Advanced Organic Chemistry, Part B, Reactions ... - ACS Publications

book reviews. Molecular Structure and Bondlng, the. Qualltatlve Molecular Orbital Approach. Benjamin M. Gimarc, Academic Press,. New York, 1979. v + 2...
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book reviews Molecular Structure and Bondlng, the Qualltatlve Molecular Orbital Approach Benjamin M. Gimarc, Academic Press, New York, 1979. v 224 pp. Figs. and tables. 23.5 X 16 em. $18.00.

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The first thing that a chemist wants t o know about a molecule is its structural farmula-that is, its atomic composition and connectivity, with a t least some broad hints of its shape. Armed only with this rather small amount of information, he finds i t possible to in surprising detail much of the spectroscopy and chemical reactivity of thesystem. Surely any contribution toour ability to anticipate molecular shapes is to be welcomed. "Molecular Structure and Bonding" makes just such a contribution. In spite of its title, this bookdoes not provide any account of the experimental elucidation of structure, nor does i t provide any but the sketchiest outline of the mathematical foundations of bonding theory, offered more or less as a glossary of the notation and vocabulary used in the main sections of the hook. Gimarc devotes his attention to qualitative methods for obtaining the variation in orbital energy as molecular geometry is altered; this permits the prediction of preferred geometries, without computation, for systems ranging in complexity from AH* to ABs and A2Bs. His methods are limited t p systems without d orbitals, and fail for ionic molecules. Many of the detailed results have appeared in the literature in reports by the author, and have been arrived a t in a less transparent way by Pearson (compare Pearson's "Symmetry Rules for Chemical Reactions"). The unified and lucid presentation makes this book a good investment-it is admirably suited to self-study by anyone who brings to it an appreciation of symmetry operations (group theory is not needed) and a fair understanding of MO theory. Probably a grasp of Huckel theory would be sufficient, though Gimarc's analysis relies heavily on the appreciation of overlap effects. I recommend that this book he used as a supplement to any advanced organic or inorganic course where the prefatory bonding theorv has been developed. I t is accessable, interesting, and useful. Carl Trindle Univemify of Virginia CharIonesviIle. VA 22901

Neptune's Om: A History of Common Salt

Robert P. Multhouf, The John Hopkins University Press, Baltimore, 1978. Figs. & tables. 26 X 18 cm. xviii 325 pp. $22.50

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To explain why he wrote this hook, the author states in his introduction, "The idea of 'progress' in the political realm, so popular in the 19th century, has come in the 20th to seem illusory. In science and technology, however, the idea of progress is still robust. But what is the relationshio between oromess . " in this particular realm and progress in other sectors of human affairs? An important obstacle to our improved ability toanswer such questions is the scarcity of studies in the A352 / Journal of Chemical Education

history of scienee and technology that carry a particular theme from the distant to the immediate past in aeomprehensive way." Common salt is so important and so widely used that any account of its history must cover a wide range of topics. ..its occurrence in nature, methods of obtaining it from natural sources, its influence on economics and politics and its uses ineveryday life and in the chemical industry. All of these topics are discussed in this book, and interwoven into an interesting story. Clearly, it is a monumental task to weave together all of the aspects of the history of salt, and the author is t o be commended for succeeding so well in doing it. The need for salt in human and animal diets has made it a critical substance since the beginning of history, and in early times the facilities far its production were often owned by royal families who used the power this ownership gave them in despotic fashion. In many countries, the tax on the salt industry served both economic and political ends. In more recent times, sources of salt have been found to be very widely dispersed, and their political importance has been lessened. However, some of the by-products of the mining of salt (e.g., compounds of potassium and baron) continued to play a political role well into the twentieth century. In ancient times, salt was obtained mostly from the sea and from salt lakes, largely by solar evaporation. This method is still in use in warm, sunny climates, but now the hyproducts which are obtained may'be worth more than the sodium chloride itself. Evaporation of salt water by heating over wood and, later, coal fires became popular early, but has been largely supplemented by mining or boring for rock salt. The growth of the chemical industry has tremendously increased the demand for salt, and its use as a raw material for the manufacture of sodium carbonate, sodium hydroxide, chlorine, and other products exceeds its culinary use many fold. Multhaufs book is divided into two main parts. . "The Age of Culinary Salt" and "The Era of Chemical Salt." These are followed by appendices which contain satistics on salt production in different countries and in different times and the oroductiou of ar-

