Keller-Kiliani reaction

A part of the specimen N-93 was extracted with chloroform, and a glycoside fi action (S-chf) was obtained. The residue was extracted with methanol. For the reference, the chloroform extracts of the roots of C. caudatum and C. wilfordii were prepared and named A-chf and B-chf, respectively. All the chloroform extracts, S-chf, A-chf and B-chf, gave positive Keller-Kiliani reaction and Liebermann-Burchard reaction, showing the presence of 2,6-dideoxysugar and steroidal skeleton in their structures, respectively. However, the HPTLC pattern of S-chf on a silica gel plate developed by CHCl3-Me0H-H20 (65 35 10, lower layer) was different fi om those of A-chf and B-chf (Fig. 1)... 

Digoxin is a crystalline glycoside obtained from Digitalis lanata and no assay is required in the standard of the B.P, For the injection and tablets, however, application is made of the Keller-Kiliani reaction. The U.S,P, assays Digoxin by an application of the w-nitrobenzene reaction and a similar method, based on the work of Honk et al. has been adopted by the A.O.A.C, For the assay of digoxin injection and tablets the IJ.S.P. also uses the Keller-Kiliani method. Suitable examples of the m-dinitrobenzene and Keller-Kiliani methods are given below ... 

In an attempt to synthesize 2-desoxy-L-ribose, Mukherjee and Todd68 treated methyl 2,3-anhydro-jS-L-ribopyranoside (LXXII) with sodium thiomethoxide and then reduced the amorphous product. The sulfur-free sirup thus obtained was inert to the action of periodate and is therefore methyl 3-desoxy-/3-L-riboside (ayn., methyl 3-desoxy-/3-L-xyloside) (LXXIV) rather than the desired 2-desoxy derivative. The methylthio intermediate (LXXIII) was consequently a 3-methylthio-L-xylose derivative rather than a 2-methylthio-L-arabinose compound. The presence of a trace of the latter, however, is not wholly excluded since the sirupy desoxypentoside (LXXIV) gave a feeble green coloration in the Keller-Kiliani test, a reaction generally accepted as being specific for 2-desoxy-sugars. 

Cassaidine is a tertiary base and like cassaine may be titrated with the same indicators. It is easily differentiated by color reactions from cassaine. With sulfuric acid it yields an orange-colored solution and with sulfovanadic acid the color is raspberry red. With the Keller-Kiliani-Cloetta reagent (ferric chloride in a mixture of sulfuric and acetic acids) it gives an intense red solution (cassaine—golden yellow). It is much less soluble in the usual organic solvents than is cassaine. 

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