Interpretation of Mars Organic Compounds
Spectra
of
Herbmt Budri!&wk, Carl Djerassi, and Dudley H . Williams, all of Stanfurd Universitv. Stanford. California. ", Holden-Day, Inc., Ssn Francisco, 1964. xiii 271 pp. Figs. and tables. 19.5 X 26 em. $8.75.
+
"Three years ago one had to search far and wide in the organic chemical Literature to h d examples of its use in structural problems. Three years hence it will be difficult to open a journal dealing with organic chemistry without encountering multiple applications of mass spectrometry. No physical tool in organic chemistry-not even infrared spectrometryis so easily appreciated by the average organic chemist, and once used, none is so difficult to do without." With this statement, which is certain to be quoted wherever organic chemists gather, and the recommendation to read the general texts and chapters on mess spectrometry, the reader is plunged directly into the fascinating world of "fishhook" chemistry. The reviewer uses the word chemistry advisedly, rather than mass spectrometry, beceuse the book under review is really a textbook of one phase of organic chemistry. The Table of Contents reads, chapter by chapter, as follows: Aliphatic and Monocyclic Carhonyl Compounds; Alcohols; Ethers, Thioethers, and Mercaptans; Aminm and Amides; Cyclic Amines; Aliphatic Cyanides and Isothiocyanates; Alkyl Halides; Bieyclic Ketones; Aromatic Hydrocarbons and Funotional Derive tives; Tropones and Tropolones; Aromatic Heterocyclics. Whereas the standard organic texb book deals with reactions initiated by chemical reagents or by thermal or actinic energy, the present book describes the consequences suffered by an organic molecule struck by an ionizing electron beam at a vapor pressure of ahout 10-5 mm Hg. The resulting unimolecular modes of decomposition are depicted by fishhooks (e which ) are to oneelectron transfer are mechrtnisms what curved arrows ( -r) to ionic mechanisms. The organic chemist very quickly finds himself at ease among the fishhooks. He recognizes that standard physical-organic concepts have been applied to rationalize the fragmentation mechanisms. The fishhook is replacing the mass spectrome trist's wiggly line (3) just as the curved arrow has replaced the double lasso ( b D ) beloved by generations of organic chemists. Previously, the tendency has been not to loeilliae the charge formed by removal of a single electron from the molecule by the electron beam. The authors achieve a pedagogic triumph by showing consistently how the locelized charge, usually on a heteroatom, triggers rational fragmentation processes. I n many cases, the mcchs.nisms have been substantiated by isotope labelling experiments. Frequently the warning signal, "plausible," is displayed, but this still seems preferable to the wiggly line designation. This book is directed primarily a t "the organic chemist working with a given
464 / Chemical Education
clasa of organic compounds-[who] wishes to know how mass spectrometry can help him, and where he can find the relevant guideposts." There is no better source than the present book for help in the interpretation of massspectra. I t will be on the desk of every organic chemist who has access to a. mass spectrometer. The authors and the publisher have performed another service by making the book available within three months after receipt of the manuscript. Some of the journal papers referred to in the book as '>. m press" appeared several months i~iter publication of the book. There were, admittedly, the favorable circumtances of proximity of authors and publisher, facilities available to the authors, and the enterprise of a new publisher in a competitive field. The unique ingredient may simply be the personality of the senior author. The reviewer considers a listing of minor errors of style and content to be a law order of gamesmanship. Under the eircumstance noted above, however, one is tempted to look for signs of undue haste. They are remarkably few and tnvial. Even the index, frequently skimped by exhausted authors, is thorough. Perhaps an editor under less pressure might have caught an occasional "due to the fact that," or "just like," or a "proverbial wiggly line." The book is an example of good "typewriter composition"; the righehand margin is not "justified." The figures are numerous and neat; they contribute greatly toreadability. The introductory remarks are eloquent, the text lucid throughout.
