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case) bearing a cis-lj3-diaxial relationship to the 66.21; H, 7.96). The structure of the 16-epi ester group and thus juxtaposed for participation. compound was confirmed by oxidation with chroThis hypothesis was tested by treatment of stro- mic acid to regenerate the original ketone. I n orphanthidin 3-acetate with dilute methanol and der to liberate the C1, hydroxyl group, both epicevine for 20 hours4; strophanthidin was isolated meric D-orthoacetates were submitted to alkaline in 66% yie1d.I hydrolysis followed by treatment with mineral The Cla acetate in the germine series also ex- acid to effect rearrangement to the C-orthoacehibits this abnormal reactivity.* Now this group t a t e ~ . 16 ~ - Epicevagenine - C - orthoacetate (11) is evidently @(axially)-oriented5which requires, on crystallized with one molecule of benzene and the basis of a 1,3-diaxial facilitation, a p(axia1)- melted a t 276-279' dec., ["Iz1D - 10' (C 1.22, chf). orientation of the Czohydroxyl. It was therefore (Found: C, 9.09; H, 7.81. The two epimeric attractive to postulate similar disposition of the C-orthoacetates were compared in their behavior Cl6 and Czohydroxyl groups in cevine. The fol- toward lead tetraacetate, and cevagenine-c-ortholowing experiments establish this point. acetates was found to react a t a strikingly slower rate than the 16-epi compound, suggesting that the 1 6 and C1.i are trans-disposed hydroxyl groups a t c in the former and cis- in the latter. Since the hydroxyl group is undoubtedly a-oriented, the f' configurations are established as I11 and 11, respectlvely . The established &configuration of the Clo hydroxyl group in cevine now points strongly to a @-configurationfor the Czo hydroxyl group-a point concerning which there has been considerable :(3 s-cti) doubt.2m10 We have noted that the Cle hydroxyl -7 (3 :-e:-:! group of 16-epicevadine-D-orthoacetate 4-acetate Hydrogenation of 16-ketocevine 3,4-diacetate2 is relatively difficult to acetylate. This fact is over platinum oxide proceeded stereoselectively to consistent with the a (equatorial)-configuration give cevine 3,4-diacetate. The molecular model for the methyl group a t CZOwhich is held rigidly of the ketone shows that the CY- is much less hin- eclipsed with the c16 a-hydroxyl group and exerts dered than the @-facefor approach to the catalyst, serious crowding. One is forced to conclude that suggesting that reaction would proceed to give a the simple rules of conformational analysis must be regarded with caution in treating complex @-orientedhydroxyl. Sodium borohydride reduction of 16-ketoceva- structures. dine-D-orthoacetate 4-acetate3 afforded a mixture (9) S. M . Kupchan, THISJOURNAL, 11, 686 (1955). of cevadine-D-orthoacetate 4-acetate4 and 16(10) F. Gautschi, 0. Jeger, V. Prelog and R . B. Woodward, Hclo. Chim. Acta, 38, 296 (1965); K. Macek and 2. J. Vejdelek, Nafurc, epicevadine-D-orthoacetate-4-acetate, m.p. 3 14-316' 1173 (1955). dec., [ a I z 14-~ 65' (c, 1.17 chf). (Found: C, 116, (11) This work was supported in part by a grant (H-2275) from the
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*v9
= =
(7) H. B. Henbest and B. J. Lowell, Chemisfry and I n d u s f r y , 278 (1956), have independently presented an elegant demonstration of this effect in the sterol series. (8) &.g., the facile methanolysis of germine-14,15-acetonide 3,16diacetate, S. M. Kupchan and C. R. Narayanan, Chemistry and Indust r y , 251 (1955).
National Heart Institute of the National Institutes of Health.
DEPARTMENT OF CHEMISTRY OF WISCONSIN S. MORRISKUPCHAN UNIVERSITY MADISON,WISCONSIN WILLIAMS. JOHNSON RECEIVEDJUNE 25, 1956
BOOK REVIEWS i
Radiological Defense Laboratory, Westinghouse Electric Conference on Effects of Radiation on Dielectric Materials. Corp., General Electric Co.,National Bureau of Standards, NAVALRESEARCH LABORATORY. OFFICE OF TECHNICAL SERVICES, DEPARTMENTOF COMMERCE,Washington, and Knolls Atomic Power Laboratory. The papers include 169 pp. surveys of the radiation chemistry of organic systems and D. C. (Publication No. PB111863). 1956. v of the radiation synthesis of polymers, three surveys of ra20 X 26.5 cm. Price, $4.25. effects in polymeric systems, four papers on various This is a compilation of reports presented at a conference diation aspects of radiation on organic materials, and on the effects of radiation on dielectrics held at the Naval deleterious Research Laboratory in December, 1954. I t serves pri- eleven papers on the radiation physics of the solid state. marily as a survey of the scope of development and of inter- The solid state papers are concerned with changes in conduction, optical transmission, magnetic susceptibility and est in the subject a t that time in various university, governmental and industrial laboratories. Among the labora- lattice parameters in inorganic crystals due both to the tories represented are the University of Notre Dame, Naval effects of y-rays and to displacements resulting from fast neutron bombardment. Research Laboratory, Carnegie Institute of Technology, The twenty-one reports vary widely in detail; a one-half Brookhaven hTational Laboratory, Argonne National Laboratory, North American Aviation Corp., Bausch and Lomb page abstract in one case and thirty pages, including eleven of references, in another. A number of the papers appear Optical Co., Oak Ridge National Laboratory, Naval
