COMMUNICATIONS TO THE EDITOR
Dec. 20, 1956
6417
the e ~ t e r , ~ *dimethoxymethylborane, 5 CHaB (0- during transfers of the peroxide in vacuo and a CH3)2, (11), but is instead dimethylborylmethyl- third during a peroxide preparation. The compound should be handled cautiously. peroxide, (CH3)zBOOCH3, (I). (I) was prepared by reaction of oxygen and triAcknowledgment.-We wish to express our apmethylborane in a flow system a t room temperature preciation to John W. Kraus for the determinaand 1C-15 mm. pressure and a 2-3 minute contact tions of the mass spectra and to Dr. Earl W. Malmtime. At molar flow ratios of oxygen to trimethyl- berg for his counsel. borane of 2:1, the reaction is quantitative (Table THEOHIOSTATEUNIVERSITY ROBERT C.PETRY I). The peroxide, which appears t o be the only COLUMBUS 10, OHIO FRANKH. VERHOEK product of this reaction, is a colorless liquid of negRECEIVED NOVEMBER 12, 1956 ligible vapor pressure at -118'. Its vapor pressure curve lies between those of the esters methoxydimethylborane and dimethoxymethylborane. THE C-3 CONFIGURATION OF CERTAIN INDOLE ALKALOIDS The peroxide liberates iodine quantitatively from a degassed sodium iodide-isopropyl alcohol solu- Sir : tion acidified with glacial acetic acid, by the I n connection with studies on the stereochemissuggested equation try of indole alkaloids containing the ring system of (CH3)zBOOCHa 212H+ + yohimbine, ajmalicine, or (CHa)zBOCHa Hz0 Iz (1) corynantheine, we have 100 Supporting evidence for equation (I) is obtained had occasion to inspect the from the reaction of the peroxide with two equiva- infrared spectra of chloro90 form solutions of various lents of anhydrous hydrogen iodide a t -78'. Methoxydimethylborane, identified by its vapor pairs of C-3 epimers. It 8o pressure curve6 and mass spectrum, was isolated became apparent that the from the reaction mixture in 80% yield together 3.4-3.7 p region of the with substantial amounts of water and iodine. C-H stretching vibration However, there is some indication that the pri- can be used to identify o, mary products of this reaction are methanol and unmistakably the stereohydroxydimethylborane, and that the products iso- configuration of the hylated result from an esterification reaction during drogen atom a t C-3 of the & 60 alkaloids or their deriva- c fractionation of the reaction mixture. The peroxide (I) rearranges in a sealed tube in tives. Thus, all comthe liquid phase and in the gas phase (air absent) pounds possessing an CY- 9 50 a t room temperature to give approximately 90% of hydrogen a t C-3, ;.e., nora compound of identical molecular weight. Pre- m a l and allo products such E liminary results show that the rearrangement in as yohimbine2 (IA), d,l40 the gas phase and in benzene solution follows first alloyohimbane2 (IIA), and b order kinetics; the half-life in the gas phase is ap- ajmalicine2s3(IIIA) (illus30 proximately 60 days a t room temperature. The trated in the Figure berearranged product is dimethoxymethylborane low). exhibit two or more (11)) and shows the same mass spectrum, vapor dis{inct and characteristic 2o pressure curve, and molecular weight as samples peaks of medium intensity of I1 (b.p. 52.5', 747 mm.) prepared by the reac- bn the high-wave length tion of trimethylborate and methyl Grignard re- side of the major 3.46 p lo , agent. band. However, those I, 11 11i The peroxide (I) forms crystalline addition com- compounds containing a pounds when allowed to react with an equivalent C3-H o-orientation, i e . , tamount of ammonia or pyridine. This reaction pseudo or epiallo products produces no substances not condensed a t liquid such as - yohimbine2 nitrogen temperature, and preliminary results in- (IB), d,l - epialloyohimy? : dicate no appreciable destruction of the peroxide bane2 (IIB), and 3-isobond by adduct formation. The ester (11) forms ajmalicine (IIIB), m.P. Wave length in p. no adduct with pyridine. 193-194' (found: C, Fig. 1. The mass spectrum of the peroxide (I) is in 71.39; H, 6.96; N, 7.79), agreement with the proposed structure and is in- prepared by a zinc-acetic acid reduction4 of 3-dehyconsistent with the alternative hydroperoxide dr~ajmalicine,~ show merely shoulders on the high(CH~)ZBCHZOOH. Similarly, the hydroperoxide wave length side of the main peak.6 is excluded by consideration of the high vapor presOn the basis of the above spectrophotometric sure of I as compared to that of hydroperoxides, (1) This work was supported in part by a research grant (M 1301) the ease of rearrangement t o the ester (11) and the from the National Institutes of Health, Public Health Service, Department of Health, Education, and Welfare. nature of the reduction products. (2) For a recent review of the stereochemistry of this compound Three explosions have been encountered thus far derivatives, cf. J. E. Saxton, Quart. Reus., 10, 108 (1956). in the course of this investigation: two occurred and(3)related E . Wenkert and D. K . Roychaudhuri, I . O r g . Chem., in press.
