123
Jan. 5, 1963
BOOK REVIEWS Introductory Organic Quantum Chemistry. By GEORGKARAGOUKIS, Professor of Physical Chemistry, University of Freiburg, Germany. Translated and Edited by F. C. h-achod, Sterling-Winthrop Research Institute, Rensselaer, Kew York. Academic Press Inc., 111 Fifth Avenue, New York 3, N. Y . 1962. viii 204 pp. 16 X 23.5 cm. Price, $6.50.
+
This book is intended as an introduction to quantum theory for organic chemists with a limited knowledge of mathematics. .I good book of this kind could be useful, although there are already several excellent texts available, but unfortunately this is not a good book. On the contrary it is one of the poorest books I have ever read on any chemical topic. I t is so badly written and so badly constructed that it would be quite unintelligible t o anyone not already acquainted with the subject while it is far too superficial and inaccurate to be of any value t o anyone else. The parts of the book dealing with quantum theory consist largely of mathematical expressions given without any derivation or adequate explanation, while the accompanying text serves only to pile obscurity on obscurity. Even the symbols appearing in the equations are often left entirely undefined. A good example typical of the whole book is provided by the section on the molecular orbital method on pp. 62-64. After a brief introduction, in which the term molecular orbital is not defined, the method is applied to benzene. First, an equation = CI$I C& . . . +C&, appears without any definition of the C1 and $1, followed by the sentence: “The coefficients CI, C: . . Cs are given by six secular equations as shown above.” KO secular equations are shown above. Next, without any explanation of any kind, comes the secular determinant for benzene, in which one symbol (Q) is left undefined. Next: “A determinant of this type does not apply t o benzene alone but quite generally for molecules with more than two a-electrons in that its rows are adopted t o the number of r-electrons. A general solution leads to:
+
~
+
.
Q - E = -2p cos (2aj/n) where n is the number of a-electrons, and j a series of numbers from 1, 2, 3, . . t o n.” Now apart from the typical obscurity of the writing this sentence contains two strange errors. First, a system with two a-electrons (e.g., ethylene) is no different from any other. Secondly, the “general solution” applies only to cyclic polyenes. One cannot believe that the authors do not know this; yet on the other hand errors of this kind abound throughout the book. Some of the errors are even more disturbing, e.g., the incorrect form of the overlap integral on p . 35. It is difficult to see how this could be a typographical error. Even t.he historical sections of the book are inaccurate; thus on p . 2 the Wien radiation law is ascribed to Planck and on p. 9 the Sommerfeld quantization condition to Bohr. The style of the book is poor, even by the lowest chemical standards. The following excerpt ( p . 13) is typical: “In 1924 de Broglie recognized that a wave nature had to be ascribed t o the moving electrons if one wanted t o impart physical significance to moving mass particles as compared to the motion of light in media of variable refractive index.” One can only hope that the original German version of the book was equally illiterate and that the translator has merely carried out his task too conscientiously. Many books are in parts like the curate’s egg and many are uniformly mediocre; this book however, is uniformly bad from cover to c0ver.l
.
(1) Except for t h e index which appears t o be quite accurate.
CHEMISTRY THE UKIVERSITY OF CHICAGO CHICAGO 37, ILLINOIS L)EPSRTRIENT O F
MICHAEL J S.L)EWAK
Stereochemistry of Carbon Compounds. By ERNESTL. ELIEL, Professor of Chemistry, University of Iiotre Dame. McGraw-Hill Book Company, Inc., 330 West 42nd Street, Sew 486 pp. 16 X 23 5 cm. Price, York 36, S. Y. 1962. xv $15.00.
