NINTH EDITION THE ORGANIC CHEM LAB SURVIVAL MANUAL A Student’s Guide to Techniques JAMES W. ZUBRICK Hudson Valley Community College For Zoë and Anne, who make it all worth the effort. VP & Executive Publisher Kaye Pace Associate Publisher Petra Recter Sponsoring Editor Joan Kalkut Editorial Assistant Ashley Gayle Marketing Manager Kristine Ruff Marketing Assistant Andrew Ginsberg Designer Seng Ping Ngieng Associate Production Manager Joyce Poh Production Editor Jolene Ling This book was set in 10/12 Times by Aptara®, Inc. and printed and bound by Courier Westford. The cover was printed by Courier Westford. This book is printed on acid free paper. Founded in 1807, John Wiley & Sons, Inc. has been a valued source of knowledge and understanding for more than 200 years, helping people around the world meet their needs and fulfi ll their aspirations. Our company is built on a foundation of principles that include responsibility to the communities we serve and where we live and work. 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QD261.Z83 2012 547.0078—dc23 2012020179 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 PREFACE TO THE NINTH EDITION This Survival Manual again presents the basic techniques of the organic chemistry laboratory, with the usual emphasis on doing the work correctly the fi rst time. And once again, I have relied on the comments of users and reviewers in guiding the changes and additions that have been made. Safety in the laboratory, always a primary concern, now has to consider the addition of such technology as the iPad, the Nook, the Kindle, and even text mes- saging, where applicable. Microscale, also where applicable, has been reviewed and updated as well. And while currently resisting the deletion of double-beam spectro- photometers altogether, a discussion of the technique of Attenuated Total Refl ectance and associated practices has been added to the section on Infrared Spectroscopy (Chapter 32). The discussion and presentation of the section on Nuclear Magnetic Reso- nance (Chapter 33) has been re-worked such that the different methods of sample preparation, and instrument operation for continuous-wave and FT-NMR have been made to contrast more sharply. A number of NMR spectra, with suggestions on pre- sentation of the data, and basic interpretation have also been added. Presentation of a more modern outline of the instrumentation of HPLC (Chapter 31) includes discussion of automatic injectors, yet there is a bit of a loss as this instrument, now highly computer-controlled, no longer has visible pumps, valves, and miles of tubing and fi ttings, just a series of fairly quiet, putty-colored boxes that produce excellent data with ease and a bit of boredom. This kind of transition has put this edition of the Survival Manual into a bit of an “equilibrium mode,” as now, at the urging of reviewers, some older techniques have been removed as newer information has been included. The actual making of TLC plates on microscope slides, which apparently needs not be done anymore, has been removed, and comments about handling and cutting pre-prepared plates have been updated and expanded (Chapter 27). I’d like to thank my reviewers, Sean O’Connor, Clemson University; Lucy Moses, Virginia Commonwealth University; Christine Rich, University of Louisville; Sean O’Connor, University of New Orleans; Jeffrey Hugdahl, Mercer University; Kathleen Peterson, University of Notre Dame; Chavonda Mills, Georgia College & State University; Beatrix Aukszi, Nova Southeastern University; Robert Stockland, Bucknell University; Jennifer Krumper, UNC-Chapel Hill; Rui Zhang, Western Kentucky University; Holly Sebahar, University of Utah; Adam List, Vanderbilt