Organic Reaction Mechanisms: An Introduction
Ronald B7eslolo, Columbia University.
BOOK
REVIEWS
W. A. Benjamin, Inc., New York, 1965. Organic Chemistry Monograph Series. xii 232 pp. Figs. and tables. 14.5 X 22 em. Clathbound, 67; paperbound, $345.
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This is a. book on organic reaction mechanisms for beginning and for intermediate students of organic chemistry. General Chemistry the chemistry of the noble gases has been Its stated intention is to present "unified added. There is a. new chapter on Eleoutlines of the field.. .together with a. W . F . Luder, Robert A . Shepad, A~thur ments of the Second Period, which gives an critical examination of the evidence ior A. Vernon, and Saverio Zuffanti, all of excellent introduction to eaoh of the famproposed mechanisms. . . which can he Northeastern University, Boston. 3rd ilies. This is followed by three chapters, read independently by undergraduates ed. W. B. Saunders Co., Philadelphia, each concerned with two families of elewho are enrolled in a good course in ele1965. xiii 560 pp. Figs. and tables. ments. Chapters on Equilibrium and mentary organic chemistry." There is, $8.75. Spontaneous Reactions, Hydroxylic Acids indeed, a. great need for such a book, as and their Derivatives, and Coordination In the third edition of this excellent most of the current beginning texts are Compounds are completely new. The textbook the authors have produced a very long on mechanisms, but very short material on Organic Chemistry makes up complete revision and reorganization. (approaching zero) on the evidence s u p the three concluding chapters entitled The content and sequence of the chepters porting t,hem. The present book is Open Chain Compounds, Closed Chain have been altered. New topira have been certainly a vast improvement over the Compounds and Natural and Synthetic added and in some cases two ch&ers of usual textbook coverage, although some Products. the earlier edition have been incorporated parts of it are better than ot,hers. A table of ionization constants has been very soccessfnlly into one. The chemistry The approach taken is, necessarily, added to the appendix and the table of of hydrogen, oxygen, water, and hydrogen illustrative rather than exhaustive, and atomic weirhts is based on Cwbon-12. peroxide has been included in the first chapthe choice a i material is generally good. New illustrations have been added and ter entitled Chemical Changes. Atomic There are c b q ~ t e r son structure, general those a t the heading of each chapter are Strncture and the Periodic Table includes theory of reaction mechanisms and rates, particularly significant and informative. material formerly in two chapters. Cheminucleophilic substit,ution, elimination and The use of different forms of type gives s. cal Bonding is introdaced early and conaddition reactions, aromatic substitution, pleasing appearance and should aid the tains new material on chemical geometry reactions of earbonyl compounds, and rcstudent in the orgsnizatition of his study. and extensiveuseof atomicenergy leveldiactions of free radicals. Each is followed The questions and problems at the agrams. The inclusion of crystal strucby s. mare detailed discussion of a special ends of the chapters as well as the reft,ure makes the chapter on the States oi tapic, illustrating and expanding on the erences to supplementary readings have Matter more complete. Chemical Kinetics paints made in l.he chapter. To this been completely revised. is treated separately instead of being reviewer the best chapters are those on The revised edition is a solid and u ~ e d as an introduction to Chemicd nucleophilic substitution, and elimination rigonru prr;wtntior> of 3,firct-ywr O,IIT*C Equilibrium. A new section on ionic reeeand addition reactions. The former, i t , genernl :h.mlctrv ar.4 Jewrvei the lions, which should be p~rticularlyhelpparticularly, seems to pick out, unerringly, n t r v n t m >oi trnvhrri ir r aitljle ncioptmn. ful to students, has been added to Soluthe illuminating experiment from the mass tions of Electrolytes. The chapter on SISTERMARYJOAN of material in this field. Its special topic Introduction to the Representative EleEmmanuel College is neighboring group participation, prements has been completely revised and Boston, Massachusetts sented very well from the Winstein-Cram point of view. Both the main chapter and the special topic are richly and judiciously footnoted. The chapter on earbonyl compounds, and especially its accompanying "special tapic," on organic redox reW . F . Luder, Roberl A . Shepard, Arthw A . Vernon, and Saverio Zu$anli, General aet,ionswas also very satisfying. Chemistry The