+
This is an excellent book ivhich can be warmly recommended t o all organic chemists and biochemists, for advanced undergraduate work, for graduate studies and as background reading for research workers. I t IS the first comprehensive book dealing with organic stcreochemistry since Freudenberg’s cldcsic treatisc (“Stereochcinie,” Dcuticke, Leipzig, 1933). Dr. Eliel is t o be
congratulated on doing the near-impossible in such an outstandingly able manner. The interest devoted to steric problems has increased dramatically during the last 10 years. I t may fairly be said of almost every problem in carbon chemistry that the chemist can gain a better understanding of i t by looking a t it in three dimensions. This is equally true for problems of structure determination, of synthesis, and of reaction mechanism and kinetics. The scope of Dr. Eliel’s book is indicated by the following list of chapters: (1,) Introduction. (2) Optical Isomerism. (3) Optical Isomerism Due to Asymmetric Carbon Atoms. (4) Racemic Modifications. ( 5 ) Configuration. (6) Conformation and Reactivity in Acyclic Compounds. ( 7 ) Some Aspects of the Stereochemistry of Ring Systems. (8) The Actual Shape of Six-membered Rings and Its Relation t o Properties and Reactivity. (9) The Shape of Rings Other Than Sixmembered Ones. (10) Fused Rings and Bridged Rings. (11) The Stereoisomerism of Allenes and Related Compounds. (12) Geometrical Isomerism and the Stereochemistry of Olefins. ( 13) The Stereochemistry of Tricovalent Carbon. (14) Optical Rotation and Optical Rotatory Dispersion. (15) Stereoselective Synthesis and Stereoregulated Polymerization. Everyone of these topics is a subject in which the organic chemist should be aware of the latest ideas-and in each case he will find in Eliel’s book a clear account, which strikes the right balance between too-easy and inadequate generalization on the one hand, and too much detail on the other hand. Detail can be found in the many good specialized reviews which are available; Eliel gives full references to these and to a well-chosen selection of the more important original papers. Dr. Eliel modestly points out that the selection of topics is partly a reflection of his own interests; however, as these are wide-ranging, the reader need feel no disquiet on this account. Eliel draws attention t o the great importance of conformational analysis as a major part of the organic chemist’s “new thinking”; t o the interest in absolute configurations (an important growing point for both organic chemistry and biochemistry); and t o the rapid growth of instrumental techniques (U.V., I.R., X M . R . , O.R.D.), powerful new arms which have added so much t o the range and speed of the organic chemist’s operations. References are up-to-date (to the end of 1960 and some in 1961; the book appeared in the Summer of 1962). The production is excellent and the numerous structural formulas and perspective diagrams, vital for a book of this kind, are as good as they ought to be. The book is, in short, an invitation to three-dimensional thinking. If more organic chemists acquire the taste for this as an everyday habit, Dr. Eliel’s book will deserve to be numbered among the outstanding organic texts. The reviewer is confident that it will. DEPARTMEKT OF CHEMISTRY WESTFIELDCOLLEGE LOSDON,S.W. 3, ENGLAKD
W. KLYKE
Trait6 de physique th6orique et de physique mathbmatique. XIV. Structure electronique des mol6cules, petites molbcules, hydrocarbures saturbs, molbcules conjugubes, molbcules, d’int6rbt biochimique. By RAYMONDDAUDEL,Professeur B la Sorbonne, Directeur du Centre de mecanique ondulatoire appliquCe du C. N. R. S. Gauthier - Villars et Cie., 55, Quai des Grands-Augustins, Paris VI, France. 1962. 