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COMMUNICATIONS TO THE EDITOR
Vol. 76
THE SYNTHESIS OF SPHINGOSINE effect, a value which stands in approximate theoretical agreement with the 2.92 f 0.07% result for Sir: the related CI3 effect according to a recent study.8 The structure of sphingosine (I) was conclusively Since the isotope effect ratio 2 is a clear prediction established by Carter and his co-workers.' Eviof the absolute rate theory, we have attempted to dence for the trans configuration of the double bond establish more firmly whether the malonic acid case has been presented recently by other investigadoes deviate by redetermining the CI3and C14intra- t o r ~ . ~We , ~ wish to announce the synthesis of molecular isotope effects, employing only mass trans - DL - erythro- 1,3-dihydroxy-2-amino-4-octadecspectrometric measurements. The results given ene (I). below are preliminary. Ethyl a-(trans-2-hexadecenoyl)-acetoacetate (II) Labeled malonic acid was synthesized v i a the (m.p. 33-34') was obtained in a 75% yield from cyanide-cyanoacetate route employed previously.6 the acid chloride and ethyl acetoacetate. Anal. The crude malonic acid was purified on a silicic Calcd. for C22H38O4: C, 72.1; H, 10.4. Found: acid column, using the n-butanol-chloroform sol- C, 72.2; H, 10.6. The Japp-Klingemann revent systemg; after preliminary concentration, action4 of (11) with benzenediazonium chloride the product was freed of solvents by sublimation afforded a 60-70% yield of the a-phenylazo ester in vacuo a t 95-100'. This material was diluted (111), m.p. 39-41'. Anal. Calcd. for C~H40N203: to the desired isotopic composition (about 1% C, 72.8; H, 9.3; N, 6.5. Found: C, 72.9; H, CI4, total carbon basis) with Eastman Kodak Co. 9.5; x, 6.2. b-hite Label acid which had been subjected to the CHI(CH~)Y~-CH=CH-CH-CH-CH~~H same manipulations. The mixture was recrystalI lized from acetone-benzene, resublimed, then OH AH2 (1) stored a t room temperature in a vacuum desiccator. CHI(CHZ)I~~!H=CH-CO-C-COOCZH~ The batch decomposition, combustion and deII X-XH-CtjHL (111) gradation techniques employed have been described in detail elsewhere8; all samples of carbon Reductive acetylation with zinc in acetic acid dioxide submitted for mass analysis were equili- gave a quantitative yield of the corresponding abrated first with standard water to eliminate the acetamido ester, m p . 62-63'. Anal. Calcd. for effect of variation in 0's content. C22H39N04: C, 69.3; H , 10.2; N, 3.6. Found: C, 69.8; H, 10.6; X, 4.0. TABLE I Selective reduction of the @-oxo group was effected with sodium borohydride under mild MOLEFRACTIONS FROM IONCURRENTRATIOS X lo6 Acetic acid Methyl carbon of conditions. The two diastereoisomeric carbinols COi evolved combustion acetic acid could be separated by crystallization. One of them 10420 10684 10661 (m.p. 64-65') was obtained in a pure state. Anal. e13 10416 10675 10657 Calcd. for C Z ~ H ~ ~ N C,O68.9; ~ : H, 10.7; S , 3.6. 10424 10681 Found: C,68.9; H, 10.8; hT,3.6. Saponification of the pure isomer with diluted 16313 8543 hydrochloric acid yielded ethyl 2-amino-3-hydroxyC14 16290 8581 4-octadecenoate hydrochloride, m.p. 110-1 12". 16299 8645 Anal. Calcd. for C20H40N03C1:C, 63.4; H, 10.7; In Table I are given the C13 and CI4 mole frac- N , 3.7; C1, 9.4. Found: C, 63.5; H , 10.6; N, tions obtained from three runs in which yields were 4.0; C1, 9.6. Direct treatment of the hydrochloride with an nearly quantitative; the results for carboxyl excess of lithium aluminum hydride gave the carbon of acetic acid were erratic, however. From (I \ . the data shown we calculate for the C14 effect desired lJ3-dihydroxy-2-aniino-4-octadecenc 3.45 f 0.46%, for the CI3 effect 2.85 f 0.09%; The erythro configuration of this base was proven the ratio of these is 1.91 f 0.17. Since the two by its hydrogenation to the corresponding dihydroheavy isotopes are present in approximately the sphingosine. The triacetyl derivative of (I) melted sharply same concentration in the carboxyl carbon atoms, the results obtained for C13 depend upon those for a t 90-91 O after one crystallization from methanol. CI4; accordingly, agreement of