SEMIMICRO AND MACRO ORGANIC CHEMISTRY BY THE SAME AUTHOR ORGANIC CHEMISTRY SEMIMICRO AND MACRO ORGANIC CHEMISTRY SEMIMICRO AND MACRO ORGANIC CHEMISTRY A LABORATORY MANUAL BY Nicholas D. Cneronis CHICAGO CITY COLLEGES NEW YORK • THOMAS Y. CROWELL COMPANY COPYRIGHT, 1942, BY THOMAS Y. CROWELL COMPANY All rights reserved. No part of this book may be reproduced in any form, by mimeograph or any other means, without permission in writing from the publisher. FIRST PRINTING, SEPTEMBER 1942 MANUFACTURED IN THE UNITED STATES OF AMERICA BY THE COLONIAL PRESS INC., CLINTON, MASS. PREFACE The present laboratory manual was developed primarily to pro- vide suitable experiments in elementary laboratory practice for all levels of students, both the average and the exceptional. Impressed by the possibilities of the semimicro technic in connection with this problem, the author began several years ago to experiment with it in his classes. After mature consideration and six years of trial and error with all types of students, he believes that it is possible to attain all the objectives of laboratory practice in elementary or- ganic chemistry using the semimicro technic. In addition, this method offers the following advantages over the traditional method: (1) it permits better adaptation of the laboratory work to the varying needs of students; (2) it teaches students greater care, cleanliness, and manipulation; (3) it is more economical; and (4) it reduces substantially the seriousness of possible accidents since the quantities of reagents and size of equipment are only some 10 to 20 per cent as great as with macro methods. It is realized, however, that a sudden and complete shift from traditional macro methods is usually not practical or desirable. For this reason, in practically all experiments, semimicro is par- alleled with the macro method. In this manner teachers may ex- periment as widely with semimicro technic and with whatever students they wish. The arrangement of the material in the manual is made accord- ing to the following plan: In the first part an attempt is made to introduce the students to the elementary technics, such as crystal- lization of solids, distillation of liquids, determination of boiling and melting points and of refractive indices, necessary for the study of organic chemistry. This is followed by a study of the preparation and properties of the simpler groups of organic com- pounds. The preparation of one or more compounds from each group serves to illustrate the general principles involved. This is followed by a systematic study designed to illustrate important group properties and variations of these among members of the same group. Beginning each experiment there is a brief introduc- tory explanation relating the material of the experiment to the previous knowledge of the student and also orienting him to the work to be done. For each group of organic compounds there are vi PREFACE usually listed several preparations. It should be emphasized that this practice does not place a premium on the amount of work done; it is rather the organization and understanding of the work done that are of primary importance. It is believed, however, that directions for several preparations will be an aid to the teacher in providing suitable work for students of different abilities and in- terests. A number of experiments are well adapted to discussion- demonstrations to be given by the instructor, and are so marked. The latter part of the manual is devoted to compounds of greater complexity. Some of these require the preparation of several com- pounds which are used in the subsequent work in order to obtain the final product. Thus it is hoped that the manual achieves unity and organization for teaching rather than being a mere collection of unrelated preparations. The author wishes to acknowledge his indebtedness to those who have aided him in this work: for suggestions, reading, and com- menting on parts of the manuscript, to Louis Sattler of Brooklyn College, Joseph B. Niederl of New York University, Gordon Pritham of the University of Scranton, Ernest R. Kline of the University of Connecticut, Louise Wendt of Nebraska State Teachers College, John Entrikin of Centenary College, and to his colleagues, Sebastian Durban, James Parsons, and Conrad Ronne- berg; to Joseph Drummond and Kurt Spitzmueller for many sug- gestions on apparatus and methods; to Milton Cooper and Michael Savoy for suggestions on the experiments for the determination of melting points; to his former students, Peter Arvan, Herman Teifeld, Alford Anderson, Richard Erhardt, and Carl Anderson