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CRC Handbook of tables for Organic Compound Identification CRC HANDBOOK of tables for ORGANIC COMPOUND IDENTIFICATION Third Edition Compiled by ZVI RAPPOPORT, Ph.D. Hebrew University of Jerusalem, Israel :V- CRC Press, Inc. Boca Raton, Florida 16 «. 12/0031150-21":" This book represents information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Every reasonable effort has been made to give reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Direct all inquiries to CRC Press, Inc., 2000 Corporate Blvd., N. W., Boca Raton, Florida, 33431. © 1967 by CRC Press, Inc. Formerly The Chemical Rubber Company International Standard Book Number (ISBN) 0-8493-0303-6 Former International Standard Book Number (ISBN) 0-87819-303-0 Library of Congress Card Number 63-19660 Printed in the United States 15 16 17 18 19 20 Printed on acid-free paper First Edition Tables for Identification of Organic Compounds Compiled by Max Frankel, Ph.D. Saul Patai, Ph.D. Assisted by Albert Zikha, Ph.D. Robert Farkas—Kadmon © I960 by SCIENCE PRESS, LTD., JERUSALEM, ISRAEL Second Edition Tables for Identification of Organic Compounds Compiled by Max Frankel, Ph.D. Saul Patai, Ph.D. Assisted by Albert Zilkha, Ph.D. Zvi Rappoport, Ph.D. Robert Farkas—Kadmon © 1964 by THE CHEMICAL RUBBER CO. Third Edition Handbook of Tables for Organic Compound Identification Compiled by Zvi Rappoport, Ph.D. CONTROLLED RELEASE PESTICIDES FORMULATIONS By Nate F. Cardarelli, M.S., University of Akron. DIFFUSE REFLECTANCE SPECTROSCOPY IN ENVIRONMENTAL PROBLEM-SOLVING By R. W. Frei, Ph.D., Sandox, Ltd. (Switzerland), and J. D. MacNeil, M.Sc., Ph.D., Canada Department of Agri- culture. DRUGS AS TERATOGENS By James L. Schaidein, B.A., M.S., Parke, Davis and Company. FUNDAMENTAL MEASURES AND CONSTANTS FOR SCIENCE AND TECHNOLOGY By Frederick D. Rossini, Ph D., Rice University, Houston. IMMUNOASSAYS FOR DRUGS SUBJECT TO ABUSE Edited by S. J. Mule, Ph.D., New York State Narcotic Addiction Control Commission, et al. MASS SPECTROSCOPY OF PESTICIDES AND POLLUTANTS By Stephen Safe, B.Sc., M.Sc., DJ>hil., and Otto Hutzinger, Ing.Chem., M.Sc., Ph.D., National Research Council of Canada. MERCURY IN THE ENVIRONMENT By Lars T. Friberg, M.D., National Institute of Public Health (Stockholm), and Jaroslav J. Vostal, M.D., Ph.D., University of Rochester. ORGANOPHOSPHORUS PESTICIDES: ORGANIC AND BIOLOGICAL CHEMISTRY By Morifusa Eto, Ph.D., Kyushu University, Japan. RECENT DEVELOPMENTS IN SEPARATION SCIENCE Edited by Norman N. Li, Sc.D., Exxon Research and Engineering Co. TRACE ELEMENT MEASUREMENTS AT THE COAL-FIRED STEAM PLANT By W. S. Lyon, Jr. B.S., M.S., Oak Ridge National Laboratory. CRC CRITICAL REVIEWS™ JOURNALS: CRC CRITICAL REVIEWS™ IN ANALYTICAL CHEMISTRY Edited by Bruce H. Campbell, Ph.D., J. T. Baker Chemical Co. CRC CRITICAL REVIEWS™ IN TOXICOLOGY Edited by Leon Golberg, M.D., B.Chii., D.Sc., D.Phil., F.R.C.Path., Chemical Industry Institute of Toxicology Direct inquiries to CRC Press, Inc. PREFACE The present volume is a revised and enlarged third edition of the book formerly titled TABLES FOR IDENTIFICATION OF ORGANIC COMPOUNDS. Four new classes of compounds, i.e., sulfonyl chlorides, sulfonamides, thiols and thioethers were added, bringing the number of classes included in the book to twenty-six. The tables of alkanes, alkenes, alkynes, aromatic hydrocarbons, phenols, nitriles and sulfonic acids were all thoroughly revised and considerably enlarged. In all, the addition of 2400 compounds to the third edition, raised the total number of parent compounds in the book to over 8150. Three tables containing the dissociation constants of more than 1050 phenols, organic acids and organic bases were added. Correlation charts for I.R., Far I.R. and N.M.R. were also included. Explanatory sections entitled "Explanations and References" precede the tables. In these sections the formulas of the derivatives and the full reaction equations for their preparation by the most important methods, together with some essential details and references to their preparations, are given. An index