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  • PRACTICALORGANIC CHEMISTRY

    byFREDERICK GEORGE MANN

    Sc-D. (Cantab.), D.Sc. (Lond.), F.R.I.C., F.R.S.FELLOW, T R I N I T Y COLLEGE, C A M B R I D G E ,

    UNIVERSITY E M E R I T U S READER IN O R G A N I C CHEMISTRY

    and

    BERNARD CHARLES SAUNDERSC.B.E., M.A., Sc.D. (Cantab.), D.Sc. (Lond.), F.R.I.C., F.R.C. Path.

    L O N G M A NLondon and New York

  • LONGMAN GROUP LIMITED

    London

    Associated companies, branches and representativesthroughout the world

    Published in the United States of Americaby Longman Inc., New York

    Fourth Edition Frederick George Mann andBernard Charles Saunders 1960

    All rights reserved. No part of this publication may bereproduced, stored in a retrieval system, or transmitted in anyform or by any means, electronic, mechanical, photocopying,recording, or otherwise, without the prior permission of the

    Copyright owner.

    First Published 1936Second Edition 1938

    New Impressions 1941,1942, 1943,I944, X946,1947, T949, *952

    Third Edition 1952New Impressions 1954, *955, I956, I957> J95

  • XEW IMPRESSION, 1974

    The last (4th) Edition of this book appeared in 1960, and has beenfollowed by four New Impressions, the last in 1967. The rapidand ceaseless changing of the presentation of organic chemistryboth theoretical and practicalwarranted an entirely new edition,but this would have entailed a massive task, for which neitherDr. B. C. Saunders nor I had time or opportunity to undertake.

    The publishers therefore suggested that a new impressionshould be prepared. This also proved a laborious task, partlybecause of the many minor changes in nomenclature andmoreparticularlythe presentation of names that the recommenda-tions of the LU.P.A.C. required, and partly because all correc-tions and additions were necessarily limited in length to thespace which the original text had occupied.

    Several of my chemical colleagues have suggested that a newedition of 'M. and S.' should now deal also with the chiefbranches of modern spectroscopy. This would be an aim bothexcellent and impracticable. Students have their own mono-graphs on spectroscopy and their own teachers, whose expositionshould clarify the branches of this subject more rapidly and easilythan the printed text. An attempt to deal adequately withspectroscopy in this volume would greatly increase its size andprobably fail in purposethe fate of several books whose authorshave attempted this ambitious programme.

    Wc are greatly indebted to Dr. D. K. C. Cooper, F.R.C.S.,who has critically examined the section on First-Aid to ensurethat it now harmonises with modern medical practice.

    F. G. Mann,University Chemical Laboratory,Cambridge.March 1973.

  • PREFACE TO FOURTH EDITION

    IN the preparation of this revised and extended edition, we havehad in mind two major factors.

    First, considerably greater emphasis has been placed on semi-micro techniques and their application to preparations, separa-tions, analysis and physical determinations such as those ofmolecular weight. We have therefore greatly expanded thesection on Manipulation on a semi-micro scale which was in theThird Edition, and we have described many more preparationson this scale, some independent and others as alternatives tothe larger-scale preparations which immediately precede them.Some 40 separate preparations on the semi-micro scale aredescribed in detail, in addition to specific directions for thepreparation of many classes of crystalline derivatives requiredfor identification purposes. The equipment required for thesesmall-scale reactions has been selected on a realistic basis, andcare has been taken not to include the very curious pieces ofapparatus sometimes suggested as necessary for working on thesemi-micro scale.

    Secondly, whilst retaining undiminished the full and cleardirections provided for students who are starting the study ofpractical organic chemistry, we have extended the scope of thework so that it covers most of the needs of students working foran Honours or Special Degree.

    To meet the needs of the advanced students, preparationshave now been included to illustrate, for example, reduction bylithium aluminium hydride and by the Meerwein-Ponndorf-Verley method, oxidation by selenium dioxide and by periodate,the Michael, Hoesch, Leuckart and Doebner-Miller Reactions,the Knorr pyrrole and the Hantzsch collidine syntheses, variousFree Radical reactions, the Pinacol-Pinacolone, Beckmann andArbusov Rearrangements, and the Bart and the Meyer Reactions,together with many others.