283 pp. 15.5 X 24 cm. Price, 48 N.F. ($10.00). This is the second in a series of three volumes on quantum chemistry, more precisely on the study of the structure and properties of molecules by the methods of wave mechanics. The first volume, published in 1956, contained the fundamental principles. Application of these to numerous actual cases make up this second volume; the third one will deal with chemical reactivity. The book opens with two brief chapters on the simplest possible systems, the one-electron (H:” molecule-ion) and the twoelectron systems (He atom and Hz molecule). I n fact these are supplements t o topics covered in volume I. Diatomics, both homo- and heteropolar, are studied in chapter 3. The rest of the book is devoted t o polynuclear molecules. After a long chapter (40 pages) on general aspects of the problem the author considers in turn classes of molecules of increasing complexity: Ch. 5, molecules with single bonds only, and no lone pairs, e.g. CHI; Ch. 6, small molecules with single bonds and lone electron pairs, e.g. H 2 0 and XH3; Ch. 7 , ethylene; Ch. 8, coiijugatcd
BOOKSRECEIVED
124
hydrocarbons treated by the so-called naive methods; Ch. 9, same, but after the more elaborate methods; Ch. 10, conjugated molecules with various substituents and heteroatoms; and finally Ch. 11, some molecules of biochemical interest. The book ends with a detailed table of contents and adequate indexes of authors and subjects. The great merit of this book is that it provides an exhaustive compilation as well as a critical evaluation of the voluminous literature in this fast growing branch of theoretical chemistry. More than one thousand references, mostly over the brief period 1950-1959, are analyzed. Some of this material was already contained in the text “Quantum Chemistry” published not so long ago by Prof. Daudel and his associates, Messrs. Lefebvre and Moser (Interscience Publishers, Inc., New York, N. Y . , 1959), but the scope and the emphasis are quite different in the French volume. The preparation was done with greater care for details than in Volume I , except perhaps for Chapter 4, especially the compilation of bond lengths and angles, where too many misprints and obsolete data remain. Apparently the author did not know of the most valuable “Tables of Interatomic Distances” published in 1958 by the Chemical Society, London (L.E. Sutton editor). The H t 0 molecule is singularly victimized in that respect: The 0-H distance is given as 1.85 A. (p. 74) the bond angle is stated variously to be 104’ or 105”, and on p. 94 there is a mention of the C-H bonds in that molecule. On the other hand, it is a pleasure for the French reader to behold some new and colorful jargon in that otherwise austere and abstruse science: to wit, the picturesque “liaison tendue” and “liaison banane,” the melodious “spinorbitale” and the utterly romantic “orbitale de coeur.” A: :f cry from Gibbs’ stern assertion: “Mathematics is a language. Because the author has chosen to confine his treatment to phenomena involving only the motions of electrons, there is no mention of such topics as molecular spectra, rotation about single bonds, tautomerism, etc. Conversely, a great variety of subjects are sketched in the last chapter, some of them definitely of the avant-garde type. One must admire Prof. Daudel for his optimism in tackling those frightfully complex problems (like the structure of carcinogens). Personally I was fascinated to learn, for instance, that the mechanism suggested by SzentGyorgi to account for respiration in sea-urchin eggs through an electric current along protein fibers, is unlikely on the basis of excessive (calculated) ohmic resistance ( D . 252). On the other hand, I am not overly impressed by t& prediction of the absorption maxima in the electronic spectra of OPPTHP or ADJTHP ( p . 264). As for physical presentation, the paper-back style adopted for this volume is a definite improvement over the first one, with its dull gray paper cover and flimsy “brochC” stack of uncut “inoctavo” Daaes. Still, considering the mice. the Dublisher could well have provided a hard cover. DEPARTMENT OF CHEMISTRY UNIVERSITBLAVAL PAUL A. GIGUERE QU~BEC CANADA ,
