BOOK REVIEWS
Methods of Elemenloorganic Chemistry. Volume 1, The Organic Compounds of Boron, Aluminum, Gallium, Indium and Thallium
A. N. Nesmeyanm and R. A . Sokolik, both of t,he Institute of ElementaOrganic Compounds, USSR Academy of Sciences, Moscow. Translated from the Russian hy Seripta Technica, Ine. The World Publishing Company, Cleveland & New York, 1967. xiii 628 pp. Figs. and tahles. 16.5 X 25 cm. $24.
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Eighteen years ago, A. N. Nesmeyanov and H.A. Kocheshkov published a baok entitled "Synthetic Methods for Organometallic Compounds of Elements of Group 111." Shortly after that time, an enormous expansion in the organic ehemistry of bornn and aluminum took place, enlarging the field so much that a new book had t,o be written. The present. volume was published in Russian in 1964, then translated by Scripta Technica, Incorporated (under the translation editorship of Paul G. Stecher of Merck, Sharo Q Dohme Research Lshoratories). and published by the North Holland Pub: lishing Co. in Amqterditm in 1967. Sixty percent of the book is devoted to arganoboron compounds, with the subject material divided into sixteen chapters wveringsynthefiisfrom other organometallic compounds, synthesis via organic compounds of the heavy metals, synt,hesis via addition of boron hydrides and halides to unsat~lrated compounds, synthesis by direct boration of organic compounds, symmetrizat,ion reactions and isomerizations, transalkylations, dealkylstion and dearylation reactions, conversions of functional groups, heterocyclic orgsnoboron compo~rnds, mmplexes, hydrogenolysis, reactions of organic subst,it,nents, and analysis. The seet,ion on organoaluminum compounds, which is much shorter (24y0 of the book), is based principally on the work of Ziegler and the corresponding Russian work. There are nine ehapt,ers, dealing with synthesis of organoalmninum eompounds by reaction of alkyl and sryl halides with aluminum, synthesis via Grignard reagents, synthesis via organamei.cmy campo~mds,synthcnis via at,her organometallic compounds, synthesis of alkyl derivatives by addition of aluminum h?-dride and its derivatives to carboncarhon mukiple bonds, synthesis by alumination, maet,ions of organoalnminum compounds, ~ynthesisof orgsnoaluminum compounds containing aluminom-oxygen bonds, and analysis. The organometallie chemistry of gsllium, iudium, and thallium has not changed m ~ ~ duriue ch the same eiehleen " vesrs., and the scarcity of our knowledge is reflected iu the sections devoted to these elements. The part on orgmogsllium eompounds constitutes only 3.3% of the book, and comprises only four topics: synthesis of organogallitm compounds by means of magnesium, aluminum, and sino reagents,
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.A64 / Journal of Chemical Education
synthesis via, orgilnomereury compounds, reactions of orgitnogallium substances, and analysis. The part devoted to indium occupies only 2.7% of the boak, and deals with analogous topies. The part on organothallium compounds reflects an earlier interest in the possible chemotherapy of such substances; it comprises 10% of the book and deals with synthesis via all of the cust,omary orgsnometallic reagents, direct synthesis, synthesis via aryldissonium and diphenylhalonium salts, then reactions and analysis. All of the material on structure and reactions is well organised and useful, of course, but the strong point of this boak lies in the complete directions for the preparation of about 700 compounds. There is no register of compounds, but all of them are listed in the subject index; physical properties and references to the original literature are given right in with the directions for preparation. The following example from page 118 is qnoted in its entirety so that the reader may form a clearer idea, about this baok: "Synthesis of organoborm of the RRCL type via reactions of olefins with boron trichloride [222]. An autoclave is charged with 90 g of BCh, 20 g of Al powder, 0.5 g of C H J and 0.5 g of AICL: the entire mixture is then heated to 120°C. Ethylene is then added in eight 4 g portions, and the mixture is kept a t 1 2 0 T for 3 hours. I t is then cooled to 50DC and the volatile products distilled off s t this temperature and about 3 mm into a cold steel cylinder. The autoclave is cooled to 2 5 T , and