for their patience and work in adapting the various preparations of organic compounds to the semimicro technic; to Walter Bur- fischer of Wilkens-Anderson Company for the many suggestions and help in the development of the semimicro apparatus; and, for assistance in the preparation of the manuscript, to Harold Wood- son, Helen Karagianes, and Denver Cummings. NICHOLAS D. CHERONIS CONTENTS BXPEBIMENT FAQS General Information 1 PART I INTRODUCTION TO LABORATORY METHODS 1. The Sources of Organic Compounds 21 2. The Purification of Solid Organic Compounds by Crys- tallization 24 3. Determination of Melting Points 41 4. Determination of Melting Points of Mixtures 53 5. The Purification of Organic Compounds by Distillation 57 6. Purification by Fractional Distillation 65 7. Micro Determination of Boiling Points 78 8. Determination of Refractive Indices 82 9. Identification of Elements in Carbon Compounds . . 87 PART II PREPARATION AND PROPERTIES OF SIMPLE ORGANIC COMPOUNDS 10. Preparation of n-Decane and n-Octane 97 11. Preparation of Ethylbenzene 103 12. Preparation of a Hydrocarbon by Decarboxylation of an Organic Acid 106 13. Unsaturated Hydrocarbons: Preparation of Cyclohexene and Amylene 108 14. The Preparation of Acetylene 118 15. The Study of Aromatic Hydrocarbons 121 16. Preparation of Hydrocarbons by the Use of the Grignard Reagent 123 17. The Reactions of Hydrocarbons 127 18. Preparation of Butyl Chlorides . 131 19. Preparation of Butyl Bromides 135 20. Preparation of Alkyl Iodides 138 21. Preparation of Bromobenzene 140 22. The Properties and Reactions of Halogen Compounds . 144 23. Grignard Synthesis of Carbinols 146 24. The Reactions of Hydroxy Compounds 150 vii viii CONTENTS EXPERIMENT PAGE 25. Preparation of Ethers 153 26. Preparation of Amines by Ammonolysis 160 27. Preparation of Aniline 163 28. Reactions of Amines 174 29. Preparation of Nitro Compounds 178 30. Important Reactions of Nitro Compounds 181 31. Oxidation of Alcohols to Aldehydes and Ketones . . 183 32. Preparation of Acetaldehyde 187 33. The Preparation of Cyclopentanone 189 34. Reactions of Aldehydes and Ketones 191 35. The Polyhalogen Compounds 196 36. Preparation of Acids by Oxidation of Alcohols . . . 199 37. Preparation of Acids by Carboxylation of the Grignard Reagent 201 38. Reactions of Carboxylic Acids 204 39. Preparation and Properties of Esters 207 40. Preparation and Properties of Acyl Chlorides . . . 211 41. Preparation and Properties of Amides 216 42. Preparation of Acid Anhydrides 219 PART III PREPARATION AND PROPERTIES OF COMPOUNDS OF GREATER COMPLEXITY 43. Preparation of Chloroacetic Acid 223 44. Preparation of a-Bromopropionic Acid 230 45. Distillation under Reduced Pressure 232 46. Determination of Optical Rotation 244 47. Esters of Polyhydroxy Compounds 248 48. Properties of Carbohydrates 252 49. Preparation and Properties of Urea 257 50. Preparation and Properties of a-Amino Acids . . . 260 51. Properties of Proteins 263 52. Preparation of Substituted Anilines 266 53. Preparation of Diazonium Salts 271 54. Replacement of the Diazo Group by Iodine 275 55. Replacement of the Diazo Group by Chlorine . . . 277 56. Replacement of the Diazo Group by a Hydroxyl Group 280 57. Reduction of the Diazo Group 282 58. Preparation of Azo and Diazoamino Compounds . . 285 59. Preparation of Sulfonic Acids 289 60. Preparation and Properties of Quinones 293 61. Preparation of Aromatic Hydrocarbons by the Friedel- Craf ts Reaction 296 62. Preparation of Ketones by the Friedel-Crafts Reaction 300 CONTENTS ix EXPEBIMENT PAGE 63. Preparation of o-Benzoylbenzoic Acid 303 64. Preparation of Anthraquinone by Ring Closure . . . 305 65. Condensations of Carbonyl Compounds 307 66. The Benzidine Rearrangement 311 67. Preparation of Heterocyclic Compounds 314 68. Physiologically Active Compounds 317 69. Preparation of Dyes and Indicators 328 70. Synthetic Polymers 343 Appendix I. Laboratory Accidents and First Aid 347 II. Suggested List of Apparatus for Elementary Or- ganic Chemistry (Macro and Semimicro) . . 350 III. List of Chemicals and Reagents 352 IV. Calibration of Thermometers 355 V. Freezing Mixtures 357 VI. Drying Agents for Organic Liquids 357 VII. Cleaning Solutions 358 VIII. Preparation of Pipettes and Pipette Droppers . 359 IX. Preparation and Sealing of a Bomb Tube . . 360 X. Densities and Percentage Compositions of Vari- ous Solutions 362 XL Vapor Pressures of Various Organic Substances . 367 XII. Reference Books for Beginners in Practical Or- ganic Chemistry and Laboratory Methods . 368 XIII. Write-Up of a Typical Experiment 369 Index 371 [...]