The general principles of stereochemistry being discussed in Stereoisomerism (q.v.), we proceed to the synthesis of glucose and fructose and then to the derivation of their configurations.
The osazone prepared from a-acrose resembled most closely the glucosazone yielded by glucose, mannose, and fructose, but it was optically inactive; also the ketose which it gave after treatment with hydrochloric acid and reduction of the osone was like ordinary fructose except that it was inactive.
It was surmised that a-acrose was a mixture of dextro and laevo fructose, a supposition which was proved correct by an indirect method.
Fischer's a-acrose therefore led to the synthesis of the dextro and laevo forms Gf mannose, glucose and fructose; and these substances have been connected synthetically with many other sugars by means of his cyanhydrin process, leading to higher sugars, and Wohl and.
The hexoses so obtained are not necessarily identical: thus cane sugar yields d-glucose and d-fructose (invert sugar); milk sugar and melibiose give d-glucose and d-galactose, whilst maltose yields only glucose.
Boletus edulis, in the Oriental Trehala and in ergot of rye; melibiose, C12H22011, formed, with fructose, on hydrolysing the trisaccharose melitose (or raffinose), C18H32016.5H20, which occurs in Australian manna and in the molasses of sugar manufacture; touranose, C12H22011, formed with d-glucose and galactose on hydrolysing another trisaccharose, melizitose, C,8H32016 2H20, which occurs in Pinus larix and in Persian manna; and agavose, C12H22011, found in the stalks of Agave americana.
The following figures obtained by Mach afford an interesting illustration of these processes At first the sugar in the juice consists entirely of dextrose, but later fructose (laevulose) is formed.
A yeast, which saccharifies starch, it is possible to tell whether maltose or levulose and fructose are formed; if the former, only those plates containing P. phosphorescens will become luminous; if the latter, only those containing P. Pflugeri.
Nor is the nature of the first formed sugar certain; the general opinion has been that it is a simple hexose such as glucose or fructose, C6Hi2O,.
Of especial note is the transformation of maltose by maltase into glucose, and of cane sugar by invertase into a mixture of glucose and fructose (invert sugar); other instances are: lactose by lactase into galactose and glucose; trehalose by trehalase into glucose; melibiose by melibiase into galactose and glucose; and of melizitose by melizitase into touranose and glucose, touranose yielding glucose also when acted upon by the enzyme touranase.
Our knowledge of the chemical structure of the monosaccharoses may be regarded as dating from 1880, when Zincke suspected some to be ketone alcohols, for it was known that glucose and fructose, for example, yielded penta-acetates, and on reduction gave hexahydric alcohols, which, when reduced by hydriodic acid, gave normal and secondary hexyliodide.
He prepared the cyanhydrins of glucose and fructose, hydrolysed them to the corresponding oxy-acids, from which the hydroxy groups were split out by reduction; it was found that glucose yielded normal heptylic acid and fructose methylbutylacetic acid; hence glucose is an aldehyde alcohol, CH 2 OH (CH OH) 4 CHO, whilst fructose is a ketone alcohol CH 2 OH (CH OH) 3 CO.
It is seen that aldoses and ketoses which differ stereochemically in only the two final carbon atoms must yield the same osazone; and since d-mannose, d-glucose, and d-fructose do form the same osazone (d-glucosazone) differences either structural or stereochemical must be placed in the two final carbon atoms.3 It may here be noticed that in the sugars there are asymmetric carbon atoms, and consequently optical isomers are to be expected.
A separation of a-acrose was made by acting with beer yeast, which destroyed the ordinary fructose and left /-fructose which was isolated as its osazone.
The ketone is also obtained when Bertrand's sorbose bacterium acts on glycerol; this medium also acts on other alcohols to yield ketoses; for example: erythrite gives erythrulose, arabite arabinulose, mannitol fructose, &c.
The reader is referred to Glucose and Fructose for an account of these substances.