PRACTICAL ORGANIC CHEMISTRY - rushim.ru

1 PRACTICALORGANIC CHEMISTRYbyFREDERICK GEORGE MANNSc-D. (Cantab.), (Lond.), , , TRINITY COLLEGE, CAMBRIDGE,UNIVERSITY EMERITUS READER IN ORGANIC CHEMISTRYandBERNARD CHARLES , , (Cantab.), (Lond.), , and New YorkLONGMAN GROUP LIMITEDL ondonAssociated companies, branches and representativesthroughout the worldPublished in the United States of Americaby Longman Inc., New YorkFourth 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 theCopyright Published 1936 Second Edition 1938 New Impressions 1941,1942, 1943,I944, X946,1947, T949, *952 Third Edition 1952 New Impressions 1954, *955, I956, I957> J95<?

2 Fourth Edition 1960 New Impressions 1961, 1962, 1964, 1967, /970, /977 Neiv Impression with revisions 1974 New Impression KJ/5 Reprinted in paper covers, igj8 British Library Cataloguing in Publication DataXEW 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 CHEMISTRY both theoretical and PRACTICAL warranted 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 publishers therefore suggested that a new impressionshould be prepared.

3 This also proved a laborious task, partlybecause of the many minor changes in nomenclature and moreparticularly the presentation of names that the recommenda-tions of the required, and partly because all correc-tions and additions were necessarily limited in length to thespace which the original text had 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.

4 An attempt to deal adequately withspectroscopy in this volume would greatly increase its size andprobably fail in purpose the fate of several books whose authorshave attempted this ambitious are greatly indebted to Dr. D. K. C. Cooper, ,who has critically examined the section on First-Aid to ensurethat it now harmonises with modern medical G. Mann,University Chemical Laboratory, TO FOURTH EDITIONIN the preparation of this revised and extended edition, we havehad in mind two major , 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.

5 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 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 , whilst retaining undiminished the full and cleardirections provided for students who are starting the study ofpractical ORGANIC CHEMISTRY .

6 We have extended the scope of thework so that it covers most of the needs of students working foran Honours or Special 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 preparations, with those noted in the Preface to theThird Edition, cover a considerable proportion of the standardsynthetic reactions.

7 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 earlier editions, Part III (Reactions and Identification ofviii PREFACE TO FOURTH EDITIONO rganic 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.

8 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.

9 The pre-paration of these crystalline derivatives gives the student afurther and very valuable exercise in semi-micro should be emphasised that in Sections 10-27 f ^ai"t HI, , 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 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 use of more complex or more costly articles of equipment,such as catalytic hydrogenation apparatus, autoclaves, polari-meters, ultraviolet absorption spectrometers, etc.

10 , has not beendescribed, because the type of such apparatus employed in differentlaboratories varies considerably, and students must be taught theuse of their own laboratory 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 TO FOURTH EDITION ixThroughout this edition the nomenclature adopted is ingeneral that recommended by the International Union of Pureand Applied CHEMISTRY , and by the Chemical Society (1959).