... the 'Semimicro Apparatus for Organic Chemistry (Chicago: Wilkens-Anderson Co.) 12 GENERAL INFORMATION Eight-inch test tube Six-inch test tube Six-inch test tube with side arm Semimicro test-tube rack for eight- and six-inch test tubes Semimicro distilling tube and flask with modified side arm (25 ml and 10 ml) Fig 2(a) Semimicro fractionating column GENERAL INFORMATION 13 Semimicro Bunsen funnel Semimicro. .. ordinary eight- or six-inch test tube Macro apparatus for Wurtz-Fittig reaction Semimicro apparatus for separation of two immiscible liquids Semimicro separatory tube in use Operation of semimicro separatory tube with one hand Semimicro apparatus for Grignard reaction Semimicro apparatus for bromination (may be used for reactions where gases, soluble in water, are evolved) Macro apparatus... a three-inch tube, or 60 milliliters by using an eight-inch tube Weighing and measuring for semimicro work In place of the horn-pan hand balance which heretofore was imported, an American-made "Sanolite" plastic-pan hand balance is recommended Solids are weighed on pieces of glazed paper An ordinary 8£ x 11 sheet of paper is folded and cut in four equal pieces which are suitable for weighing 2-5 g of... ILLUSTRATIONS FIGUHE PAGES 1 Macro apparatus commonly used in elementary organic chemistry 2 Semimicro apparatus recommended for elementary organic chemistry 3 Apparatus for experiment on the products obtained by the carbonization of coal 4 Flask with reflux condenser for heating liquids 5 Semimicro apparatus for heating under reflux 6 Macro apparatus for ordinary filtration 7 Semimicro apparatus for... under reduced pressure, using eight-inch tube 59 Semimicro apparatus for distillation under reduced pressure, using Claisen tube 60 Polarizer P and analyzer A in parallel position 61 Polarizer P and analyzer A at right angles 62 Polarimeter 63 Semimicro constant-temperature bath xiii PAGE 239 240 244 244 245 330 GENERAL INFORMATION PURPOSE OF LABORATORY WORK Organic chemistry is an experimental science;... Work slowly and carefully It is better to do a small amount of work neatly and to understand it, than to do a large amount hastily, carelessly, and to be vague about what you have done (7) Cleanliness is extremely important in all laboratory work Begin your work with clean apparatus and a clean bench, and end your work in the same manner; the desk top and reagent bottles should be cleaned and arranged... Heating baths Beakers, of 125 ml and 250 ml capacity, may serve as water-heating baths in semimicro work Small tin cans of two to three inches in diameter serve the same purpose without any danger of breakage A three-purpose heating bath, specially developed for semimicro work in organic chemistry, is shown in Figure 2(6) The bath is made of metal and is 70 mm in depth and 90 mm in diameter The top is... 16 Melting-point-composition diagram involving compound formation 17 Melting-point-composition diagram involving solid solutions 18 Heating bath (beaker) for determination of melting points 19 Heating bath (flask) for determination of melting points 20 Modified Thiele heating bath for melting-point determination 21 Melting points of three mixtures of /3-naphthol and an unknown (/3-naphthol and unknown... distilling tube Semimicro condenser Porcelain disc used with Bunsen funnel to serve as semimicro suction funnel Semimicro Buchner funnel Semimicro Monelblade spatula Semimicro calcium chloride tube Separatory tube used in semimicro work in place of separatory or dropping funnel Fig 2(6) Heating bath used in semimicro work, adaptable as water bath, steam-distillation bath, or constant-temperature bath... a r y for boiling-point d e t e r m i n a t i o n (enlarged) (B) Boiling-point setup using capillary (A) (C) Boiling-point setup using modified melting-point capillary (D) Capillary for boiling-point determination, according to Emich Refractometer (Abbe) Refractometer (Fisher) Apparatus for the detection of carbon and hydrogen Semimicro apparatus for Wurtz-Fittig reaction Semimicro distillation . SEMIMICRO AND MACRO ORGANIC CHEMISTRY BY THE SAME AUTHOR ORGANIC CHEMISTRY SEMIMICRO AND MACRO ORGANIC CHEMISTRY SEMIMICRO AND MACRO ORGANIC CHEMISTRY A LABORATORY MANUAL BY Nicholas D. Cneronis CHICAGO. Anderson, Richard Erhardt, and Carl Anderson for their patience and work in adapting the various preparations of organic compounds to the semimicro technic; to Walter Bur- fischer of Wilkens-Anderson. of Dyes and Indicators 328 70. Synthetic Polymers 343 Appendix I. Laboratory Accidents and First Aid 347 II. Suggested List of Apparatus for Elementary Or- ganic Chemistry (Macro and Semimicro)