covering both the names and synonyms of the compounds was added at the end of the book. An index listing the names of all tables and major subjects was also added. The main objective of this book is to assist chemists in the identification of organic compounds. The organization of the compounds in classes according to increasing boiling points should also assist in the search for standard vapor phase chromatography work. For further information of techniques of organic analysis one or more of the following books should be consulted: N. D. Cheronis, J. B. Entrikin and E. M. Hodnett, Semimicro Qualitative Organic Analysis, 3rd Ed., Interscience Publishers, New York, 1965. L. Meites, Handbook of Analytical Chemistry, McGraw Hill Book Co., 1963. F. Feigl, Spot Tests in Organic Analysis, 6th Ed., Elsevier Publishing Co., 1960. A. I. Vogel, A Textbook of Practical Organic Chemistry, 3rd Ed., Longmans Green and Co., London, 1957. R. L. Shriner, R. C. Fuson and D. Y. Curtin, The Systematic Identification of Organic Compounds, 4th Ed., John Wiley and Sons, New York, 1956. F. Wild, Characterization of Organic Compounds, 2nd Ed., Cambridge University Press, 1958. The publication of the third edition would not have been possible without the work of those involved in the preparation of the earlier editions. The editor is thankful for the part in the earlier work contributed by Professors M. Frankel, S. Patai and A. Zilkha, and the late Mr. R. Farkas-Kadmon. Thanks are due also to Mrs. E. Shohamy and Mr. A. Glazer for assisting in collection of new data, to Mrs. Y. Elmaleh for typing the index, and especially to Prof. S. Patai, who as consulting editor, read all the new material and gave many helpful suggestions. The cooperation of Dr. Robert C. Weast and Mrs. F. Thomas in the publication of the book is gratefully acknowledged. Z. R. Jerusalem January 1967 Handbook of tables for Organic Compound Identification, © 1967 CRC LIST OF ABBREVIATIONS USED specific rotation um fuming pr prisms Ma D acid j;Iac glacial purp purple abs absolute 'lit glittering pyr pyndine abt about ?lyc glycerol rac racemic ac a acetic acid gran granular (or racemate) ac anh acetic anhydride grn green reel rectangular acet acetone , hot recr recrystallization add addition htng heating redsh reddish al alcohol hyd hydrate or rhomb rhombic alk alkali hydrolyses r rapid amor amorphous hyg , hygr hygroscopic rh rapid heating anh anhydrous ; inactive s soluble arom aromatic i insoluble sec secondary aqu aqueous ign ignites scar scarcely asym , as asymmetric msol insoluble s h slow heating blue 1 ,L levorotatory sh short (or L-configura- si slightly blk black boil boiling tion) sld solid bp.B P boiling point leaf. If leaflets slend slender br brown lg large sm fsmm aolill bz benzene 'gr ligroin soft softens brt bright hq liquid sol , soln solution(s) brnsh brownish Ing long solv solvent(s) Q cold It light st steel CcQaust acabuosutitc I/Tvis- lmeacvtses sstuabbl sstuabblliemes chl chloroform me , meth methyl sym symmetrical cl -bz chlorobenzene micr microscopic tab , tabl tablet(s), tables col colorless mixt mixture ten tertiary comp compound ml milliliter tetr tetragonal cone concentrated mod modification tol toluene cor corrected monohyd monohydrate trans transparent cr , cryst crystals monocl monochnic thk thick d decomposes m p , M P melting point tncl tnchmc d,D dextrorotatory need , nd needles trim tnmenc (or D-configuration) 0- ortho uns unsymmetrical dcnv derivative ol olive unst unstable dehq deliquescent or orange vac vacuum, in vacuo dil dilute ord ordinary V very dist distillate org organic var variable dk dark orth orthorhombic vic- vicinal dl , d,l, D,L racemic oxid oxidation V1SC viscous efflor efflorescent P- para volat volatile or volatilizes et ethyl pa pale vlt violet et ac ethyl acetate part partly w water eth ether pet petroleum wh white exp explodes pet eth petroleum ether yel yellow fi from ph phenyl yelsh, ylsh yellowish fl flakes ph hydraz phenyl hydrazine > above, greater than fluores fluorescent PhNO2 nitrobenzene < below, smaller than fp freezing point pl plates oo irascible frz freezes