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t o have been hastily written in order t o satisfy the obligation CLAUDELIEBECQ(edited by). “Proceedings of the Third for having spoken a t the Conference. In general the reInternational Congress of Biochemistry Brussels 1955.” ports are brief and heterogeneous in style. They do not Academic Press, Inc., Publishers, 125 East 23rd Street, serve t o give the reader any unified over-all comprehension Y. 1956. 544 pp. $15.00. New York 10, hT. of the subject matter of the Conference. “Proceedings of the International Conference on the PeaceThe content of this volume is extremely specialized. ful Uses of Atomic Energy.” Held in Geneva, 8 AugustWorkers in the field will find it useful as a catalog of work in Geology of Uranium and 20 August 1955. Volume 6. progress although the delay in publishing of over a year is Thorium.” .Columbia University Press, 2960 Broadway, somewhat unfortunate. It is not recommended to the genNew York 27, N. Y. 1956. 825 pp, $10.00. eral reader who merely wants a cursory review of the physical and chemical effects of radiation. “Proceedings of the International Conference on the Peaceful Uses of Atomic Energy.” H,fld in Geneva, 8 XugustCHEMISTRY DEPARTMENT 20 August 1955. Volume 7. Nuclear Chemistry and WATIONAL LABORATORY BROOKHAVEX Effects of Irradiation.” Columbia University Press, VPTON, L. I . , N. Y. ROBERTH . SCHULER 2960 Broadway, New York 27, N. Y. 1956. 691 pp. $10.00. “Proceedings of the International Conference on the PeaceProgress in Organic Chemistry. Volume 3. By J. ’CV. ful Uses of Atomic Energy.” Held in Geneva, 8 August-20 COOK,D. Sc., F.R.S., Editor, Principal, University ColAugust 1955. Volume 8. “Productiori Technology for lege of The South West of England, Exeter, Fellow of the Materials used for Nuclear Energy.” Columbia University College, London. Academic Press, Inc , University Press, 2960 Broadway, New York 27, N . Y . Publishers, 125 East 23rd Street, New York 10, N. Y. 1956. 627 pp. 110.00. 1955. viii 273 pp. 16 X 25 cm. Price, $7.80. “Proceedings of the International Conference on the PesceVolume 3 maintains the same high standards set in the ful Uses of rltomic Energy.” Held in Geneva, 8 Xugustpreceding two volumes. This particular work in the prog20 August 1955. Volume 9. “Reactor Technology and ress series is devoted to five topics. These topics are, (1) Chemical Processing.” Columbia University Press, 2960 Total Synthesis of Steroids (43 pages) by J. W. Cornforth, Broadway, New York 27, N. Y. 1956. 771 pp. S10.00. (2) Non-benzenoid Aromatic Compounds (37 pages) by W. Baker and J . F. W.McOmie, (3) The Fulvenes (97 pages) “Proceedings of the International Conference on the Peaceful Uses of Atomic Eneigy.” Held in Geneva, 8 Augustby Ernst D. Bergmann, ( 4 ) Organic Compounds of Lithium 20 August 1955. X’olume 15. “Atmlications of Radio(46 pages) by E . A. Braude and (5) Indole Alkaloids (49 active ysotopes and Fission Products*in Research and Inpages) by V. Boekelheide and V. Prelog. I n accordance dustry.” Columbia University Press, 2960 Broadway, Kew with the announced editorial policy of this series, Dr. Cook York 27, N. Y. 1956. 327pp. $7.50. has been eminently successful in obtaining contributors who are actively engaged in the development of the topics dis- “Proceedings of the International Conference on the Peacecussed in this volume. ful Uses of Atomic Energy.” Held in Geneva, 8 AugustThis is a well written book, and the reviewer has enjoyed 20 August 1955, Volume 16. “Record of the Conferreading these chapters. Synthetic schemes, interrelationence.” Columbia University Press, 2960 Broadway, New ships amongst complex compounds, discussions and arguYork27, S . Y . 1956. 203pp. $5.00.( ments, etc., have been clearly and concisely presented. Organic chemists xi11 find this a valuable review of the M. L . SMITH(edited by). “Electromagnetically Enriched Isotopes and Mass Spectrometry.” Academic Press, five topics covered in this volume. Inc., Publishers, 125 East 23rd Street, New York 10, N.Y. DEPARTMENT O F CHEMISTRY 1956. 272 pp. $8.00. WALTERM .LAUER USIVERSITYOF MIXNESOTA A. STOLL,T . L. JoIissox, J. .I. HOGG,J. K O R ~ I C N. ,M. MIXNEAPOLIS 14, MINSESOTA SUTER,G. E. ULLYOTAKD J. F. KERTVIN. Medicinal Chemistry.” Volume 11. A Series of Reviews Prepared under the Auspices of the Division of Medicinal Chemistry of the American Chemical Society.” John Wiley and Sons, Inc., 440 Fourth Avenue, New York 16, N. Y. BOOKS RECEIVED 1956. 311 pp. $10.00. Julie 10, 1956-July 10, 1956 MARVINJ. UDY (edited by). “Chromium. Chemistry of Chromium and Its Compounds.” Volume I . h C S HANSA . BETHEASD PHILIPMORRISOS. “Elementary S u Monograph KO, 132. Reinhold Publishing Corporation. clear Theory.” Second Edition. John Wiley and Sons, 430 Park Avenue, Sew York 22, K. Y. 1956. 433 pp. Inc., 440 Fourth Avenue, Kew York 16, X. Y. 1956. $11.00. 274pp. $6.25 DAVIDE. GREET, Editor. “Currents in Biochemical Re- HIROOMIUMEZAWA.“Quantum Field Theory.” Interscience Publishers, Inc., 250 Fifth Bvenue, ATery York 1, search 1956.” Interscience Publishers, Inc., 260 Fifth N . Y . 1956. 364pp. $9.75. .%venue, Kem York 1, N. Y . 1956. 697 pp. 510.00
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