structure problems. There are essentially no discussion questions, thought-provoking mechanistic questions, or questions involving decisions other than tho% eoncerned with selection of reagents. However, although the problems omit several vital subject areas and essential mental processes in modern organic chemistry, the book is excellent,in furnishingan unusually extensive number of problems using timehonored reactiona of functional groups-its avowed purpose. FRANKL. LAMBERT Occidental College Los Angeles, Calijo-nia
Synthetic Methods of Organic Chemirtry. Volume 16
W . Thedheimer. Interscience Publishers (a Division of John Wiley and Sans, 508 pp. Inc.), New York, 1962. xvi 16.5 X 23 em. $48.
+
Valunle 16 is the first of a fourth series of volumes. It contains 996 monographs in 443 pp, of text and includes 56 pp. of indexes. Although it is the first of a new series, there are many references to syntheses in previous volumes. Trends in Synthetic Organic Chemistry again draws together publications which were published too late to be included in the body of the text. Some random examples of interest are the use of arsenic ylids in place of phosphorus ylids in the Wittig synthesis; room temperature esterifications using tetrachloraaluminio acid ether complex; "one-shot" syntheses of ROBERTM. SILVERSTEIN oligopeptides and p-lactsms from the Stanford Reseamh Institute simultaneous reaction of from 2 to 5 reactants; trimerizations of acetylenes to Menlo Park, Calijornio benzene derivatives using a Ziegler catalyst ~ r e ~ a r efrom d triethvlaluminum and tita&m tetrachloride; "and the preparation Problems in Organic Chemistry: A of D-norsteraids by ring contraction of nFunctional Group Approach diazoketones. Ralp,+ Daniels and Ludwig Bauer, UniThe monographs in the text itself are versity of Illinois, Chicago. 2nd ed. taken primarily from 1960 and 1961. F. A. Davis Co., Philadelphia, 1964. Some of the monographs which were a& vii 220 pp. 15 X 22.5 em. Psipertractive to the reviewer are: selective bound. $3.75. 0-deacylation in the presence of a formamide group; low pressure reduction of The second edition of Daniels and Bauer nitriles in 91-100% using Rsney metal is identical to the first except for the apcatalyst in acetic anhydride along with a pending of 23 pages of answers to selected basic ca-catalyst; the disproportionation problems in this new edition. In broad of ditropyl ether to tropune and cyeloformat this problem hook is similar to heptatriene; the vinylation of benzene Hansch and Helmkamp or Rietz and sulfonic acid; the direct conversion of Pollard: some 24 chapters arranged seamines or ketimines to m-aminoketones; cording to functional groups, plus special the apparent solvolysis of half the cyano topics such as stereoisomerism. Daniels groups in tetracyanoethylene with ethylend Bauer contains no descriptive material ene glycol to pyridia cyclic aeetal; the on reactions or mechanisms. I t employs formation of pyridines starting with an the unified treatment of aromatic and eneyne-one through the pyryllium salt; aliphatic compounds. conjugate Diels-Alder addition to a vinylThe general arrangement of each chapter cyclopropane to give a cyeluheptene derivincludes a fairly extensive nomenclature ative; conversion of Ziodophend to 2section, a. summary of functional group hydroxyhipbenyl in 6(t70Y0 in a one-step reactions in a "starburst" chart showing photochemical reaction; the synthesis of the results of treating a, type compound spira-[4.2]-1,3-heptadiene;and a synthesirr ~ i t many h different reagents, and several of 9-(p-~hlorobenayl1de11e)fluurene via. an pages of problems. Practically all of the arsaniunl salt. thousands of problems are concerned with "give reagents," "synthesize," "distinERNEST I. BECKER guish," "convert." There are nomenclaPolyleehnie Inatllute of Brooklyn ture questions also, e very few regurgitaBrooklyn, New York tion questions on mechanisms, some (Continued on page ,4590) separations, and some "compound A"
+
