INTERNATIONAL CHEMICAL SERIES H. P. TALBOT, Pu.D., Consuntina Eprror PRINCIPLES OF ORGANIC CHEMISTRYINTERNATIONAL CHEMICAL SERIES (H. P. Tatzor, Pu.D., Sc.D., Consunmna Eprror) Bancroft ‘ABBLIED COLLOID CHEM- ISTRY Bingham— cEbUibiry AND PLasTicITY cal ‘ORGANIC CHEMISTRY ‘GENERAL CHEMISTRY Origin ‘ECHNICAL METHODS OF ANALYSIS As Employed in the Labora- tories of Arthur D. Little, Inc. Hall and Williams— CHEMICAL AND METALLO- GRAPHIC EXAMINATION ‘STEEL AND Hamilton and Simpson— CALCULATIONS OF. TITATIVE, CHE: ANALYSIS Loeb— PROTEINS AND THI SGEORY oF COLLOIDAL BEHAVIOR Lord and Demorest— METALLURGICAL ANALY- ourth dition QUANTITATIVE ANALYSIS Second Edition Mahin and Carr— QUANTITATIVE _AGRICUL- TURAL ANALYSIS UAN- ICAL Millard— PHYSICAL CHEMISTRY FOR COLLEGES Moore— HISTORY OF CHEMISTRY Norris— TEXTBOOK OF INORGANIC CHEMISTRY FOR COL- LEGES Norris and Mark— LABORATORY EXERCISES IN INORGANIC CHEMIS- Norrie— ORGANIC CHEMISTRY Second Edition Norrie— EXPERIMENTAL ORGANIC CHEMISTRY Parr— ANALYSIS OF FUEL, GAS. WATER AND LUBRICANTS ‘Third Edition Robinson— THE ELEMENTS OF FRAC- TIONAL DISTILLATION White— TECHNICAL GAS AND FUEL ANALYSIS. Second Edition Williams— PRINCIPLES OF METALLO- GRAPHY Woodman— FOOD ANALYSISTHE PRINCIPLES OF ORGANIC CHEMISTRY BY JAMES F. NORRIS Proressor or Orcanic Cuemistry Massacausers INstITUTE oP TrcuNotocy; AUTHOR or “EXPERIMENTAL OrGaNic CHEMISTRY;” “A Text Boox or Ivorcanic Caemistry ror CouLEGEs” anp (wits K. L, Marx) “Lasoratory EXercises 1N Inorganic Czmanstry” Seconp Eprrion Fourrn Impression Total Issue, 38,000 McGRAW-HILL BOOK COMPANY, Inc. NEW YORK: 370 SEVENTH AVENUE LONDON: 6 & 8 BOUVERIE ST., E. C4 1922Copyriaur, 1912, 1922, By THE McGraw-Hitt Boox Company PRINTED IN THE UNITED STATES OF AMERICA THE MAPLE PRESS YORE PAPREFACE TO THE SECOND EDITION The development which has taken place in organic chemistry since this book was published has made it necessary to prepare a new edition. This development has been marked on both the theoretical and the practical sides of the subject. While the advances in the pure science have been largely of such a character that they should not be included in an elementary textbook, the development of industrial organic chemistry has tended to vitalize the subject and to arouse the interest of the beginner As the result of the recent war there was an increased demand for a large number of organic compounds of industrial importance. The search for new methods of preparing these substances on the large scale led to the utilization of reactions which were formerly of theoretical interest only, or to the application of newer methods such as those of catalysis and electro-chemistry. These new industrial processes have been emphasized as fully as is con- sistent with the scope of the book. The growth of the dyestuff industry in America made it desirable to broaden to some extent the treatment of the aro- matic compounds and to include brief descriptions of the more important intermediates and of the sulphur and vat dyes. The increasing use of the organic derivatives of mercury and of arsenic in combating disease made it necessary to introduce an elementary consideration of the general reactions underlying the preparation of such compounds. The renewed interest in the application of organic compounds in warfare has led to the description of the more important war gases and the new explosives. The consideration of the chemis- try of the fats, carbohydrates, and proteins has been extended to include the physiological aspects of the subject. The additions to the text in the field of the pure science have been limited in number. It is the opinion of the author that the newer theories, such, for example, as the interpretation of the reactions of organic compounds by means of the electronic vvi PREFACE TO THE SECOND EDITION conception of matter, should not be included in the first element- ary presentation of the subject, with the resultant exclusion of important theoretical material based on a more substantial experimental foundation. In this edition the theory of partial valence and the relation between chemical structure and color are briefly discussed. There is given, also, an account of the recent work on the structure of tannins and the coloring matter of flowers. The space given to the additions to the text has been limited by the scope of the book. It has been the aim of the author to keep the amount of the material and its treatment within the limits suitable for a