first two chapters, on structure and Ronald B~eslow,Organic Reaction Mechanisms: An Introduction rate theory, predictably, present difficulties, because the intended audience is Russell S. Drago, Physical Methods in Inorganic Chemistry lacking in the background and sophisticaCharles Wallcr, Steady-State Applications in Enzyme Kinet,ics tion required for R mund treatment of these subjects beyond the elementary D. M. Adams and J . B . Ralino~,Advanced Practical Inorganic Chemistry level. Since the audience could not follow N. Haissinsky and J. P . Adloff,Radiochemical Survey of the Elements the appropriate derivations, these chapters tend to be arbitrary and dogmatic. Michael Hanaek, Conformation Theory They are, also, much loss well footnoted than the rest of the book; probably beThomas M. Dunn, Donald S . MeClure, and Ralph G. Pewson, Some Aspeet,s of muse the audience wouldn't understand Crystal Field Theory t,he appropriate original literature. The B. Trdmilla, Les ~Pparationspar les resines &changeusemd'ions chapter on aromatic substitution is d i appointing to me because it does not preK. G. Dmbigh, Chemicai Reect,or Theory sent much oi the lovely, classical work of R. A . Bernheim, Optical Pumping: An Introduction Ingold and his co-workers. I t seems to me that the author has been led down the Daniel A . Greenberg, Mathematics for Introductory Science Courses: Calculus garden path by spectacular recent experiand Veet,ors ments. some of whirth mav not be correctlv ~,~~ F& Wolf, Das Lustige Atom interpreted and which do not seem, to me, as pertinent as the earlier studies. Albert I,. Lehninger, Bioenerget,ies As already mentioned, many pertinent 12. 0.C. N o n a n and R. Taylor, Eleetrophilie Substitution in Benzenoid Comresults are footnoted with references to the pound~ original literature, in pleasant contrast with elementary texts. Unhappily, this
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'olume 43, Number 4, April 1966
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book vontil~uesthe use of "rertrliou roordinate diagrams'' ilk wlrivh the rbsrissa has uu mealliug. The typography seems dear and I found no typogritphieal errors. Tlrp figures are generally well drawn and illumiuating. I found unly one trivial error ill a figure. All iu all, this book should significantly enrich most beginning orgsnir. chemistry courser, alld it should uot he beyowl theabilities of their students. I inlend to use it for my course.
.\I.AI.KICE A l . KHEETDI I'nivrrsil!, of Minncsolrr .Ilinnmpolia
Physical Methods in inorganic Chemistry
Russell S. D m p , 1:niversily of 1llinui.-. Urbarm Reillhold Publishil,g C o q . , New Ywk, I ! . sviii 430 pp. Figs. aid tables. 16 X 2 3 5 rm, 14.50.
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111 a prefatory stat,ement by the ?onculliug editors the reader is reminded that there are numerous books whivh provide the baser for applirstion of physirnl metlrnds to illorgallir. or organic chemistry, hot that, "There are, however, few hooks whirh within a single vnlume, treat the more imporla~tt physiral methods in a. manner which makes it convenient for ihr student or p r a r t i v i ~ qrhemist t o lean, how to use ~ a v hmethod and t h e kind of iuforrnatiuu which can he ohtained h o m each." This book and the course for (or f t ~ r n ) whirh i t was prepared are dearly addressed to that admirable goal. It is 1101 usual for many universities to present a raurxe of thii type al present for the seuior 01. first year graduate dudent, hut granted the existewe of such a program, the11 Professor Ilrago's test appears lo be well considered both with respect t o content and to level. There are three int~ndurtot.yrhapters on atomic structure and bondiug, induding inlrodurtiour t o ligand field and molerulrr orbital theory, whirh serve as a basis for the resl of the material. No1.mal1.v the :;tudeota should have been exposed lo wrlr material in the more usual sort of senior or heginning graduate course in inorgmir chemistry, but the iwlusin~lof these chapters would make it possihle to present a self-contained course, with little prior k~mvledgeof illorganic chemistry (aside from a hit of knowledge of some of the farts of inorganic chemistry) being required. The physiral methods whirh are rotrsidered can all be classed xi;spectroscopic methods, including mass spectroscopy. The topic.; are, in order, symmetry, character tables, etc., leading t o a general introduction t o spectroscopy and then t,o electronic spectroscopy (visible and ultraviolet absorption spectrometry), vibrational and rotational (infrared, Raman, and microwave), nuclear magnetic resonance, electron spin resonance, hIBssbauer, and mass speetroscopy.