the present CI3 Anal. Calcd. for C24H43r\j06:C, 67.7; H, 10.1; ' , 8.3. Found: C, 6'7.9; H, 10.3; S , 3.6. figure with that obtained previously by the same h The presence of an allylic system involving the techniques applied to unlabeled starting material* increases our confidence in the CI4 result. We carbon atoms 3 , 4 and 5 was demonstrated by believe that these results indicate strongly that the hydrogenolysis of the secondary acetoxy group (1). the triacetyl derivative was shaken with iiialonic acid case can no longer be considered deviant from the predictions of the absolute rate platinum oxide and hydrogen, approxiitiately 50-607& of the theoretical amount o f acetic acid was theory. produced. SOYES LABORATORY OF CHEMISTRY PETER E. YANKWICH The infrared spectrum of the triacetyl coi~ipound UXIVERSITY O F ILLINOIS ALBERTL. PROMISWW URBANA, ILLINOIS ROBERT F. NYSTROhf showed the characteristic trans-peak2 near 1 0 . 3 ~ . (1) 13. E . Carter, E'. G . Glick, W. P. Sotris and G. E. Phillips, RECEIVED SEPTEMBER10, 1954 (8) i
P E I'ankaich and A. L Promislow, 'Ims J O U R V ~ I . 76, 4648
1554)
( 9 ) C 3 l f a f v e l and K D
an&, h d , 7 3 . 2642 (I55U)
J . Bioi. Chem., 170, 285 (1547,. ( 2 ) K. Mislow.THrs J O U R N A L , 74, 5155 ( l Y s 5 2 1 i Y ) G. Fodor, Ndture, 171, 651 (1853). , A j R . Jepp and F, Klinpcmann, Bzi.., 20, ?Y4'?, 2'234, 33YY I I Y Y 7 1 .
BOOK REVIEWS
Nov. 20, 1954
Further peaks were observed a t 9.53, 7.3, 6.82, 6.65, 5.99, 5.76, 3.4 and 2 . 9 ~ . These data are in good agreement with the infrared analysis of the triacetyl derivative of natural sphingosine recently reported b y Mislow.2 As a preliminary study of this route we carried out the above sequence of reactions on ethyl palmitoylacetoacetate and obtained the expected di-
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hydrosphingosine in good over-all yield. A synthesis of the latter involving a-phenylhydrazonop-oxo-stearic acid has been realized p r e v i o ~ s l y . ~ (6) crosby, Thesis, University of Illinois, 1848.
DANIELSIEFFRESEARCH INSTITUTE
wEIZMANN INSTITUTE OF SCIENCE
DAVIDSHAPIRO KHYAIM SEGAL REHOVOTII, ISRAEL RECEIVED SEPTEMBER 2, 1954
BOOK REVIEWS Flow Properties of Disperse Systems. Volume V of to be complimented on the diversity and scope of the areas Deformation and Flow Series. Edited by J. J. HERMANS,covered, which include the following topics: The PolyProfessor of Physical Chemistry, University, Leiden. morphism of Glycerides by T. Malkin, 50 pp., Autoxidation Interscience Publishers, Inc., 250 Fifth Avenue, New of Fats and Related Substances by Ralph T. Holman, 48 445 pp. 16.5 X 23.5 cm. pp., Nutritional Significance of the Fats by Harry J. Deuel, York 1, N. Y. 1953. xi Jr., 94 pp., The Surface Properties of Fatty Acids and AlPrice, 989.90. lied Substances by D. G. Dervichian, 50 pp.. Urea Inclusion This volume comprises reviews on a variety of topics, by Compounds of Fatty Acids by H. Schlenk, 25 pp., Infrared a number of authors, all of European origin. It therefore Absorption Spectroscopy in Fats and Oils by D. H. Wheeler, reflects the state of rheological thought in Europe, and while 24 pp., and Countercurrent Fractionation of Lipids by H. J. invaluable for this presentation perhaps does less than justice Dutton, 34 pp. to work in this field done in this hemisphere. The disperse The practice of assigning a particular subject to a specialsystems discussed include all types from coarse suspensions ist in the field is continued in Volume 2. Thus, Malkin preto macromolecular solutions such as the proteins. R . sents a strong argument for existence of four solid forms of Roscoe in a short section has given a lucid account of most triglyceride rather than the three proposed by Lutton. I t of the phenomena such as dilatancy, thixotropy and rheo- is unfortunate that Lutton’s views were not mentioned in pexy encountered in suspensions. E. G. Richardson de- greater detail. I t also seemed to this reviewer that since scribes the flow characteristics of emulsions and also con- Holman’s views on the autoxidation of fat differ from those tributes a section on liquid sprays, a subject which received of Hilditch, a brief