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(4) J R Johnson and M G Van Campen, Jr , Tsrs JOURNAL, 60, 1 2 1 (1938) (5) E brankland, I C h m Soc , 16, 363 (1862) (0) 4 B Burg and K I Wagder, THISJ O U R N A L , 7 6 , 3872 (1953)
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(4) F. L. Weisenborn and P. A . Diassi, THISJOURNAL, 7 8 , 2022 (1956). (5) Egiallo compounds containing 18-aroyloxy groups, e.g., reserpine, show a fully developed extra peak instead of one of the shoulders.
ti318
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BOOKREVIEW
method, the following compounds are normal or nllo systems : yohimbine, yohimbone, yohimbane, &yohimbine, corynanthine, alloyohimbine, rauwolscine, 11-methoxyalloyohimbane and its racemate, methyl isoreserpate, corynantheine, ajmalicine, and tetrahydroalstonine,6 while the succeeding substances : reserpine, rescinnamine, deserpidine, methyl reserpate, 3-epi-a-yohimbine, $-yohimbine, and $-yohimbane,' m.p. 96-97' (found : C, 81.32; H, 8.57; N , 9.59), prepared by a zincacetic acid reduction4 of 3-dehydr0yohimbane,~ belong to the pseudo or epinllo series. The configurational assignment of these twenty compounds is in complete accord with their previously designated stereochemistry.2pa Infrared analysis suggests that the formerly proposed pseudo structure for serpineg and epiallo formula for methyl lS-desoxydeserpidatelO require reassignment into the normal or aIlo series. ( 6 ) Catalytic hydrogenation or sodium borohydride reduction r,f 3-dehydro or ring C tetradehydro compounds, c.E., alstonine, yields o n l y novnial or nllo products (as yet unpublished observations in this laboratory and cf. ref 3 and refermces contained therein). ( 7 ) T h e prep:irntim of this compound not only makes available t h e fourth and last, till now unknown, isomer of yohimbane, b u t also constitutes a total synthesis nf the same in view of its derivation from yohimbane and t h e formation of t h e latter from totally synthetic yohimhone [ O . 4 . Swan, J . Chem. SOL.,1534 (1950); J. Jost, Heiv. C h i m . Acta, 32, 1301 (1940)l. (8) (a) C . F. Huebner, M. E. Kuehne, B . Rorzun, and E. Schlittler, Exfiwic?ztia, 12, 249 (1956) and preceding papers; (b) E. E. van Tamelen. P. E. Aldrich, and T. J. Katz, Chemistry a n d Indtrstvy, 793 ( 1 9.W). (9) A. Chatterjee and S. Rnse, E+perientia, 10, 216 (1954).
The authors are most grateful t o Dr. Hochstein for informing them of t h e fact t h a t serpine is a mixture of yohimbine and rauwolscine (F. A. IIochstein, J . 0i.y. CIzem., in press). ( I O ) H. B. AlacPhillamy, C. F. I-Iuebner, E . Schlittler. A . F. St. Andre, and P. R . Ulshofer, THTSJ O U R N A L , 7'7, 433.5 (195.5). T h e authors are most thankful t o Dr. Huebner fur instructing them of t h e
Annual Review of Biochemistry. X'olnme 23. By J. MURR A Y LUCK,Editor, Stanford University, FRASK U'. ALLEN, Associate Editor, University of California, and GORDON MACKINSEY,Associate Editor, IJniversity of California. Annual Reviews, Iric,, Palo Alto, California. 39.56. is 794 pp. 16.5 X 23 cm. Price, $7.00.
