book reviews nistic basis. The text consists of ten chapters including, in sequence, a hrief general discussion of the field; preparation of highly fluorinated compounds; selective fluorinations; influence of fluoraearbon groups a n reactive centers; nucleophilic displacement of halogen from fluorocarbon systems; elimination reactions; polyfluoroalkanes, alkenes, and alkynes; functional compounds containing oxygen, sulfur, and nitrogen; a long chapter (73 pages) on polyfluoroaromatie eompounds (in which the author has made major contributions); and organometallic compounds. The chapter on t h e influence of fluorocarbon groups on reactive centers provides a good treatment of the electronic effects of perfluoroalkyl groups on acidities of acids and alcohols and an excellent discussion of fluorocarbocations and fluorocarbanions. I was a bit disappointed that no mention was made of the significant effects of high fluorination on the properties (e.g., infrared spectra, keto-end equilibria) of ketones, P-dicarhonyl compounds, and a.0-unsaturated carbonyl systems, perhaps reflecting the reviewer's bias. The entire presentation is lucid and well organized and the bibliographic material (through early 1972) is quite thorough. Mechanisms are liberally interspersed in the discussion. I noted few errors, e.g., reference 54a (p. 96) is missing and the formula on the bottom of page 102 should he ShF4-F rather than SbF3-F. In contrast to other works in the field, uir., Sheppard and Sharts, "Organic Fluorine Chemistry" and Hudlicky, "Chemistry of Organic Fluorine Compounds," detailed tabulations are absent. Instead, the author has given us a highly readable and enjoyable book on organic reactions involving fluorine, which should be on the shelf of anyone interested in this subject. Robert Filler lllinois lnstlMe of Technoicgy Chicago, Illinols 60616
Organlc Syntheses Vla Boranes
Herbert C. Brown, Purdue University. John Wiley and Sons, New York, 1975. xix 283 pp. Figs. and tables. 23.5 X 15 cm. $17.50.
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The author's hope "that this book will serve to acquaint working chemists, teachers, and students with the chemistry and techniques of arganoborane chemistry," is a very modest expectation indeed. The book will do this function excellently and will s t the same time provide valuable information in areas that hooks rarely cover. It is in a sense three concurrent books and each will provide the careful reader with its own message. ~ 2 7 4/ Journal of Chemical Education
I t is first a simply written hut highly knowledgable source of information on the ehemistrv and teehniaues of omanohorme chemist&. The additibn of the-chapter a n laboratory operations with air sensitive substances provides information unavailable elsewhere on simple hench-top methods. The potential utility of this book t o organic chemists on the level of "What Can he Done?," and "How to do it?" is douhtlessly high. The second concurrent book is read as a tapestry of 19 years of extremely successful research. What emerges are insights into the planning and development of a research program. This is typically not the mast developed strength of most chemists and sadly it is never taught. Given that one finds an interesting reaction such as the facile addition of horon-hydrogen bonds to carbon-carbon multiple bonds, what then? How do you marshall your forces so that some years later the fabric of organic chemistry is changed and every elementary organic chemistry texthwk includes hydrohoration. The answers t o thesequestions are t o he found hv activelv readine the chaoter surveys and n o t q carefullv the specific compounds rhosen for dernmstration. The furmer is based on the breadth of knowledge of organic syntheses and a vital sense of what types of conversions are apt t o be desirable. The latter is based on a realistic understanding that the general method must be used to prepare specific difficulty obtainable eompounds if the method is to achieve any currency. It is no accident for example, that P. 158 provides a stereospecifie synthesis of the thermadynamieally less favored trans-l-hydrindanone from vinyl cyclohexene. The third "concurrent" b w k provides insights into organic laboratory experimentation from one of the most successful lahoratories in the world. Early in my chemical career I became painfully aware of the truth of the expression "any pair of hands can mix reagents hut only s chemist can get the desired compound out of the reaction mixture in good yield and high purity." What one learns in going from "a pair of hands" to "a chemist" is the ineredihle attention that is required during "workup." There are few better teachers of this difficult, though critical part of organic chemistry, than Professor H. C. Brown. This book captures much of thatinvaluable teaching, and abounds with examples of this kind of attention of detail that leads to good results. Among the many eaamples, note 4 on page 187, is representative even though tetrahydrofaron and the product boil approximately 50°C apart, careful fractionation is required t o obtain a pure product.'' This is a hook that can and should be read in different ways. From the upper Level undergraduate t o the busy professor i t will provide value. Shelton Bank State Univemily of New York at Albany Albany. 12222
Creatfvity In Organlc Synthesis. Volume 1
Josjit S. Bindra and R a j a Bindra, Pfizer.. Ine.. Graton. Connecticut. Academie Press, Inc., New Ymk, 19'5. xiv 322 pp. Flow Charts. 24 X 19 cm. S11.50.