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Journal o f Chemical Education
11, ad, chapter the fundamentel principles are introdured and then the kiuds of i~lformat,iont o be obtained, the iimiratiow of the method, aud same examples of xppliretions (drawn heavily from Prafessol. Drsgo's own rnwan.11) of each method are desrribed. The level a1 whirh the presentation is aimed seems t o be well chosen. The student or rhemict, uninitiated ill a particular mdlrod, ought to benble to reed this text (perhaps eveu ill bed) a ~ i d determine whether a given r n ~ t h o drvould be suited t o his needs. FIR xvuuld probably learn enough about the method to read further or ronsult with wme expert and pursue a solution l o hi.; o s u problem. I n gel~eralthe orgallisation and a-riting i . ~good, hut there are places where strings ge, and CARL11. B I L T . B A IJw. ~ ? , paper chrrmntography. The next two d l irhiyan Slate l~nitw..~il!, elmpters rutltni~lexperimenls designed to Easl I.on.sU,q aequaiut the sttldeut with the chemistry of selected elemwts from the periodic tahle. Among the experiments are ornny syntheses, mostly laken from t,he ' I ~ m r g a n i r Syntheses" series, \V. G. Palmer's "h:xperimental Illorganic Chemistry'' (CamSteady-State Applications in bridge, 1954), strd IT. F. Walton'i "InEnzyme Kinetics organic Pr~pamtions" (Pwutiv-IIdl, 1048). The f i t d frmrteen c1raptel.i are Chnrlo. l,ValtP~.,U~~iversit~y of Tennessee, short expositions of variotw advanced 3lernphis. The Ronald Press Co., techniques s ~ a% ~ infrared h spe~~lroscopy, Sen- york, 1965. vi 263 pp. Figs. high-temperature preparations, vaeuimand talk*. 16 X 24 rm. $12. line preparations, and narr-sq~~eo~ls idvents. Some wdl-rho.ien syutheses are This hook represents a u~tified treatincl~lded to iIlit*trate these i d ~ n i q u e s , ment of t h r steady-st,at,e equations in h ~ l ti ~ rmmly ra-e.: the directiwr.; are so enzyme kiuetirs. The emphasis is on the abbreviated t h a t most studeuti n-crdd m a t h e m a t i d relabionship between me&-have difficult>-in ohlaining good yieldn. wed rates and kinetic aoust.ants rather The authors lrave not given r d i l to tlran on the vhemistry of enzyme react.ions. The book opens with three introductory all their sources of material. 3lill.h of their disc~~ssion, on pages 25-28, of the vhapters on nomenclature, a stimulating ~chararterisalion of sodium t~~ipliasphr~te short historical account and thermaand Lriphosphoric acid has hren lifted dyanmirr. Startiug from Chapter 4, the from pages .5G and 147-148 in my lexl, author gives an admirable disnwsion of "Syuthetic Innrgauir Chemirtv?' (Prew produvt conrentrat,ion as a. funrtiolr of tire-Hdl, 1960). time. Dim!! and Wehh's treat.ment of the Some of the experiments (sllrli as those involving the qualitative study of the chemistry of the elements and the h i nothor's own contributions t o more comrhiometry of reactions) wollld be applex euzyme mechanisms, ordered sepropriate for freshmen. Other esperiquences, and reversible enzyme react,ionr. rnents (mch as the syntheses of the phosThe last rhapt,er gives a brief discosrion of phonitrilic halides and bis(~-eyclnpeotaintegrated rate equations and a list of dienyl)titaoium(IV)dichloride) r o t d d be same useful integrated expressions. appropriate for seniors and graduale Some of the examples could be made studeuts. T h e discusions of synthetic more interest,ing by illustrations s i t h techniques and methods of characlerisaactual experimental data instead of tion are generally too brief to be of much hypothetiral reaction curves. There are use. Thus it is hard to imagine where t,lii.; occasional misprints where equations are
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