first course in organic chemistry. As a consequence, the book contains only about fifty pages more than the earlier edition. By restricting the space given to each addi- tion, an attempt has been made to have the new edition repre- sent the present status of that part of the science which is considered, without unduly increasing the size of the book. James F, Norris. Canprincz, Mass. May, 1922PREFACE TO THE FIRST EDITION Tus book is the outcome of a number of years’ experience in teaching the elements of organic chemistry to classes of beginners in the subject. In it an attempt has been made to emphasize the fundamental principles of the science, and to describe in some detail the organic compounds of practical importance. The substances considered have been selected from this point of view. As a consequence, many compounds of interest to the more ad- vanced student have been omitted; the space gained in this way has been devoted to a fuller consideration of the more important typical reactions of organic compounds, and the applications of the science have been treated at greater length than is customary in elementary text-books. The order in which the several classes of compounds are dis- cussed differs from that usually followed, and is the result of the emphasis placed on the effect of the nature of organic radicals on the properties of compounds containing them. To bring out clearly this effect, the radicals are referred to hydrogen as a stand- ard; those more base-forming than hydrogen are classed as posi- tive, and those more acid-forming as negative. The selection of the terms positive and negative is, perhaps, unfortunate, on ac- count of the fact that these words have been used in other con- nections with a different meaning from that employed here. But no more expressive terms appear to be available, and they have been often used in organic chemistry with the significance assigned to them in this book. Alcohols consist of a positive radical in combination with the hydroxyl group, and acids of a negative radical with this group. This view leads to a consideration of acids after alcohols have been described. The relationship exist- ing between the two classes of compounds and their analogies to inorganic bases and acids, can be clearly emphasized from this point of view. Next are considered ethers, anhydrides, and esters, viiviii PREFACE TO THE FIRST EDITION compounds which contain respectively, two positive radicals, two negative radicals, and one positive and one negative radical linked to oxygen. The classing of these three types of compounds together makes it possible to bring out the relationship between the properties of compounds and the character of the radicals they contain. The consideration of alkyl and acyl halides, and of amines and amides in a similar way facilitates markedly the study of the properties of these compounds. On account of the increasing attention paid to organic chemistry as a basis for the study of foods, the carbohydrates, fats, and pro- teins have been treated more fully than is customary in elementary text-books. Although the investigations of Fischer and his co- workers have placed the study of the proteins on a scientific basis, work has not advanced sufficiently far to warrant a strictly chemi- cal classification of these compounds. The proteins are con- sidered, therefore, according to the classification adopted by the American Society of Biological Chemists and the American Physi- ological Society. Some of the more important results of Fischer in the study of the hydrolysis of proteins and the syntheses of polypeptids have been given. The methods used in the identification of organic substances have been described and illustrated by examples. The reactions of analytical significance of the various classes of compounds have been summarized in Chapter XVII. The identification of simple substances is becoming more and more a part of the laboratory practise in organic chemistry. The experience of the author has convinced him that this kind of work has great pedagogical value and can replace profitably a part of the synthetic work of the student. The book aims to furnish the elementary facts required for such work. In Chapter XVII the methods of deducing the structure of a compound from the results of the ultimate analysis of the compound and certain of its derivatives are illustrated by examples. Problems are given at the end of most of the chapters. These are not merely “quiz” questions