D-Glucose ring

As noted previously, it is difficult to closely combine starch and poly(s-caprolactone), because there is little interaction between these two molecules to promote miscibility. For this reason, it may be advantageous to chemically modify the poly(sacchaiide) chains, e.g. by esterifying the lydroxyl functional groups of the a-D-glucose rings with formic add (FA) as illustrated in Figure 10.15. 

Haworth formulas are satisfactory for representing configurational relationships in pyranose forms but are uninformative as to carbohydrate conformations X ray crystal lographic studies of a large number of carbohydrates reveal that the six membered pyra nose ring of D glucose adopts a chair conformation... 

The main raw material required for the production of viscose is ceUulose (qv), a natural polymer of D-glucose (Fig. 1). The repeating monomer unit is a pair of anhydroglucose units (AGU). CeUulose and starch (qv) are identical but for the way in which the ring oxygen atoms alternate from side to side of the polymer chain (beta linkages) in ceUulose, but remain on the same side (alpha linkages) in starch. 

Fig. 3. Equilibiium mistuie of D-glucose forms in solution. Pyranose ring forms predominate.

As a final example we consider noncovalent molecular complex formation with the macrocyclic ligand a-cyclodextrin, a natural product consisting of six a-D-glucose units linked 1-4 to form a torus whose cavity is capable of including molecules the size of an aromatic ring. Table 4-3 gives some rate constants for this reaction, where L represents the cyclodextrin and S is the substrate ... 

The widespread occurrence of long-range couplings in both furanose and pyranose derivatives explains why so many of the P.M.R. spectra of carbohydrate derivatives are apparently poorly resolved, even when the resolution of the spectrometer is above reproach. For example, the Hi resonance of the 1,6-anhydro-D-glucose derivative (12) is coupled to all of the other six ring protons. A further example of the line-broadening effect follows a consideration of the spectrum of 5,6-dideoxy-5,6-epithio-l,2-0-isopropylidene-/ -L-idofuranose for which the half-height... 

Fischer s original method for conversion of the nitrile into an aldehyde involved hydrolysis to a carboxylic acid, ring closure to a cyclic ester (lactone), and subsequent reduction. A modern improvement is to reduce the nitrile over a palladium catalyst, yielding an imine intermediate that is hydrolyzed to an aldehyde. Note that the cyanohydrin is formed as a mixture of stereoisomers at the new chirality center, so two new aldoses, differing only in their stereochemistry at C2, Tesult from Kiliani-Fischer synthesis. Chain extension of D-arabinose, for example, yields a mixture of D-glucose and o-mannose. 

D-Glucose or (+)-D-glucose D-Fructose or (-)-D-fructose DL-Glucose or (+)-glucose 2-Carb-S. Cyclic forms and their representation 2-Carb-5.1. Ring size... 

The following schematic representation of pyranose ring closure in D-glucose shows the reorientation at C-5 necessary to allow ring formation this process corresponds to the change from Fischer to modified Fischer projection. 

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