important present-day topics of concern to chemists, other scientists and engineers, such as energy, health, safety, toxicology, and new materials. Also included are articles on polymer and plastics technology, fuels and energy, inorganic and solid state chemistry, composite materials, fermentation and enzymes, coatings, pharmaceuticals, surfactant technology fibers and textiles. Approximately 1,000 completely revised and updated articles written by 1,2W specialists and reflecting the chanees and growth in all aswcts of chemical tmhrhoev ~,.< tiroueh ,. the 19f0's from the core ui the third edition. S I and traditicmal trniu nreusrd stmul~anrously.('hrm~ral.Ahstmc~u registry numbers are employed throughout. Volume 1 includes conversion factors, ahbreviations and unit symbols, followed by topics ranging from abherents to alkanolamines. Hiehliehts of this volume include .. arelic acid 311d d e r i v d v ~ s~, ~ e t y l r narr. w sols, air p o l l u ~ ~ oalcoh&, n, alknl~,and chlorine products. Volume 2 contains topics from metal alkoxides to antibiotics. Items of special interest in this volume are alkvlation, aluminum and aluminum compounds, analgesics, and analvtical methods. ~. Vdumr 3 begins w~rhanrihioticsandends with Meaching agents. Asbrstoa, batteries and elertrw rells, brer, brwene, iwryllium compounds, biomedical automated instrumentation, and biopolymers are the subjects stressed. Volume 4 contains topics from h l w d coagulants and anti-coagulants to cardiovascular agents. Interesting tapics in this volume include boron compounds, optical brighteners, bromine, cadmium and cadmium compounds, calorimetry, carbonated beverages, and carboxylic acids. Volume 5 deals with topics from castor oil to chlorosulfuric acid. Phase-transfer catalysis, cement, chemiluminescence, chemotherapeutics and certain compounds of chlorine are the topics emphasized in this volume. WTL ~

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raphy and a good index. Teachers of chemistry who believe that the study of general chemistry is a part of a liberal education, or who want to enliven their lectures with bits of history or economics will do well to read this book. It will not be of and molecular orbitals. John C. Bailar. Jr. University of lliinois Urbana. N. 6 180 1

Klrk-Olhmer Encyclopedia of Chemical Technology, 3rd Edition Martin Grayson, Exec. Editor; A WileyInterscience Publication, John Wiley & Sons, New Yark, 1978. Vols. 1-5. Figs. and tables. 26 X 19 em. Each vol. -1,000 pp. $120 separate volume/$95 subscription. The first five volumes of the 3rd edition of this oooular and authoritative encvclo~edia . . havenipeared In additim to updating tradlrlonal topiui, the new editiun rmphasirei

Advanced Organlc Chemistry, Part 8. Reactions and Synthesis

F. A. Carey and R. J. Sundberg, Plenum Press, New York, 1977. Figs. and tables. 26 cm. Carey and Sundherg have written a twopart text suitable for a two-semester beginning graduate or advaneed undergraduate level course in organic chemistry. Both parts are also well-suited for reference texts. for self-study, and for brushing up. "part A, Structure and Mechanisms" is a prerequisite for a full understanding of "Part B, Reactions and Synthesis;" only the latter work is reviewed here. The first nine of eleven chapters, organized by reaction type rather than functional groups, are entitled: (1) "Alkylation of Carbon via Enolatesand Enamines," (2) "Reaetions of Nucleaphilic Carbon Species with Carhonyl Groups," (3) "Addition Reactions of Carbon-Carbon Multiple Bonds," (4) "Reduction of Carhonyl and Other Functional Groups," (5) "Organomatallie Campounds," ( 6 ) "Cycloadditions and Unimoleeular Rearrangements and Eliminations," (Continued on page A3541

