Jan. 20, 1958 &I),
COMMUNICATIONS TO THE EDITOR
evaluated a t c1 = 0) I
497
The presence of delphoccine (whose properties we shall describe elsewhere) in Couch's material accounts for the fact that Couch's formula and constants differ from ours. The functionality of deltaline is C17H18(-OCOCH3)(-OCH20-)(-OCH&(>
NCH2CH3)(+C-CH3)(OH).3'4 Replacement of the hydroxyl group of deltaline with hydrogen and conversion of the acetoxyl group to hydroxyl produces delpheline.6*6 Treatment of deltaline with highly purified thionyl chlowhere y1 is the activity coefficient of solute 1. In this form, the result bears a striking resem- ride a t room temperature yielded chloroacetyldelblance to Svedberg's equation.8 Measurement of pheline, m.p. 173.3-173.5' (evac. cap.; cor.), the required quantities presents no unusual diffi- [CY]~'D-40.7' (CHCl3). Anal. Calcd. for Cz~H40culty. Provided that s1 >> SZ, the determination CINO7: C, 61.64; H, 7.66; C1, 6.74; N, 2.66; of SI is straightforward. The Gouy diffusiometer 0, 21.29. Found: C, 61.54; H, 7.66; C1, 6.69; has been used to determine the four diffusion coeffi- N, 2.65; 0 (Unterzaucher), 21.09. The reaction of chloroacetyldelpheline with LiAlH4 in refluxing cients of several three-component system~.~J~~6J Certain other methods for determining the molec- ethyl ether gave an excellent yield of delpheline, ular weight of a solute in a three-component sys- identical in m.p., mixed m.p., infrared spectrum, tem contain terms of the form c2(bIn yl/bc2): for Rr value, and optical rotation with specimens isoexample, light-scatteringlZand sedimentation equi- lated by us from D. occidentale and D. barbeyi and with a specimen kindly supplied by Dr. R. C. Cooklibrium. 13 I am much indebted to Dr. L. J. Gosting for son. The chromic acid oxidation' of lycoctonine helpful suggestions and advice. [(Ci,Hm(-OH HO-)(-OCH3)4(>NCHzCH3)(> CC(12) 1. G. Kirkwood and R. J. Goldberg, J . Chcm. Phyr., 18, 64 H20H) ] yields the aldehyde, l y c ~ c t o n a l ,reduci~ (1950). ble to the base, desoxylycoctonine, containing two (13) M.Wales and J. W. Williams, J . Polymer Sci., 8,449 (1952). C-methyl groups. DEPARTMENTS OF BIOCHEMISTRY AND DAIRYAND FOODINDUSTRIES We have synthesized desoxylycoctonine from OF WISCONSIN R. L. BALDWIN delpheline in two steps. The secondary hydroxyl UNIVERSITY 6 , WISCONSIN MADISON group of delpheline, corresponding to the acetoxyl RECEIVED DECEMBER 12, 1957 group in deltaline, was methylated by means of sodium hydride and methyl iodide. The resulting THE STRUCTURAL RELATIONSHIP OF DELTALINE, 0-methyldelpheline melts a t 102.5-103' (evac. DELPHELINE AND LYCOCTONINE' ~ (CHC13). Anal. Calcd. cap.: cor.); [ a I z 4-6.3' Sir: for CzsHdlNOe: C, 67.37; H, 8.92; N, 3.02; The alkaloid deltaline has been chemically CH30 (4), 26.78. Found: C, 67.44; H, 9.07; N, transformed into delpheline and the latter into 3.19; CH3O (Zeisel), 24.6. Hydrolysis of the acedesoxylycoctonine, a known degradation product tal function of 0-methyldelpheline with hot 10% of lycoctonine. These interconversions prove that sulfuric acid yielded desoxylycoctonine, identical lycoctonine, delpheline, and deltaline possess the in m.p., mixed m.p., infrared spectrum, and Rr same skeleton structure, and establish the func- value with the product prepared from lycoctonine tional relationship of these three important Del- by the procedure of Edwards and Marion.? phinium alkaloids, thus unifying much hitherto un(3) J. Harvey, Jr., Ph.D. Dissertation, University of Pennsylvania, related structural evidence. Moreover, we have February, 1953; Dissertation Abstr., 18, 178 (1953); C. A . . 48, found that all three alkaloids occur together in 27341 (1954). (4) E. W. Martin, Ph.D. Dissertation, Univeraity of Pennsylvania, Delphinium barbeyi Huth, along with traces of (1949). several other closely related bases. (5) J. A. Goodson, J . Chcm. SOC.,665 (1944). (6) R. C. Cookson and M. E. Trevett, ibid., 984, 2688 (1956). Deltaline was isolated as the major base of D. (7) 0. E. Edwards and L. Marion, Can. J . Chcm., 30, 627 (1952). barbeyi and D. occidentale. It melts a t 193.5-194' (evac. cap.; cor.), [crIaa~-28.5' (CH30H). DEPARTMENT OF CHEMISTRY MARVINCARMACK OF PENNSYLVANIA JAMES P. FERRIS Anal. Calcd. for C Z ~ H ~ ~ N C,O63.88; ~: H, 8.14; UNIVERSITY PENNSYLVANIA JOHNHARVEY,JR. N, 2.76; 0, 25.22; CH3 on carbon (3) 8.86; active PHILADELPHIA, OF CHEMISTRY PHYLLIS L.MAGAT DEPARTMENT H (l), 0.20; CH30 (3), 18.34. Found: C, 63.83; INDIANA UNIVERSITY ERICW. MARTIN INDIANA DANAW. MAYO H, 8.21; N, 2.79; 0 (Unterzaucher), 25.32; CHS BLOOMINGTON, RECEIVED DECEMBER 3, 1957 on carbon (Kuhn-Roth), 7.49; active H (Zerewitinoff), 0.20; CH3O (Zeisel), 18.75, 18.13. Deltaline was first isolated from I). occidentale by Couch.' An examination of specimens of deltaline COMPOSITION AND ENZYMATIC SYNTHESIS OF N-ACETYLNEURAMINIC ACID (SIALIC ACID) given to one of us (M. C.) by Couch revealed the invariable presence of another alkaloid, delphoc- Sir: Previous reports1m2ra indicated N-acetylneurcine, not previously reported and not readily separable from deltaline except by chromatography. aminic acid (NANA) to be an 11 carbon keto acid. (1) Presented before the Section of Pharmaceutlcal Chedstry and Biochemistry at the Fourth Pan-American Congress of Pharmacy and Biochemistry in Washlngton, D. C., November 7,1957. (2) J. F. Couch, TEXS JOURNAL, 58, 684 (1936).
(1) G. Blix, E. Llndberg, L. Odin and I. Werner, Acta SOC.Mcd.
Upial., 61, 1 (1958). (2) E. Klenk, Angcw. Chcm., 68, 849 (1956). (3) A. Gottschalk, Nature, 176, 881 (1955).