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This is a collection of synthetic routes to more than 67 natural products selected from the literature from mid-1969 to mid1974. Each compound or group of related compounds is covered as a separate section including a hrief description of the eompound, its source, any unusual characteristics, and a few comments on the strategy or more unique steps in the synthesis. This is followed by a flow chart showing the reagents and intermediates in each step ledding t o the product, and also the percent yield for about half of the steps. Thwe who are familiar with "Art in Organic Synthesis" hy N. Anand,.J. S. Bindm, and S. Rangmathan, Holden-Day, Inc., San Francisco, 1970, will recognize this format. The present baok continues in the literature where the fir@ finished. The structures and type are larger and more attractive in the new book, and the coverage has been narrowed. excludine the still verv active area of rynthezis of unnnturnl compounds wrth high strain o r geumetrml interest Anyone involved in synthesis of complex molecules will find this a valuable resource. I t can be scanned far more rapidly than journal accounts t o learn strategy or notice applications of many new selective reagents. I t is also a concentrated source of examples suitable for study in a course in advanced synthesis. The inevitable small errors will be no problem for most readers; for example the iodolactonization (p. 211) was actually carried out with NaI 12. The reducing agent on p. 117 is actually sodium bis(2-metboxyethoxy) aluminum hydride. Disiamyl borane 1s incorrectly formulated on p. 154, and 1-hromo-3-methyl-2-butene is shown as a higher homolog on p. 106. This book is a unique source for rapid scanning of synthetic routes and would be of interest t o most chemists practicing or studvine .. advanced svnthesis. I t is. hawever, a selectiun of c&s and shouldnut be considered as a review or an indication uf the overall scope of modern synthesis. , ~
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John C. Stowell Unlverrlty of New Orleans New Orleans. Louisiana
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Topics In Nonbenzenold Aromatlc Chemistry. Volume 1 Edited by Tetsuo Nome, Tohoku University, Ronald Breslow, Columbia University, Sho Ito, Tohoku University, Klaus Hafner, Teehnische Hochshule Darmstadt, and Ichiro Murofo, Osaka University. John Wiley and Sons, New York, 1973.295 + pp. Figs. and tables. 23 X 15.5 em. $21.50. If the potential buyer is concerned that this baok will simply be a rehash of the
topics covered in earlier hooks of similar titles by Ginsberg, Lloyd, and Snyder, let that fear he dispelled. The first apparent difference is that the usual first chapter a n the "concept of aromaticity" has been tastefully omitted. Next we find that the subject matter is, on the whole, quite different. There are 11 chapters, each written by a specialist in the particular area: heteronins (Anastassiou). heotsfulvenes (Bertelli), dihydropyrenes (Boekelheid), &lopentadienyl cations (Bredow), systems containing 4-membered rings (Garratt), monocyclic lor-electron systems (KempJones and Masamune), the phenalenyl system (Murate), snnulenes containing chmulenie and acetylenic linkages (Nakagawa), uranoeene (Streitwieser). oerturbedll2lan-
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of authors is excellent and the small amount of bickering over "who did what first" only serves t o convince the reader that the authors themselves really are involved in whatever i t is. In general the writing is clear and in the style found in Accounts of Chemieol Research. In spots the printing leaves something to be desired as some pages are significantly darker than orhem and all of the drawings are mmiarurired. Rut ahat can one exwrt for $21.50?!! With regard t o the qukstian of currentness, the copyright date is 1973 and over half of the chapters include references from that year. For this the editors are t o he congratulated. Although a considerable portion of the material covered in this hook has appeared in the form of review artides (notahly the chapters by Anastassiou and by Kemp-Jones and Masamune), this hook, and probably the remainder of the series, belongs in all chemical libraries. The worker in the field of nonbenzenoid aromatic chemistry will buy i t without urging and the nonspecialist really does not need a personal copy. Thomas J. Barton bwa State University Ames, Iowa 50010
Sulfur Ylldes. Emerglng Synthetic Intermedlates
Barry M Trost and Lawrence S. Meluin, University of Wisconsin. Academic Press, New York, 1975. x 344 pp. Figs. and tables. 23.5 X 16 cm. $39.50.