University for their comments and suggestions, most of which have been iii iv PREFACE TO THE NINTH EDITION incorporated in this work. Finally, I’d like to thank Petra Recter, Associate Publisher, Chemistry and Physics, for the chance to perform this update, and Joan Kalkut, Sponsoring Editor, for her tremendous patience and support during a personally diffi cult time. J. W. Zubrick Hudson Valley Community College CONTENTS CHAPTER 1 SAFETY FIRST, LAST, AND ALWAYS 1 Accidents Will Not Happen 5 Disposing of Waste 5 Mixed Waste 7 Material Safety Data Sheet (MSDS) 8 Green Chemistry and Planning an Organic Synthesis 9 An iBag for Your iThing 10 Exercises 10 CHAPTER 2 KEEPING A NOTEBOOK 11 A Technique Experiment 12 Notebook Notes 13 A Synthesis Experiment 13 Notebook Notes 13 Calculation of Percent Yield (Not Yeild!) 23 Estimation Is Your Friend 25 The Acid Test 25 Notebook Mortal Sin 25 Exercises 26 CHAPTER 3 INTERPRETING A HANDBOOK 27 CRC Handbook 28 Entry: 1-Bromobutane 28 Entry: Benzoic Acid 29 Lange’s 31 Entry: 1-Bromobutane 31 Entry: Benzoic Acid 31 Merck Index 31 Entry: 1-Bromobutane 33 Entry: Benzoic Acid 34 There’s a CD 34 The Aldrich Catalog 35 Entry: 1-Bromobutane 35 Entry: Benzoic Acid 36 Not Clear–Clear? 36 Info on the Internet 37 Exercises 37 v vi CONTENTS CHAPTER 4 JOINTWARE 38 Stoppers with Only One Number 39 Another Episode of Love of Laboratory 40 Hall of Blunders and Things Not Quite Right 42 Round-Bottom Flasks 42 Columns and Condensers 43 The Adapter with Lots of Names 43 Forgetting the Glass 45 Inserting Adapter Upside Down 45 Inserting Adapter Upside Down sans Glass 46 The O-Ring and Cap Branch Out 46 Greasing the Joints 46 To Grease or Not to Grease 47 Preparation of the Joints 47 Into the Grease Pit 47 Storing Stuff and Sticking Stoppers 48 Corking a Vessel 48 CHAPTER 5 MICROSCALE JOINTWARE 50 Microscale: A Few Words 51 Uh-Oh Rings 51 The O-Ring Cap Seal 51 Skinny Apparatus 51 Not-So-Skinny Apparatus 52 Sizing Up the Situation 52 Why I Don’t Really Know How Vacuum-Tight These Seals Are 54 The Comical Vial (That’s Conical!) 54 The Conical Vial as Vial 55 Packaging Oops 55 Tare to the Analytical Balance 55 The Electronic Analytical Balance 56 Heating These Vials 56 The Microscale Drying Tube 57 Gas Collection Apparatus 58 Generating the Gas 59 Isolating the Product 61 CHAPTER 6 OTHER INTERESTING EQUIPMENT 62 Funnels, and Beakers, and Flasks—Oh My! 63 The Flexible Double-Ended Stainless Steel Spatula 63 CONTENTS vii CHAPTER 7 PIPET TIPS 66 Pre-Preparing Pasteur Pipets 67 Calibration 68 Operation 68 Amelioration 68 Pipet Cutting 70 Pipet Filtering—Liquids 70 Pipet Filtering—Solids 71 CHAPTER 8 SYRINGES, NEEDLES, AND SEPTA 73 The Rubber Septum 75 CHAPTER 9 CLEAN AND DRY 77 Drying Your Glassware When You Don’t Need To 78 Drying Your Glassware When You Do Need To 79 CHAPTER 10 DRYING AGENTS 80 Typical Drying Agents 81 Using a Drying Agent 82 Following Directions and Losing Product Anyway 82 Drying Agents: Microscale 83 Drying in Stages: The Capacity and Effi ciency of Drying Agents 83 Exercises 83 CHAPTER 11 ON PRODUCTS 84 Solid Product Problems 85 Liquid Product Problems 85 The Sample Vial 85 Hold It! Don’t Touch That Vial 86 CHAPTER 12 THE MELTING-POINT EXPERIMENT 87 Sample Preparation 88 Loading the Melting-Point Tube 89 Closing Off Melting-Point Tubes 90 Melting-Point Hints 90 The Mel-Temp Apparatus 91 Operation of the Mel-Temp Apparatus 92 The Fisher-Johns Apparatus 93 Operation of the Fisher-Johns Apparatus 94 The Thomas-Hoover Apparatus 95 Operation of the Thomas-Hoover Apparatus 97 viii CONTENTS Using the Thiele Tube 99 Cleaning the Tube 100 Getting the Sample Ready 101 Dunking the Melting-Point Tube 102 Heating the Sample 103 Exercises