on the text; their solution in- volves, in most cases, a careful study of the principles discussed and their intelligent application. The solution of problems such as those given has been found to be of the greatest value to the student.PREFACE TO THE FIRST EDITION ix The author wishes to express his thanks to Prof. W. T. Hall, of the Massachusetts Institute of Technology and Prof. Alice F. Blood, of Simmons College, for valuable criticism and suggestions. He is especially grateful to his wife, who copied the entire manu- script of the book, assisted in proof-reading, and helped in many ways that made the preparation of the book possible. J. F. Norris. Boston, Mass., March, 1912.CONTENT! Pace Prerace To Seconp Epition. ..... - ee v Prerace To First Epition. . . 2. ee ee ee vii Cuarrer I. Scope anp Meruops or OraaNic CHEMISTRY. . . . . . - 1 II, Hyprocarsons or THE MetHaNe Suries. . . . . aoe 22 Ill. Hyprocarsons or THE Eraytene Series... .... . 47 IV. Hyprocarsons or THE AcETYLENE Serres: Dioterines. . 60 V. SaruraTep ALCOHOLS... .. ~~. - 72 VI. UnsaruraTep ALconoLé Pouyayproxr- ALconots. . 105 VII. Monopasic Actos... .-. . 1s ee 116 VIII. PonypastcAcms ........- se se . 146 IX. Erasers, ANnypRIpEs, AND Esters. ...... - 157 X. Aupenypes anp Ketonzs...... . . . 187 XI. Amines anp Amipzs, . wae . . 211 XII. Cyanocen anp RELATED Compounns ee . 236 XIIIl. Hatogen Compounps..... . + +. 251 XIV. Compounps Contarnine Two Untixe / Supstrrvenrs +. + 276 XV. CarponypRaTEs, . . . » 825 XVI. Compounps Contamina PHosrHors, ARSENIC, Soxeaun METIS... 7... e . 359 XVI. Tae IpENTIFICATION OF Oneante “Compounns | AND THE DETERMINATION OF THEIR STRUCTURE... .. 2... 371 XVIII. Uric Activ anp Retatep Compounns . . we ss B86 XIX. Cycuic Hyprocarpons...-.-- 0. eee ee 392 XX. DETERMINATION OF THE Smucrure \ or ‘Anomatic Com- pounps. Nitro Compounps AND SutrHonic Acips . . . . 424 XXI. Hatogen Derivatives or Aromatic HypRocaRBons. » . 440 XXII Aromatic Amines AND OTHER ReEpucTION PRopucts oF Nirro Compounps......... oe - - 450 XXIII. Diazo Compounps........ 2... soe ee + 466 XXIV. Aromatic ALconots, PHENOLS, AND Erners we ee 476 XXV. Aromatic Acips. .........-- see. 490 XXVI Anowaric Atppnypes, Ketones, AND QUINONES . . 502 XXVII. Aromatic Compounps Contarnina Two or More UNLIKE Groups... 1. eee ee ee ee see . 518 XXVIU. Dyes... 2. ee ee eee E . 551 XXIX. Terrenes anp CaMPHoRS...... . . - 569 XXX. Hersrocyciic Compounps....... eee eee. 5B XXXI, Proves... . . be eee be ee 588ORGANIC CHEMISTRY CHAPTER I SCOPE AND METHODS OF ORGANIC CHEMISTRY 1, About the middle of the seventeenth century the study of the substances which occur in nature had so far developed that chemists grouped them, in an endeavor to systematize their knowledge, according to what they called the “three kingdoms” of nature. Chemistry was thus divided into three branches: animal, vegetable, and mineral. It was only when it was dis- covered later that certain compounds are formed in the growth of both animals and plants, that the distinction between animal and vegetable chemistry disappeared, and all substances pro- duced as the result of organized life-processes were designated by the term organic. It was believed that organic compounds were formed as the result of the so-called “vital force” in living things, and that they could not be produced by the chemist. In 1828, however, Wéhler discovered that ammonium cyanate, a so-called inorganic compound, could be transformed into urea, a typical organic substance, which results from the changes that certain foods undergo in the body. As the study of organic compounds advanced, it was found that many of them could be prepared in the laboratory from the elements of which they are composed. The sharp distinction between inorganic and organic compounds based on the vital force, accordingly, dis- appeared. The term organic chemistry has survived, however. In this division of the science of chemistry, not only the sub- stances formed as a result of life-energy in plants and animals are studied, but also the compounds prepared from these sub- stances, of which many thousands are known. The element carbon is present in all these so-called organic compounds, and as a consequence, organic .chemistry may be defined as the chemistry of the carbon compounds. The student is already familiar with the chemistry of carbon in the elementary 12 ORGANIC CHEMISTRY condition, of carbon monoxide and dioxide, and of the carbonates As these substances are constituents of the mineral world they are considered as a part of inorganic chemistry. All other carbon compounds are classified, for convenience, under organic chemistry. 