COMMUNICATIONS TO THE EDITOR
3930
Vol. 77
have made theoretical calculations of the l / R 3 force modifications of the spectrum to be expected for myristamide (using both of the angles given it1 Fig. 1). These calculations support the interpretation of the 2120-2250 A. absorption as a crystal transition, in that the long-wave-length allowed component is predicted to occur in the a axis direction, split off by ca. 100 to 150 A., just as observed (and regardless of which angle is chosen). We have also made quantum-theoretical calculations of the direction of the transition moment for an amide model. I n the model an amide is regarded as a perturbed allyl anion5 with the nitrogen represented by a deepening of the coulomb potential on one of the end carbon atoms and the oxygen considered as being the same as carbon. The result is that the direction should be close to the nitrogen-oxygen line, but inclined toward the carbon nitrogen line. Of the two values fouiid in our experiments the one with an angle of 9.1' from the nitrogen-oxygen line is thus favored. Both the experimental and theoretical aspects of this investigation will be reported in detail in a forthcoming paper.
sive confirmation obtained through an 1I-methoxyalloyohimbane (IIa, R = R' = H ) (reserpane) synthesis which is stereochemically unambiguous insofar as the CI6-Cznasymmetric centers are con~erned.~ 6-Methoxytryptaminee (obtained through the route : 6-methoxyindole -t 6-methoxygramine methosulfate -t 6-methoxyindoleacetonitrile -+ 6-methoxytryptamine) was alkylated in boiling dimethylformamide by ethyl dl-cis-2-bromomethylcyclohexaneacetate,'~~ affording the lactam of dZ-cis-N-(P-3'indolylethyl) -2-aminomethylcyclohexaneacetic acid (111) [benzene solvate), m.p. 72.5-74.0" (Calcd. for CnoHa6Sz02.C6H6: C, 77.19; H, 7.97. Found: C, 77.02; H, 7.93). Heating I11 with phosphorus oxychloride in benzene, followed by platinum-catalyzed reduction of the unisolated A"ring-closed product, yielded the desired til-all0 base IIa, which melted a t 209-210" after crystallization from methanol. Infrared spectral comparison of chloroforni solutions of IIa and a reserpane derived by reduction from reserpone (IIb, IC, R ' = 0)9 showed the two substances to be, apart from the racemic nature of the former, identical.'" DEPARTMEKT OF CHEMISTRY D. L. PE-I.ERSOX~ Publication of our views on the nature of the remaining asymmetric centers in reserpine and deOF WASHISGTOS TI., T. Srhwsos UNIVERSITY SEATTLE, WASHINGTOS serpidine, including evidence relating thereto, is RECEIVED J U T E 1.3, 1955 :i 11 ticipatcd. 15) Calculation waF facilitated by use of full conlixuration interacAcknowledgment.--The authors wish to express tion A.S.IVf.0. calculations on allyl anion (H. D H u n t , D L Peterson their gratitude t o the Department of Health, Weland Tir. T. Simpson, t o be published) fare and Education for financial support (Grant NO. (6) National Science Foundation Predoctoral Fellow 19.54-195.5. G-3S92'! and t o S. R.Penick and Co. for a gift of reserpine. ( 5 ) T h e matter of t h e stereochemistry a t C Ain o m synthetic prodiict
T H E D/E CIS RING JUNCTURE O F RESERPINE
Sir: Reserpine, the potent hypotensive agent obtained from various species of Rauwolfia, has been Because of its proxiassigned the structure I
is deferred for t h e present. (0) S.Akabori and K. Saito, B e y . , 6SB, 2245 (1930).
( 7 ) G . Stork and R . Hill, THISJOURNAL, 76, 949 (1954). ( 8 ) Unpiiblished results obtained in this Laboratory. (9) C . P. Iluehner, H . B. hIacPhillamy, A . F. S t . Snrlr6 and E. Schlittler, Tins J O ~ J R N A I . ,7 7 , 473 (195.5). ( I O ) n ' c should like t u thank Dr. Schlittler and Dr. St. Andr6 for their n;siitance in establishing t h e identity of t h e two specimens. Tn addition, o u r base Ita was shown t o be identical with material obtained b y them via a different synthetic route.
DEPARTMEXT OF CHEMISTRY EUGENE E. VAS TAMELEN USIVERSITYOF WISCOXSIS PAULD. HANCE MADISON, WISCOSSIS KENNETH V. SIEBRASSE PAULE. ALDRICH RECEIVED MAY3, 1955 OCH3
I
R
R'
TIa, b
POLY-GLUTAMYL PTERIDINE COENZYMES
.%: It was recently demonstrated that the conversion mate relation to deserpidine (formula I with the 11methoxyl replaced by - H ) , Schlittler, et al., sur- of serine to glycine by a bacterial extract is demised that reserpine too possesses a D/E cis (allo) pendent upon DPX, Mn++, pyridoxal phosphate, ring juncture3; and Wintersteiner, et u Z . , ~ on the orthophosphate and catalytic levels of a new coenbasis of the intramolecular N-4 quaternization of zyme, Co C.1,2 Co C is isolated from Clostridium methyl reserpate tosylate, inferred the same rela- cylindrosporum, and substitutes for b u t is not identionship. We wish to report for this view conclu- tical with known folic acid derivatives. By means of fractional acetone precipitation, chromatography (1) L. Dorfman, A . Furlenmeier, C. F. Huebner, R . Lncas, H . B. on cellulose columns, and repeated paper chromaMacPhillamy, J. hl. Muller, E. Schlittler, R. Schwyzer and A. F. tography in various solvent systems,3five groups of St. Andre, H d v . Chim. Acta, 37,59 (1954). (2) N. Neuss, H . E. Boaz and J. W. Forbes, THISJOURNAL,76, pteridine derivatives with Co C activity have been 2463 (1954). separated in relatively pure form from extracts of
(3) H . B. MacPhillamy, L. Dorfman, C. F. Huebner, E. Schlittler and A. F. St. Andre, ibid.,77,1071 (1955). (4) P. A. Diassi, F. I.. Weisenborn, C . M. Dylion and 0. Wintersteiner, ibid., 77, 2028 (1955).
(1) B. E. Wright, Biochini el Biophys. Acta, 16, 165 (1955) ( 2 ) B. E . Wright, F e d . PTOC., 14, 308 (1955). (3) B. E ITright and E. R. Stadtman, unpublished data.
