Oct., 1945
COMMUNXCATIONS TO THE
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1866
have as the second substituent a hydrogen atom. 166'. The first b o p of dulcitol gave 95% recovThe basis for this statement, as well as the basis ery with m. p. 187-188' (accepted value 188'). for the structure assigned to the free radical A mixture, in disproportionate amounts, of 1,4: formed in step 3, will be presented in our next 3,6-dianhydrosorbitol1 1,4:3,6-dianhydro-~-manpublication dealing with this interesting reaction. nitol, and 1,4:3,6-dianhydro-~-iditol was chromatographed to show three zones. The rate of GEORGE HERBERT JONES LABORATORY M. s. KHARASCH UNIVER6ITY OF CHICAGO ELWOOD V. JENSEN lactonization and delactonization of D-gluconic CHICAGO, ILLINOIS W. H. URRY acid was followed qualitatively since the acid and RECEIVED SEPTEMBER 14, 1945 the lactones occupied different positions on the column. Lemon juice was chromatographed and the ascorbic acid content was concentrated into a zone detectable by 2,6-dichlorophenolindophenol, CHROMATOGRAPHY OF CARBOHYDRATES AND Work is being continued on this method and SOME RELATED COMPOUNDS details will be communicated at a later date. Sir : LABORATORY B. W. L E W ~ We wish to report that we have developed a CHEMICAL "HE OHIO STATE UNIVERSITY M. L. WOLFROM method for the chromatography of the carbo- COLUMBUS, OHIO R. MAXGOEPP,J R . ~ hydrates and related polyhydroxy compounds. RECEIVED SEPTEMBER 19, 1945 Columns of adsorptive clays were used as ad(1) Atlas Powder Company Research Associate of The Ohio State sorbents; an example is a Florida clay sold by Research Foundation. the Floridin Co. of Warren, Pennsylvania, under University (2) Research Department, The Atlaa Powder Company Wilming. the name Florex XXX. As developer we have ton, Delaware. used various low molecular weight hydrophilic solvents such as the alcohols, hydroxylic ethers, ether, dioxane, ketones, acids, pyridine, and water, THE CONFIGURATION OF THE PYRANOSE RINGS IN POLYSACCHARIDES either singly or in admixture. Streak reagents that have been used on the ex- Sir. truded columns to detect the zones are alkaline If one accepts the assumption that the C-C permanganate, 2,Ci-dichlorophenolindophenol and and C-0 bond angles and distances occurring in acid-base indicators. Water was the eluting polysaccharides are those found in simple moleagent. cules, then two trans configurations are possible By the use of this method we have arranged a for a pyranose ring. The important difference large number of the members of this class of com- between these two trans configurations is the pounds in an adsorption series. This chromato- angle which the CI-and C4-to-glycosidic-oxygen graphic sequence shows the pxition each com- bond makes with the "plane" of the pyranose pound occupies on the adsorption column in rela- ring. tion to the other members. We have included in In the prcsent discussion we are concerned only this series three pentoses, nine hexoses, two hep- with those polysaccharides in which the glycosidic toses, six disaccharides, two trisaccharides, one oxygens are trans to one another. This includes tetrasaccharide, two other oligosaccharides, four polymers of @-glucose (cellulose), p-mannuronic glycosides, twenty polyhydric alcohols,seven poly- acid (alginic acid) and a-galacturonic acid hydric alcohol inner ethers, and ten acids, lactones (pectic acid), With this restriction it follows, or salts. Several positions in the sequence are then, that in one trans configuration of the occupied by more than one compound with the pyranose ring (I) the two carbon-glycosidic bonds make an angle of about 20' with the "plane" degree of resolution currently in use. As examples of the applicability of this method of the pyranose ring. In the other trans conthe following are given. On chromatographing figuration (11) this angle is about 90'. This a mixture containing equal amounts of sorbitol difference in angle results in a difference in the and D-glucose, the separated D-glucose zone fiber identity period when units of the same conshowed the presence of 1 0 0 ~ of o the added sugar figuration are joined together to make a long chain. by a reducing sugar determination, and the sor- A chain made with I has a projection per pyranose bitol zone showed 99.7% of the sorbitol by per- unit in the direction of the fiber axis equal to iodic acid oxidation. The sorbitol zone gave a 5.15 A., while $he projection for a chain made negative reaction toward Fehling solution. A from I1 is 4.37 A. mixture containing 98y0 sorbitol and 2% DIt is now generally accepted that the pyranose mannitol was chromatographed to exhibit the rings in cellulose are I.' Recent X-ray studies presence of two zones. A mixture of equal on fibers of sodium pectate2 and alginic acid' amounts of D-mannitol and dulcitol was chromato(1) Astbury and Davies, Nolure, 154, 84 (1944); Cox, ibid,, 164, graphed and each component eluted and crystal- 84 (1944). (2) Palmer and Lotzkar, Tms JOURNAL, 67, 883 (1945); Palmer lized. The first crop of mannitol gave a recovibid., in press. ery of 90% with m. p. 166-167'; a second crop and(8)Hartzog, Astbury, Nature, 155, 667 (1945). We wish to express our gave a further 6% with the same melting point. thank. to Dr. Astbiiry for kindly sending 11s a mpy of this paprr The accepted value for the m. p. of D-mannitol is before publication