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of epoaides from carhonyl compounds, cyclopropanes from Michael-type carhon-carban double bonds, and homoallylie sulfides via sigmatropic rearrangement. As in the case of the ylide preparations, the formation of three-memhered rings is categorized according t o the nature of the ylide. These include "methylide," "alkylide" and "stabilized ylide" processes. A brief but useful comparative evaluation of alternative synthetic methods leading t o the major reaction products of ylides is provided. Next, in a very useful complement for those interested in auulvine.. the chemical reactions, 27 experimental pmcedurer relared 1 . 0 sulfonium inl~.r, ylidcr, ep. oxides, ryclopropanes, and rearrangement .produck are provided. Approximately one-half of the hook ronsists of s com~rehenuivetabular disulav of examples in dhieh the three kinds ajp&tinent reactions have been applied. The style of presentation, whieh is similar t o that in "Organic Reactions," includes starting materials and products (name or structure), reaction conditions, yields, and references. The topics are: (1) Epoxidations with Methylides: Ketones; (2) Epoxidations with Methylides: Aldehydes; (3) Epoxidations with Substituted Ylides: (.4 ) Cvelo, prupanatwn with Methylides: r S ) Cyclopropanations with Substituted Ylides: 16) Rearrangements: [2,3]Sigmatropie; and (7) Rearrangements: 1.2-Shift or Stevens
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For the moat part the three types of applications of reactions of sulfur ylides were first looked a t extensively in the late 1960's. Books predating this period do not present too much overlap in synthetic chemistry, although the synthesis of epoxides from ylides is thoroughly covered through January, 1966 [Johnson, A. William, "Ylide Chemistry," Academic Press, Inc., New York, 1966, pp. 3063661. The greatest overlap of information for synthetic application probably appears in "Modern Synthetic Reactions" [House, H. O., "Modern Synthetic Reactions," W. A. Benjamin, Inc., Menlo Park, California, 2nd Ed., 1972, pp. 709-7331, whieh deals with ylide sources, epoxide formation, and cyclopropanation in a much more limited sense.
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The monograph on sulfur ylides was written primarily for the use of synthetic organic chemists, hut with a supplementary general, non-comprehensive treatment of the structural and mechanistic aspects of the subject. According t o the authors, i t is for those "who must face the prohlem of constructing molecules" and it is intended "to stimulate new research in this exciting area." The scope, approach, and style serve this purpose well. The formation of new carhon-carbon bonds through the use of the ylides (r-sulfuranes) most nearly describes the goal of the presentation. The authors describe the synthesis of sulfonium salts and their analogous ylides, with efnphasis on the so-called stabilized (e.g., with adjacent carhonyl groups) and
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unstahilized forms. Suhseouentlv. the use of t h e x ylides is deacrrhed in the formallon
George K. Helmhmp univwsity of Califmia Riverride, Califwnia 92502
Natural Products Chemistry. Volume 1 Edited by Koji Nakonishi, Toshio Goto, Sho Zto, Shimaku Natori, and Shigea Nozoe. Academic Press, Ine., New York, 1974. x 562 p. Figs. and tahles. 19 X 26 em. $32.
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Volume 1covers the structure, synthesis, and hiosynthesis of terpenes and steroids. The stated intent of the series is t o fill the gap between the organic chemistry texthooks and the comprehensive treatise, and the intended audience consists of both the specialist and non-specialist. (Continued on page A2761 Volume 53.Number 5, May 1976 / A275
