5.10 _ PRACTICAL ORGANIC CHEMISTRY ANEXO N° 2, Mutarrotacién de la D-Glucosa H OH H._cHO HOw, CHO HeCHO HOw" mie HY So HO” ~CH,OH HO” ~CH,OH (R)-2.3-D-dihydroxy~ (2R,3R)-2.3,4- (2S,3R)-2,3,4+ propanal trihydroxybutanal tihydroxybutanal (glyceraldehyde) (D-erythrose) (D-threose) Similar representations may be drawn for the open-chain structures of the other compounds, and the (R,S)-convention applied. A more detailed study on the structure of p-glucose based upon physical data and chemical reactivity has revealed that the open-chain formulation of the aldopentoses, aldohexoses, ketopentoses and ketohexoses is however an over- simplification. Thus, for example, in solution D-glucose exists as an equilibrium HO- HO. HH He. Oi Be on OH @ a B-p-glucopyranose e-D-glucopyranose in (3b) Aldehydo-D -glucose a \ HOW HOW. H HO~¥ 0. HO. ° OH OH OH ‘OH ‘OH ‘OH (4) (s) @-D-glucofuranose B-D-glucofuranose RGBrencia.- Furniss, B. et al., (Ed 10k of Practical Organic Chemistry,AUPHATIC COMPDUKDS 5.10 mixture of five forms. The cyclic structures are those which arise from hemi- acetal formation involving the carbonyl function of C-1 of the open-chain form (3a/b) with either (i) the hydroxyl group on C-5 (in 3a) to give two pyranose ring structures (1), @,D-glucopyranose, and (2), B-D-glucopyranose, or (ii) the hydroxy! group on C-4 (in 36) to give two furanose structures (4), a-p-gluco- furanose, and (5) B-p-glucofuranose. The open-chain structure has been drawn to emphasise the spatial relationships of the carbon-skeletal arrangement and the dispositions of the hydroxyl groups for hemi-acctal formation. The five- membered (furanose) ring structure is at right angles to the plane of the paper. The pyranose structure adopts the characteristic chair conformation of six- membered rings, Structures (1) and (2) differ from one another only in the configuration at the anomeric carbon atom (C-1), the hydroxyl group being axial («) in (1) and equa- torial (8) in (2). In the case of structures (3) and (4) the configuration at the anomeric carbon is that in which the hydroxyl group lies either below (a) [in (4)], or above (f) [in (5)] the general plane of the ring. In solution the equilib- rium ratio of the four cyclic and the acyclic structures is dependent upon the nature of the solvent; in aqueous solution at room temperature the percentage composition is (1), 36 per cent; (2), 64 per cent; (3), 0.0026 per cent; (4) + (5), <1 per cent. The composition reflects the relative thermodynamic stabilities of the relevant molecules under these conditions. The change in optical rotation which is observed when crystalline a-p-glucopyranose is dissolved in a solvent, and which results from the attainment of this equilibrium is termed mutarotation. X-ray crystallographic studies have shown that crystalline D-glucose as com- monly isolated exists in the x-D-glucopyranose form. Furthermore the stable chair conformation (1), in which the hydroxyl groups on C-2, C-3 and C-4, and the hydroxymethyl group on C-5 are equatorial, is preferred to the alternative chair conformation (6) in which these groups occupy axial positions. HO HON on HO! io oH SG ‘OH Ho. oI OH OH OH Oy (6) There has been a considerable amount of discussion over recent years on the nomenclature to be used to describe the various conformations which these ring structures may adopt. Several authoritative accounts are available.'*? Most, if not all, of the stable forms of crystalline aldose and ketose mono- saccharides exist in the pyranose structure. Each in solution, as with D-glucose, exists as an equilibrium mixture of open chain and of a- and f-anomers of the cyclic forms. The cyclic five- and six-membered structures formulated below are an illustrative selection of monosaccharides. 641