book reviews

combination of properties by inexpensive physical means. Just as chemical comhination of monomers in random or alternating copolymers or polymer blocks in sequential (block or graft) copolymers may lead to new, (7) "Aromatic Substitution Reactions," (8) sometimes unexpected properties, physical "Reactions Involving Carbenes, Nitrenes, and mixing, hlending or "alloying" two or more Other Eleetron-Deficient Intermediates," polymers may also give rise to new and useful and (9) "Oxidations." Chapter 10, "Multistep combination of properties. The complexity Synthesis," makes use of material from the and subtlety of principles governing the orecedine nine chanters and discusses oromixing of polymers is astounding, and eaeh tectiw group.; and synthetic rtrarrgs. Chapter 1 I, "Syntheiiu of hlarrumuicr~~les." contributor renders a most valuable service by making his expertise bear on the hriefly c o v e n industrial polymers, peptdrs. subjects. and polynueleotides. The first volume starts with a brief (15 Every chapter is divided into three to ten PP.); but useful "Background and Perspeesections with references conveniently placed tive" bv one of the editors. Paul.-in which a t the hottom of each page. Numerous wellmanv of the mvsteries.. e.e..effect of molec-. referenced tables exemplifying the reactions uinr weight. i p e c f ~ emfcractims, and morunder discussion accompany these sections p l ~ h g streated , Inter in drtail in individunl and are a big help to the reader. Several ~hapters,are intn,dured. Subsequent w n general references are a t the end of eaeh tributions seem t o center around the three chapter. All references date from 1974 and major themes thermodynamics, viscoelasearlier and are intentionally from English ticity, and properties. The second, a major language journals, mostly American, partiechapter by Krause is an excellent up-to-date ularly J. Amer. Chem. Soc. and J. Org. virtually comprehensive tabulation of polyChem. mer-oolvmer with an exam. . hlends toeether " Each chanter ends with an excellent set of ination cdth~rmodvnamicsof compar~hility. iitrrarwe-hnsed, referenced pnhlcm5 - 2 G , I hia is tldlowrd h) a diwussim ofstatistiuil in all. Since many contain wvrral p.wtr, there t h r r m d y n a w i ~of~irlrndi by Snnrhrv. Next, arc arrunlly uver 500 exercises! A thirteen phase relationships in polymer blends are page subject index concludes the hwk. treated by Kwei and Wang. The following Certain topics, such as heterocyclic chapter by McKnight, Karasz, and Fried chemistry and carbohydrates, are not covered contains a useful examination of criteria for systematically, since the book is organized miscibility and measurement and limitation around reaction types nor is their omission of Tg information for assessing compatibility. important in this appropriately-sized, one Foundations far viseoelastic properties and semester text. Rather, the chemistry dismelt flow of incompatible disperse phases are cussed is what most synthetic organic chemprovided in subsequent chapters by Wu on ists consider central to their subject today. interfacial energy and structure, and by Van Compared t o two other fine, fairly recent, Oene on the mierorheology of suspensions of texts, "Advanced Organic Chemistry" by J. rigid particles in viseoelastic fluids, deformMarch and "Highlights of Organic Chemisable drodets. and oalvblends. This is foltry" by W. J. LeNoble, Carey and Sundberg lowed h; a =hap& on small-deformation would be my choice for a course on synthesis. mechanical properties of multiphase polyThe large number of problems certainly is blends by Dickie. In the two final excellent advantageous for both classroom use and chapters of the first volume Stein addresses home study. March and LeNoble are prohaoptical behavior, and Hopfenberg and Paul hly more useful as grnrrnl reference hooks. discuss transport phenomena in poly"Resctimsnnd Synthmis" ~srlenrlywrltblends. tm inrn*llv ondersrnndnhle English. it rov. The second volume starts with a concise ers a suitable, hut not excessive, amount of chapter by Thomas and Sperling on interimoortant svnthetic oreanic chemistrv in a penetrating polymer networks and a lucid ihgirni, wdl-miwed manner; nnd it pn9vides presentation by Paul on interfacial agents a grmt numher of pnthlpms and examples to "eompatihilizers" for polyblends. The next hrip the student martar the material. ('arey two chapters concern polyblends of rubbers and Sundberg have written a unique text and glassy polymers. Recent efforts of which fills a real need in the chemistry curtoughening various glassy polymers by rubriculum. hers is empirically overviewed by Newman Kenneth K. Andersen and the relationship between structure and University of New Hampshire fracture resistance is expertly reviewed by Dwham. NH 03824 Bucknall. These are followed hy a very good survey on coextruded multi!ayer polymer Polymer Blends. Vols. 1-11 films and sheets by Schrenk and Alfrey, and a highly readable overview on fibers from Editors D. R. Paul and Seymour Newpolyblends by Paul. The next chapter on man, Academic Press, New York, 1978. polymeric plasticizers hy Hammer mainly Figs. & tables. 23.5 X 16 cm. ix 501 pp. concerns PVC. A brief chapter by Kraus on $47.50. block copolymers in hlends with other homopolymers or random copolymers follows. This is a very valuable and timely eompiThen McDonet, Baranwal, and Andries lation of 23 articles concerning the physical highlight common characterization methods, and mechanical properties of polymer blends practical mixing techniques, and properties or "polyblends" written by a knowledgeable of elastomer blends in tires. This is followed set of authors. The editors have elected to by a succinct chapter by Kresge, on useful define a polyhlend as any combination of two 'rubbery thermoplastic blends obtainable by or more polymers resulting from common modifying thermoplastic elastomers with processing steps. homopolymers or by hlending a nonthermoThe science and technology of polyblends plastic elastomer with high modulus plastics. is the subject of current intense investigations The chapter by Plochoeki of Warsaw, Poland, as an avenue toward the creation of desirable