    These preparations, with those noted in the Preface to theThird Edition, cover a considerable proportion of the standardsynthetic reactions. Most of these preparations come towards theend of Part II (Preparations), and both elementary and advancedstudents should have no difficulty in selecting the preparativework they require.

    In earlier editions, Part III (Reactions and Identification of

  • viii PREFACE TO FOURTH EDITION

    Organic Compounds) was designed to give students a thoroughtraining in the general reactions of the simpler members of eachof the main classes of organic compounds, and in the methodsby which an unknown compound could be first allocated to itsclass and then identified. Clearly, more advanced students willmeet a wider range of members of each class of compound, andthe final identification must usually be based on the melting-points of crystalline derivatives. We have therefore inserted inthe account of each class a note of the types of crystalline deriva-tives which can be most rapidly and reliably prepared, with fullexperimental details. Our Tables of Melting-points of deriva-tives, given at the end of the book, have been very considerablyextended, so that the advanced student, who, like the elementarystudent, must first allocate his unknown compound to its class,can now prepare one or more crystalline derivatives, and com-plete the identification by reference to these tables. The pre-paration of these crystalline derivatives gives the student afurther and very valuable exercise in semi-micro preparations.It should be emphasised that in Sections 10-27 f ^ai"t HI,i.e., the sections which are each devoted to one class of com-pound, the simpler or more common members are still clearlyspecified, and their reactions discussed, so that again the lessadvanced student can readily discern the range of the materialwhich is his immediate concern.

    For the more advanced student, we have extended the sectionon Quantitative Semi-micro Analysis, and we have included asection dealing with Special Techniques in Separation andPurification, namely Adsorption Chromatography, Paper Chro-matography, and Ion-Exchange Processes.

    The use of more complex or more costly articles of equipment,such as catalytic hydrogenation apparatus, autoclaves, polari-meters, ultraviolet absorption spectrometers, etc., has not beendescribed, because the type of such apparatus employed in differentlaboratories varies considerably, and students must be taught theuse of their own laboratory equipment.

    In the First Edition of this book, we included a short sectionto illustrate some of the more simple or the more clearly definedreactions which are promoted by enz\mes. It was hoped thatthis section might stimulate the interest of younger chemists inthe preparative value oi such Tcactioris, but organic chemists stilllargely ignore this branch oi preparative work. We have nowdeleted certain portions of this section, and emphasised otherportions having greater current interest.

  • PREFACE TO FOURTH EDITION ix

    Throughout this edition the nomenclature adopted is ingeneral that recommended by the International Union of Pureand Applied Chemistry, and by the Chemical Society (1959).

    In the preparation of this edition, we are indebted for muchhelp to many of our colleagues, and in particular to Dr. P. Sykes,Dr. F. B. Kipping, Dr. P. Maitland, Dr. J. Harley-Mason andDr. R. E. D. Clark. We have maintained the standard whichwas self-imposed \vhen this book was first written, namely, thatall the experiments in the book had been critically examined,and then performed either by the authors, or under their super-vision. The heavy load of work \vhich this has involved wouldhave been impossible without the will ing, patient, and veryconsiderable help of AIr. F. C. Baker and Mr. F. E. G. Smith.

    F. G. M.Cambridge, 1960 B.C.S.

  • PREFACE TO THIRD EDITION

    FOR the production of this edition, we have made a thorough andcritical revision of the whole contents of the book, based on ourexperience of its use in the laboratory and on the general advancein organic chemical practice. In addition to this general revision.however, we have extended the book in three main directions.

    The book as originally planned was intended to meet the needsprimarily of pupils'in the senior forms at schools and of under-graduates up to the level of a Pass Degree. We have extendedParts II and III dealing with Preparations and with the Reactionsand Identification of Organic Compounds so that the book shouldnow cater fully for the needs of students working for HonoursDegrees. In particular, the Preparations now include examplesof most of the more simple standard reactions: for this pur-pose we have now added, for example, preparations illustratingthe Benzidine Transformation, the Ullmann Condensation,the Benzilic Acid Rearrangement, the Reformatsky Reaction, theClemmensen Reduction, the Fischer Indolisation Reaction, theMannich Reaction, and the Diels-Alder Reaction. It is probablethat preparative work on a much smaller scale than has hithertobeen customary in teaching laboratories will become morecommon in future. To meet this need, we have added a shortsection to Part I, describing the design and use of apparatus forthis pu

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