The Systematic Identification of Organic Compounds

Preface ix

About the Companion Website xi

Chapter 1 Introduction 1

1.1 Systematic Identification of Organic Compounds: The Need for Organic Qualitative Analysis 1

1.2 Suggestions to Students and Instructors 3

Chapter 2 Laboratory Safety 7

2.1 Working Safely in the Laboratory 7

2.2 Training 10

2.3 Personal Protection Equipment 10

2.4 Safety Data Sheets 11

2.5 Storage of Chemicals 12

2.6 Disposal of Chemicals 13

2.7 Safely Using Equipment in the Laboratory 13

Chapter 3 Identification of Unknowns 15

3.1 Discussion of Report Form 15

3.2 Preliminary Examination 22

3.3 Physical Properties 22

3.4 Molecular Weight Determination 22

3.5 Molecular Formula Determination 23

3.6 Solubility Tests 23

3.7 Infrared, Nuclear Magnetic Resonance, and Mass Spectra Analyses 24

3.8 Classification Tests 24

3.9 Preparation of a Satisfactory Derivative 25

3.10 Mixtures 26

3.11 Report Forms 26

Chapter 4 Preliminary Examination, Physical Properties, and Elemental Analysis 31

4.1 Preliminary Examination 32

4.2 Determination of Physical Properties 34

4.3 Optical Rotation 53

4.4 Recrystallization 58

4.5 Qualitative Elemental Analysis 61

4.6 Quantitative Elemental Analysis 69

Chapter 5 Classification of Organic Compounds by Solubility 75

5.1 Solubility in Water, Aqueous Acids and Bases, and Ether 76

5.2 Solubility in Organic Solvents 95

Chapter 6 Separation of Mixtures 99

6.1 Preliminary Examinations of Mixtures 100

6.2 Distillation and Sublimation 101

6.3 Extractions: Separations Based Upon

6.4 Chromatography 119

Chapter 7 Nuclear Magnetic Resonance Spectrometry 145

7.1 Theory of Nuclear Magnetic Resonance 145

7.2 Preparation of the Sample 149

7.3 Proton Spectra 151

7.4 13C Spectra 165

7.5 DEPT 179

7.6 COSY 188

7.7 HSQC 190

Chapter 8 Infrared Spectrometry 227

8.1 Theory of Infrared Spectrometry 227

8.2 Preparation of the Sample 230

8.3 Functional Group Identification 234

Chapter 9 Mass Spectrometry 269

9.1 Theory of Mass Spectrometry 269

9.2 Cleavage Reactions 271

Chapter 10 Chemical Tests for Functional Groups 293

10.1 Acid Anhydrides 296

10.2 Acyl Halides 306

10.3 Alcohols 307

10.4 Aldehydes 323

10.5 Amides 332

10.6 Amines and Amine Salts 334

10.7 Amino Acids 349

10.8 Carbohydrates 351

10.9 Carboxylic Acids 359

10.10 Esters 360

10.11 Ethers 361

10.12 Halides 365

10.13 Hydrocarbons--Alkanes 371

10.14 Hydrocarbons--Alkenes 371

10.15 Hydrocarbons--Alkynes 378

10.16 Hydrocarbons--Aromatic 379

10.17 Ketones 384

10.18 Nitriles 386

10.19 Nitro Compounds 386

10.20 Phenols 389

10.21 Sulfonamides, Sulfonic Acids, Sulfonyl Chlorides 393

Chapter 11 The Preparation of Derivatives 397

11.1 Carboxylic Acids, Acid Anhydrides, Acid Halides 397

11.2 Alcohols 409

11.3 Aldehydes And Ketones 414

11.4 Amides 420

11.5 Amines 424

11.6 Amino Acids 432

11.7 Carbohydrates 437

11.8 Esters 440

11.9 Ethers--Aliphatic 450

11.10 Ethers--Aromatic 451

11.11 Halides--Alkyl 454

11.12 Halides--Aromatic 457

11.13 Hydrocarbons--Aromatic 460

11.14 Nitriles 462

11.15 Nitro Compounds 467

11.16 Phenols 468

11.17 Sulfonic Acids, Sulfonyl Chlorides, Sulfonamides 472

Chapter 12 Chemical Literature 479

12.1 Handbooks 480

12.2 Compendia 480

12.3 Spectral Collections 481

12.4 Journals 482

12.5 Abstracts and Indexes 483

12.6 Monographs 486

Appendix I Handy Tables for the Organic Laboratory 487

APPENDIX II Table of Derivatives 493

Appendix III Equipment and Chemicals for the Laboratory 677

Index 685