powd powder xyl xylene Handbook of tables for Organic Compound Identification, © 1967 CRC EXPLANATIONS AND REFERENCES TO THE TABLES The following section gives explanations and references for the preparation of the derivatives appear- ing in the Tables Formulas of the derivatives as well as the mam methods for their preparation are given Usually, only the reagents and the solvents required for the preparation of a derivative are mentioned without specific details for the reaction conditions and the exact procedure The aim of these notes is mainly to enable the worker to choose the method preferable in the conditions and the reagents available to him in his laboratory for the denvatization of his specific compound However, THIS IS ONLY A REFERENCE SECTION AND NOT AN INSTRUCTION MANUAL AND THE QUOTED REFERENCES SHOULD BE CON- SULTED FOR THE ACTUAL PREPARATION OF DERIVATIVES, ESPECIALLY REGARDING SAFETY HAZARDS INVOLVED IN THE WORK. References are usually given for the preparation of all the derivatives having separate columns in the Tables, as well as for important ones listed in the "miscellaneous" section of the Tables References to five different popular analytical textbooks are given, assuming that at least one of them, or another equivalent publication, would be available to the worker These are N D Cheroms, J B Entnkin and E M Hodnett, Semimicro Qualitative Organic Analysis, 3rd edition, Interscience, New York, 1965, quoted in the text as "Cheroms " R P Linstead and B C L Weedon, A Guide to Qualitative Organic Chemical Analysis, Butterworth Scien- tific Publication, London, 1956, quoted in the text as "Linstead " R L Shnner, R C Fuson and D Y Curtin, The Systematic Identification of Organic Compounds, 4th edition, John Wiley and Sons, New York, 1956, quoted in the text as "Shnner " A I Vogel, A Textbook of Practical Organic Chemistry, 3rd edition, Longmans, Green and Co , London, 1957, quoted in the text as "Vogel " F Wild, Characterization of Organic Compounds, 2nd edition, Cambridge University Press, Cambridge, 1958, quoted in the text as "Wild " In addition, leading references from the original literature are also given Although the literature cover- age is not complete (especially for the common derivatives) it was attempted to describe different methods, and to give as many references as possible to less common derivatives having limited scope More references can be found in the textbooks mentioned above Derivatives appear either in a separate column or in the "miscellaneous" section in the Tables, where separate columns are usually given for derivatives which should be tried first, and for which enough data are available Derivatives which should be tried as a second choice, or preferred derivatives for which not enough data are available appear in the "miscellaneous" section The explanations and the references for the different derivatives are arranged usually in the same order as in the Tables Occasionally, this order is changed in the explanatory notes in order to describe the derivatives in a logical order (eg, in Table 17 the phenylurethane appears in a separate column, while the phenylhydantom appears in the "miscellaneous" section in the "explanations and references" section the phenylhydantom appears directly after the phenylurethane) Derivatives which are followed by an asterisk are those recommended for first trial Other derivatives should be tried after these Although "Ar" usually stands for monovalent aromatic group, we used it a few times in the following sections as a polyvalent aromatic residue This was done only for demonstration purposes Handbook of tables for Organic Compound Identification, © 1967 CRC Handbook of tables for Organic Compound Identification, © 1967 CRC EXPLANATIONS AND REFERENCES TO TABLE I As a result of their inertness no general suitable derivative exists for alkanes and cycloalkanes Charac- terization is based only on the physical constants given in the Table melting and boiling points, index of re- fraction and density Any laboratory text-book will give adequate directions for the determination of these constants ,,r*„