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The current volume of the Annual Review of Biochctnistry represents the twenty-fifth anniversary of a n undcrtaking which has proved of tremendous valuc t o the busy scientist who wishes t o keep abreast of the biochemical litcraturc. As stated in 1932 by Dr. J . Mrirray Luck and his adviiory committec, it was hoped t h a t critical surveys of the literature would minimize the task of referring constantly t o original works. This goal has been admirably achieved by the Reviews in spite of the increasingly difficult task of examining critically the burgeoning field of biochemistry. The present volume includes among its many discriminating surveys a chapter completed by the friends and colleagues of Seymour Korkes as a tribute t o his memory. A prefatory chapter is devoted t o the life and work of Sir Edward Mellanby. The contents are as follows: Sir Edward Mellanby by n . S. Platt; Nonoxidative and Konproteolytic Enzymes by A . Meister; Proteolytic Enzymes by J . S. Fruton and M . J . hfycek; Carbohydrate Chemistry by E. J . Bourne and R .
Finally, the new analytical method permits the classification of fifteen alkaloids of unknown configuration. Aricine," tetraphylline," reserpinine," mayumbine,2 isoreserpiline,2 and corynaritheidinel2belong to the normal or allo series, while isorauhimbine,2 raunescine,13 i~oraunescine,'~ raujemidine, l 4 pseudoreserpine,'j isoreserpinine," raumitorine,*.l6 reserpiline,2.16and akuammigine2 are part of the pseudo or epiallo series of alkaloids. l7 DEPARTMEST OF CHEMISTRY IOWASTATECOLLEGE .AMPS, IO\\'A
ERSEST \ v E N K E R T
DILIP K. ROYCHAUDHURI
RECEIVEDNOVEMBER j,1956 fact t h a t he has succeeded in proving b y chemical means t h a t t h e above deserpidine derivative possesses t h e allo configuration. (11) T h e authors are most grateful t o Drs. Djerassi and Dias,i fin the information of t h e fact t h a t mercuric acetate oxidation, f < > l lowed by reduction, of the cited alkaloids has led t o the same stereo chemical assignment (C. Djerassi, J . Fishman, hf. Gorman, and J. 1'. Kutney, ibid., in press). ( 1 2 ) When considered along with the chemical evidence (ref. 8 b ) , t h e infrared d a t a suggest t h e d o configuration for this alkaloid. (13) N. Hosansky and E. Smith, J . Am. Plrarm. Assoc., Sci. Ed., 4 4 , 639 (1955). (14) P . R. Ulshafer, M . L. Pandow, and R. H . Xugent, J . Ovg. Chem., 21, 923 (19561. (15) Taken in conjunction Kith previous chemical evidence [M. \V Klohs, F. Keller, R . E. Williams, and G. W.Kusserow, Chemisfry a n d I n d u s t r y , 187 (1056)1, t h e infrared spectrum reveals t h e alkaloid t i , be a trimethoxybenzoyl derivative of methyl 17-demethyl-reserpatr (16) T h e stereochemical identification of these two substances can be considered only tentative a t this time because of t h e uncertainty r'f their spectra. I t would appear t h a t available samples might br admixed with an impurity t h a t absorbs also a t 3.4-3 7 p . (17) T h e authors are greatly indebted t o Professor Janot, Sir Robert Robinson and Drs. Aghoramurthy, Hofmann, Huebner. Klohs, Seuss, and Ulshafer f o r supplying them with samples and/or infrared spectra for this study and t o t h e Institute of Atomic Research. Iowa State College, for the use of a Baird infrared spectrophotometer
Stcphcns; Chemistry of the Lipides by 1'. I3. Shorlantl: Metaboliirn of Purines and Pyrimidines by C . E. Carter; Riochetnistrp of Viruses by F. \\/. Putnam; Metabolism of T,ipides by S. Rergitrijm and R . Rorgstrom; Riochrmistry of Cellular Particles by r\. C. Schneider and G . Hogebooni; Chemistry of the Fungi by C. E. Stickings and H . Raistrick; Biological Oxidations by S. F. L'elick; The Chemistry of Protcins and Peptides by H . Fraenkel-Conrat; The Henioglobins by H . A . Itano; hletabolism of Amino Acids and Proteins by E. A . Adelberg and M . Habinovitz; 1Vater-Soluble \'itamin