concerns a review of melt rheology of polyolefin hlends and is teeming with 312 references. A brief survey on hlends containing poly(waprolactone) by Koleske follows and the volume ends with a brief exposition by Atkins of low-shrink fiber-reinforced unsaturated polyester resins obtained by blending with thermoplastics. In these two volumes the editors went a long way toward achieving their goal of compiling an authoriative treatise on principles and techniques available to the contemporary seientist/teehnologist for the creation of desirable balanced combination of polymer properties by physical blending. Joseph P. Kennedy Ths University of Akron Akron. Ohio 44325

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Mew Volumes in Continuing Series The following titles are those of uolumes in continuing series. Many of these aerie8 are familiar to readers who am best served by pTompt announcement of the appearance of the new titles. The policy of T H I S JOURNAL will be lo publish full revims only of inaugural volumes in n m series.

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A354 / Journal of Chemical Education

Molecular Biology, Biochemistry, and Biophysics-Chemical Relaxation in Molecular Bloiogy. Volume 24. Edited by I. Peeht and R. Rigler, Springer-Verlag. New York, 1978. VIII 418 pp. Figures and tables 24.5 X.17 em. $36.80.

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Contributors: M. Ehrenberg, E. Grell, D. N. Hague, G. Ilgenfritz, T. M. Jovin, D. Lancet, D. Magde, I. Oherbaumer, I. Pecht, F. M. Polh, D. Porsehke, R. Rigler, P. Schuster, G. Striker, D. Tusius, K. Tortschanoff W. Wintermeyer, P. Wolschimn. Table ofcontents: Theory and Simulation of Chemical Relaxation Spectra; Concentration Correlation Analysis and Chemical Kinetics; Dynamics of Substitution a t Metal Ions; Dynamics of Proton Transfer in Solution; Elementary Steps of Base Recognition and Helix-Coil Transitions in Nucleie Acids; Structural Dynamics of t-RNA. A Fluorescence Relaxation Study of t-RNAyeast; Chemical Relaxation of E. coli RNA Polymerase Binding to poly/d(A-TI/ Using Ethidium Bromide as a Fluorescence Probe: Protein Folding and Unfolding; Kinetics oi Antibody-Hapten Interactions; Glutamate Dehydrogenase Self-Assembly . . . ;Dynamic Aspects of Carrier-Mediated Cation Transport Through Membranes Methanol Technology and Application in Motor Fuels. Chemical Technology Review no. 114, Energy Technology Review no. 31.

Edited by J. K. Paul, Noues Data Corporation, Park Ridge, NJ, 1978. v 470 pp. Figures and tables 24.5 X 16 em. $54.00.

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(Continued on page A356)

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