177 with ethyldiisopropylamine gave the enone 178, which furnished compounds 179 and 180 on sodium borohydride reduction. 0-Desilylation, catalytic hydrogenation, 0-debenzyIation, and acetylation converted 179 into the pentaacetate 93 and 5a-carba-a-L-ido-pyranose pentaacetate (181). 

For methanol-insoluble, nondialyzable material. 6 Used 20 g. of D-glucose/50 ml. of methyl sulfoxide. Used 10 g. of D-glucose in 20 ml. of methyl sulfoxide. d In 20 ml. of methyl sulfoxide. Used 6 g. of monomer in 10 ml. of methyl sulfoxide, with the catalyst mixture given, i Used 13.3 g. of lactose/SO ml. of methyl sulfoxide. 

Phase equilibria in water have been described by Kelly, who studied the effect of hexoses, sucrose, and inorganic salts on each other. The conclusion was reached that, for sucrose, the solubility of the second solute influences the composition at the invariant point, but for D-fructose, this effect is zero because of the high solubility of this sugar in water. Viscosity and density have also been evaluated at different temperatmes in methyl sulfoxide, and were fitted to appropriate equations by use of least-squares methods. The apparent molal volume calculated in this way is in perfect agreement with the theoretical data, whereas the differences for D-glucose and sucrose are 8 and 4%, respectively. 

Many other amylose complexes are water-insoluble, and the complexes with methanol, 1-propanol, acetone, and butanone may be precipitated from solutions of amylose in methyl sulfoxide, as well as from aqueous solution. As amylose frequently forms crystalline complexes. X-ray diffraction patterns have been obtained for a number of them. Amylose-methyl sulfoxide complexes have a structure almost identical to those of amylose-ethylenediamine complexes, in which the complexing ratio is one ethylenediamine molecule per two n-glucose residues. The helix packing-diameter of the complexes, at least for complexes with linear aliphatic ketones, is dependent upon the chain-length of the molecule complexed, although other factors are also involved. ... 

CiP was also used in the synthesis of heteroaryl methyl sulfoxides combined with glucose oxidase as a hydrogen peroxide source, as shown in Scheme 6.1 [21]. Optically active heteroaryl alkyl sulfoxides are interesting compounds in organic chemistry, as they present a chelating center that can be used in asymmetric s mthe-sis. Moderate to good results were achieved depending on the substrate structure. The best results were obtained for the oxidation of sulfides with electron-rich heterocycles. 

Cyclodextrins, toroidal molecules composed of 6, 7 and 8 D-glucose units, are now commercially available at reasonable cost. They form inclusion compounds with a variety of molecules and often differentially include sulfoxide enantiomers29,30. This property has been used to partially resolve some benzyl alkyl, phenyl alkyl and p-tolyl alkyl sulfoxides. The enantiomeric purities after one inclusion process ranged from 1.1 % for t-butyl p-tolyl sulfoxide to 14.5% for benzyl r-butyl sulfoxide. Repeating the process on methyl p-tolyl sulfoxide (10) increased its enantiomeric purity from 8.1% to 11.4% four recrystallizations raised the value to 71.5%. The use of cyclodextrins in asymmetric oxidations is discussed in Section II.C.l and in the resolution of sulfmate esters in Section II.B.l. 

Both enantiomers of methyl p-tolyl sulfoxide are also prepared from diacetyl D-glucose giving, with mesyl chloride, and according to the base used, the (S)-methyl sulfinate with diisopropylethy-lamine or the (J )-methyl sulfinate with pyridine, which are then transformed with p-tolyhnagnesium bromide into the corresponding (5)- or (f )-methyl p-tolyl sulfoxide (eq 3). ... 

In redox reactions, isolated oxidative enzymes such as laccase C from Trametes and horseradish/soybean peroxidases (with mediators) have been shown to possess good catalytic activity in common ILs on syringaldizine and veratryl alcohol, respectively [35]. Recently, oxidase-peroxidase-catalyzed chemo- and stereoselective sulfoxidations of thioanisole and methyl-2-naphthyl sulfide have been successfully carried out with a system of Coprinus cinereus (CiP) peroxidase and Aspergillus niger glucose oxidase (GOD) in 10% water in [BMIM][PF6] (Scheme 2). An enantiomeric... 

The unsaturated ester 154 derived from D-glucose reacted stereospecifically with lithiated methyl methylthiomethyl sulfoxide to give the Michael s adduct... 

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