Jan., 1935
COMMUNICATIONS TO THE EDITOR
229
These compounds yielded on pyrolysis isomeric pound. Under such alkaline conditions it is hydrocarbons of the composition C21H16 (m. p. possible for this derivative of glyceric aldehyde to 119 and 270", respectively), indicating that the undergo the well-known Lobry de Bruyn and method of synthesis is practical and that pyrolysis van Ekenstein rearrangement to give glucoIt was furthermore proceeds without migration of the aroyl group in sidodihydroxyacetone. the naphthalene nucleus. The ketone I was then pointed out that the alkaline degradation of melisynthesized as follows : p-bromotoluene was con- biose (6-galactosidoglucose) should yield 3-gaverted by the Blanc reaction into a mixture of lactosido-glyceric aldehyde as aE intermediate the two chloromethyl derivatives; this was treated stage in the reaction. Through the Koenig and Knorr reaction, with sodium malonic ester and the product was hydrolyzed and decarboxylated. Ring closure with powdered "Drierite" as a desiccant in the through the acid chloride mixture gave an easily chloroform, we have recently synthesized the separated mixture of two methylbromohydrin- glucosidodihydroxyacetone pentaacetate in good dones (m. p. 154 and 95") which on reduction yields by the use of bromoacetoglucose tetraby the Clemmensen method yielded the same acetate and dihydroxyacetone monoacetate rehydrindenr (b. p. 265-267"). The Grignard re- ported by Fischer, Baer and Feldmann [Ber.,63, agent from this hydrindene on reaction with a- 1732 (1930)]. This compound crystallized from naphthoyl chloride gave the ketone I (liquid) and ether, having in. p. 103" (corr.); [ a ] g -25.2" on pyrolysis of I there was obtained a yellow (CHCl3); an acetyl number equivalent to 10.81 hydrocarbon ( A n d . Calcd. for CzlHl6: c, 93.98; cc. of 0.1 N NaOH per 0.10 g. (calcd., 10.82). H, 6.02. Found: C, 04.11, 94.18; H, 6.26, 5.96) Its p-nitrophenylhydrazone crystallizes from alwhich when purified through the picrate formed cohol as a yellow derivative with m. p. 187" yellow needles melting at 176.5-17i.ti "; picrate (corr.); [a]:" -129.8" (CHC4); an acetyl 180-181". No depression in the melting points number equivalent to 8.37 cc. of 0.1 N NaOH per was observed on admixture with samples of methyl- 0.10 g. (calcd., 8.37). The study of the behavior of glucosidodicholanthrene (m. p. 176-177 ") and its picrate (m. p. hydroxyacetone pentaacetate toward deacetyla178-179 ") prepared from desoxycholic acid. This synthesis of a bile acid degradation product tion reagents as well as potassium hydroxide after having 21 of the 24 original carbon atoms and all the manner of Evans and Hockett (Zoc. cit.) is four of the original rings serves to confirm the now in progress in this Laboratory. The synaccepted structures and it opens the way to the theses of the corresponding galactosido compounds preparation of other hydrocarbons of interest in as well as the corresponding hexosido-glyceric the study of carcinogenic activity. Further work aldehyde ones are also being studied. in this direction is in progress. Before reporting DEPARTMENT OF CHEMISTRY L. C. KREIDER OHIO STATE UNIVERSITY WM. LLOYDEVANS the details of the above synthesis we are attempt- THE OHIO COLUMBUS, ing to establish the structures of the intermediates RECEIVED DECEMBER 20, 1934 obtained in the preparation of the ketone I, although this is not essential to a knowledge of STRUCTURE OF VITAMIN B the structure of the latter compound. Sir: LOUIS F. FIESBR CONVERSE MEMORIAL LABORATORY HARVARD UNIVERSITY ARNOLDM. SELIGMAX On treatment with sulfite the vitamin is quanCAMBRIDGE, MASSACHUSETTS titatively split into C6HBN3S03(I) and C6HeNS0 RECEIVED DECEMBER 17, 1934 (11). (I) on the basis of ultraviolet absorption and chemical evidence is a ti-aminopyrimidine THE PREPARATION OF GLUCOSIDODIsulfonic acid. We provisionally allocate -S03H HYDROXYACETONE PENTAACETATE to position 5 and --C~HS to position 4. Sir: The second cleavage product has been subIt has been pointed out by Evans and Hockett mitted to Dr. H. T. Clarke for examination. [THISJOURNAL, 53, 4384 (1931)] that in the alka- He has proposed a thiazole ring nucleus, which line degradation of gentiobiose (6-glucosidoglri- finding is confirmed by ultraviolet absorption cose) to lactic acid, 3-glucosidb-glyceric aldehyde studies. This base contains a free -OH group also present in the vitamin, gives a negative io&$ t'r a theoretically possible intermediate corn