2. Although the compounds of carbon follow in their trans- formations the same fundamental laws as do the compounds of other elements, nevertheless, it is advisable to study them in detail after a knowledge of inorganic chemistry has been gained. A number of reasons have led to this setting off of the compounds of carbon for separate treatment. The chemical properties of these substances are different from those of the analogous compounds of other elements; for example, the chlorides of the metals react with silver nitrate in aqueous solution, and are decomposed by concentrated sulphuric acid, whereas the chloride of carbon is comparatively inert and is not readily affected by these reagents. Again, when oxygen and hydrogen in the form of the hydroxyl group are in combination with carbon, as in alcohol, C2H;.OH, the substance is not affected by dilute acids or alkalies, whereas this group in combination with other elements imparts to the resulting compound acidic or basic proper- ties. These differences between organic and inorganic com- pounds, and many others of a similar nature, are due to the fact that most inorganic compounds are broken down into ions when brought into solution, and act readily with other ionized sub- stances, whereas in the case of organic compounds, a small number only undergo such ionization. Organic chemistry in- volves to a large extent the study of reactions between molecules, whereas in inorganic chemistry ionic reactions are of prime importance. Many compounds of carbon exist which are unlike any known compounds of other elements. This is due to the fact that the carbon atom has the power to unite with itself and form molecules of great complexity. Compounds have been studied which contain over 60 carbon atoms in the molecule. Where so many atoms are present there is, evidently, opportunity for a number of different arrangements of the atoms; for example, there are 86 compounds of the formula CioH1203. This is an added source of complexity, and methods of study must be devised and usedSCOPE AND METHODS OF ORGANIC CHEMISTRY 3 which are not necessary in inorganic chemistry where such complexity does not exist. ImpoRTANCE AND APPLICATIONS OF ORGANIC CHEMISTRY 8. The field covered by organic chemistry is a wide one, The changes which take place in our bodies involve the trans- formation of organic substances; the digestion and assimilation of food are chemical processes in which complex carbon com- pounds take part. As a consequence, a correct understanding of physiology requires a knowledge of physiological chemistry, which is a branch of organic chemistry. The investigation of the composition of foods and the study of methods for their analysis must be preceded by a study of the principles of organic chemistry upon which such investigation is based. The science of medicine makes use of many organic compounds on account of their effect on the body. An important branch of organic chemistry involves the preparation of new substances and a study of their action as drugs. We come in contact with many organic compounds in our daily life on account of their useful or esthetic value, and such compounds assume an important placein commerce. In addition to foods, may be mentioned condiments, paints, illuminating oils, dyes, etc. The study of such substances involves the determination of the properties of the individual compounds and the changes which they undergo under a variety of circum- stances. These transformations give the chemist such a clear conception of the nature of the compounds that in many cases it has been found possible to synthesize (i.e. build up) a sub- stance which occurs in nature, from other simple and readily obtainable substances. The synthesis of Turkey red, a highly prized dye found in madder root, is an interesting example. Some years ago thousands of acres of land were given up to the growing of madder, in order to produce this dye. The substance, which is a definite chemical compound, was extracted in pure condition, and carefully studied. As a result, a method was devised to build up the dye from anthracene, a comparatively cheap substance, which is found in the tar formed when coal is distilled in the preparation of coal gas. As the result of this application of organic chemistry the synthetic dye replaced that