BOOKS RECEIVED November 10, 1962-December 10, 1962 MAURICE P. CROSLAND.“Historical Studies in the Language of Chemistry.” Harvard University Press, Cambridge, Massachusetts. 1962. 406 pp. $9.00. S. P. DATTAAND J. H. OTTAWAY.“Aids to Biochemistry.” Sixth Edition. The Williams and Wilkins Company, Baltimore 2, Maryland. 1962. 327 pp. $3.75. MARCEL FLORKINAND ELMERH. STOTZ,Edited by. “Comprehensive Biochemistry.” Volume 1. “Atomic and Molecular Structure.” American Elsevier Publishing Company,
Vol. 85
Inc., 52 Vanderbilt Avenue, New York, 17, N. Y. 1962. 256pp. $11.50 MARCELFLORKIN AND ELMERH. STOTZ, Edited by. “Comprehensive Biochemistry.” Volume 3. “Methods for the Study of Molecules.” American Elsevier Publishing Company, Inc., 52 Vanderbilt Avenue, New York 17, N. Y. 1962. 324 pp. $14.50. PAUL A. GIGUSREET MAURICEBOISVERT. “Tables des Fonctions Thermodynamiques de Debye.” Les Presses de I’Universite Laval, Quebec, Canada. 1962. 185 pp. $3.50. DR. -ING.WILHELMGUMZ. Nach dem Tode des Verfqgsers zu Ende gefuhrt von DR. RER. NAT. LOTHARHARDT. Kurzes Handbuch der Brennstoff- und Feuerungstechnik.” Dritte verbesserte Auflage. Springer-Verlag, Heidelberger Platz 3, Berlin-Wilmersdorf, Germany. 1962. 749 pp. DM. 88.--. OSAMUHAYAISHI, Edited by. “Oxygenases.” Academic Press Inc., 111 Fifth Avenue, New York 3, N. Y. 1962. 588 pp. $17.50. INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY. “Macromolecular Chemistry. Special Lectures presented a t the International Symposium on Macromolecular Chemistry held in Montreal, Canada, 27th July to 1st August, 1961.” Butterworth Inc., 7235 Wisconsin Avenue, Washington 14, D. C. 1962. 54Opp. $9.50. C. E. H. KNAPMAN, Edited by. C. G. Scott, Assistant Editor. “Gas Chromatography Abstracts. 1961.” Sponsored by the Gas Chromatography Discussion Group (Associated with the. Hydrocarbon Research Group of the Institute of Petroleum). Butterworth Inc., 7235 Wisconsin Avenue, Washington 14, D. C. 1962. 219pp. $8.50. THELATED. E. LEA. “Actions of Radiations on Living Cells.” Second Edition. Cambridge University Press, 32 East 57th Street, New York 22, N. Y. 1962. 416 pp. $2.95. J. D. MACKENZIE, Edited by. “Modern Aspects of the Vitreous State.” Volume 2. Butterworth Inc., 7235 Wisconsin Avenue, Washington 14, D. C. 1962. 260 pp. $11.50. THE OFFICE OF CRITICALTABLES. “Consolidated Index of Selected Property Values: Physical Chemistry and Thermodynamics.” Publication 976. Printing and Publishing Office, National Academy of Sciences-National Research Council, 2101 Constitution Avenue, N. W., Washington 25, D. C. 1962. 274pp. $6.00. E. G. V. PERCIVAL. ELIZABETH PERCIVAL, Revised by. “Structural Carbohydrate Chemistry.” J. Garnet Miller, Ltd., 13 Tottenham Street, London, W. 1, England. 1962. 360 pp. 40s. THBODORE POSTERNAK.“Les Cyclitols. Chimie, Biochitriie, Biologie.” Actualit& Scientifiques et Industrielles 1294. Editions Hermann, 115, Boulevard Saint-Germain, Paris VI, France. 1962. 491 pp. 48 NF. Proceedings of the Seventh International Conference on Coordination Chemistry, Stockholm and Uppsala, Sweden, June 2529, 1962. Abstracts.” Almqvist and Wiksell, 26 Gamla Brogatan, Stockholm C, Sweden. 1962. 392 pp. Sw. kr. 40.--. B. STEVENS.“Atomic Structure and Valency for General Students of Chemistry.” Chapman and Hall Ltd., Thirty Seven Essex Street, London, W. C. 2, England. 1962. 103 pp. 12s. 6d. HERBERTTEICHMANN UND GERHARDLEHMANN.“Sitzungsberichte der Deutschen Akademie der Wissenschaften zu Berlin. Klasse fur Chemie, Geologie und Biologie. Jahrgang 1962 Nr. 5. Untersuchungen an Thiophosphorsaureestern.” Akademie-Verlag, Leipziger Str. 3-4, Berlin W 1, Germany. 1962. 61 pp. DM. 7.--. W. THEILHEIMER. “Synthetic Methods of Organic Chemistry. Yearbook.” Vol. 16. Interscience Division, John Wiley and Sons, Inc., 440 Park Avenue, New York 16. N. Y. 1962 508 pp. $48.00. R. G. WARD. “An Introduction t o the Physical Chemistry of Iron and Steel Making.” St. Martin’s Press, Inc., 175 Fifth Avenue, New York 10, N. Y. 1962. 238 pp. $8.50.