review of Hilditch’s theories might have much study during the war years. The chapters on smoke been included. Deuel’s chapter on the Nutritional Signifiand atomization of liquids written by H . L. Green of the cance of Fats is very well done, the presentation is balanced British Chemical Defence Experimental Establishment by the inclusion of both sides of controversial issues. The likewise have military application and give the present state wide scope of material is well classified and well written. of theoretical knowledge in these subjects. The theory of The last four chapters provide valuable reference materialdilute solutions is covered in sections by Ch. Sadron and the chapter on Urea Inclusion Compounds seemed particuJ . J: Hermans, the former dealing with impenetrable rigid larly timely. particles while the latter gives the statistical approach to The physical aspects of this volume are, indeed, satisfacthe rheological behavior of flexible, long-chain molecules. tory. The book is attractively and durably bound, with the J. J. Hermans has contributed also a chapter on gels, their title in gold print. The printed text is clear and easily readswelling and elastic behavior, which, while valuable in it- able. Only one error in spelling was noted. Each chapter self, seems somewhat out of place in this volume. The be- contained many helpful sub-titles. I felt that a table of havior of foams is described by R. Matalon, while Mrs. B.S. contents a t the beginning of each chapter would have been Neumann treats the interesting but little understood flow desirable. phenomena encountered with powders of finely divided Volume I1 of Progress in the Chemistry of Fats and Other materials such as clay, flour and cement. Lipids is certainly to be recommended to all scientists interThis is a well documented book, carefully written and ested in the chemistry and biochemistry of lipids. would seem to be an essential for any worker in the field. DEPARTMENT OF BIOCHEMISTRY AND NUTRITION DEPARTMENT OF CHEMICAL ENGINEERING OF SOUTHERN CALIFORNIA UNIVERSITY USIVERSITY O F ROCHESTER Los ANGELES7, CALIFORNIA ROSLYNB. ALFIN-SLATER ROCHESTER 3, N.Y. G. BROUGHTON~
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(1) Deceased September 10, 1954.
Cell Chemistry, In Honor of Otto Warburg. Edited by DEANBURR,Foreign Member, Max Planck Institute for Progress in the Chemistry of Fats and Other Lipids. Edited Cell Physiology, Berlin-Dahlem (Germany), and Head by R. T. HOLMAN,Associate Professor of Physiological of Cytochemistry Section, National Institutes of Health, Chemistry, Hormel Institute of Minnesota, W. 0. LUNDUnited States Public Health Service, Bethesda, Md. BERG, Director, Hormel Institute of Minnesota and T. (U.S.A.). Elsevier Press, 402 Lovett Blvd., Houston, MALKIN,Reader in Organic Chemistry, University of Texas. 1953. 362 pp. 17.5 X 25.5 cm. Price, $7.50. Bristol. Academic Press, Inc., Publishers, 125 E. 23rd This is a ‘Testband” in the German tradition. I t was 347 pp. Street, New York 10, N. Y. 1954. vii published originally as Volume X I I , Numbers 1and 2 of the 16 X 24.5 cm. Price, $9.80. journal, Biochimia et Biophysica Acta, 1953. Its title is Although the structure of fats had been known long before perhaps more descriptive of Warburg’s activity than it is the structure of proteins or carbohydrates was elucidated, of the contents of the book, being as it is a collection of it is only recently that there has been an upsurge of interest thirty-seven articles and having as its only unification Some in lipid substances. This interest is reflected in the increas- contact with Warburg, either as a teacher or scientist. ing number of current books on this subject. The second The subject matter of these essays, although primarily series of “Progress in the Chemistry of Fats and Other biochemical in nature, varies all the way from straight orLipids” presents 3. review of the recent work in the whole ganic and physical chemistry through a major collectiori of range of fat c,icmistr I- mid biochrmiitry. The editor3 are biochemical cmtributions into cellul~r physiology itid
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