the sludge remaining in it is removed and filtered. The filtrate is added to the fraction boiling a t 50°C/5 mm. Distillation of this fraction yields 14 g of C.H6BC1%,bp 52.5'C; the structure of this product can be demonstrated by I R spectra and by hydrolysis to C1HaB(OH)2. Analysis of the remaining fractions (30 g, contaminated with hydrocarbons) shows t,he presence of C4HsBCln(hp 100°C) and ClrHlnBCll(bp 10'J0C/30 mm). "Boron triehlaride and propylene (55 g) react analogously. The liquid re~idue is filtered after collecting the volatile products. Distillation of the crrtde organoboron material (about 140 g) yields fractions bailing a t 65 to lXOoC/4 mm; t,hese contain about 6 g of n-propylbaron dichloride (bp 78"C), whose presence may be confirmed by I R spectrnscopy. The remaining fractions contain a mirture of alkylbaron halides a ~ ~ hydrod carbons (confirmed by mass-rpectrometric analysis). "Similar reactions occur between BCI3 and 1- and 2-butenes." For anyone wit,h research interests in organnmetsllie chemistry, this volume is a very handy new addition to the standard reference works, especially since it brings so much of the less readily-available Russian work into sharp focus and convenient summary. The diagrams and the photo offset printing are clear, and the complete anthor and subject indexes (SO often missing in Rossian books) are a n extra dividend.
EUGENE G. Rocnow Haward University Cambridge, Massachusetts
A Textbook of Pharmaceutical Analysis
K a n e l h A. Connors, University of Wisconsin, Madison. John Wiley & Sons, Inc., New York, 1967. xvii 614 pp. Figs. and tables. 16 X 23.5 em. $12.50.
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Thi? boak is intended as a. text for a drug assay course based an one semester of introductory quantitative analysis, one year of organic chemistry, and, if possible, some physical chemistry. I t is a functional texthook-not a catalog of specific drug assays-organized into six parts: (1) Fundamental Titrimetric Analysis, (2) Physical Methods of Analysis, (3) Separation Techniques, (4) Elemental Analysis, (5) Functional Group Analysis, and (6) Additional Topics. Part One consists of 8, conventional snslyticd treatment of aqueous and nonaqueous ncid-base titrations,,precipitatian, complexometric, and redox tltrations; this oart is l a r d "v n comorehensive review of topics nsudly included in introductory quantitative chemistry, except for the welcome chapter on non-aqueous titrimetry. Systematic pH calculations, including those for polyfunctionsl acids, are pastponed until Part Six. Part Two contains reasonably detailed discussions of several physical techniques, incloding potentiometry, voltammetry, absorption spectroscopy (UV, visible, IR), fluorescence analysis, refrsctametry, palarimetry, phase solubility analysis, and density messurements. The general treatment in this part is considerably more detailed t h a n in the first, although still rather limited in same aspects, such as infrared soeetroscoov and ouantitative aoolications
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chromatography, ion exchange, and malecular sieve processes, while Part Four discusses only nitrogen and mercury in detail (the analytical chemistry of several other metals and nowmetals of pharmaceutical interest is briefly outlined in introduction and summary of this part, however). Part Five contains chapters an hydroxy compounds, carbanyl compounds, carboxylic acids and esters, amines, smides and related compounds, and other classes of compounds, as well as rather strangely placed (though vsluable) chapters on water and on enzymes as anslytical reagents. Additional topics in Part Six are systematic pH ealculrttians, the analytical problem (including sampling and statistical interpretation of data), the analytical literature, and the selection of methods. Appendixes include procedures for preparing potassium chromate spectropho-
tometer~bsorhancestandards(whichmight have been induded in the chapter on ahsorption spectroscopy), a list of "name" reagents, tests, and methods which will be useful to students, as will the solution of quadratic equations, answers to about onefourth of t.he 200-odd problems appearing throughout the boak, four-place lognrithms and an adequate index. The text is. in eeneral. well written and
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