Micro scale Approach to Organic Lab rotary Techniques 5th Edition, Formulas and forms for Chemistry. University of Utah (UT)

Micro scale Approach to Organic Lab rotary Techniques 5th Edition, Formulas and forms for Chemistry. University of Utah (UT)

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Microscale Approach to Organic Lab Techniques, 5th ed.

Common Organic Solvents

Solvent Boiling Point (°C) Density (g/mL)

Acetic acid 118 1.05 Acetic anhydride 140 1.08 Acetone 56 0.79 Benzene* 80 0.88 Carbon tetrachloride* 77 1.59 Chloroform* 61 1.48 Cyclohexane 81 0.78 Dimethylformamide (DMF) 153 0.94 Dimethyl sulfoxide (DMSO) 189 1.10 Ethanol 78 0.80 Ether (diethyl) 35 0.71 Ethyl acetate 77 0.90 Heptane 98 0.68 Hexane 69 0.66 Ligroin 60–90 0.68 Methanol 65 0.79 Methylene chloride 40 1.32 Pentane 36 0.63 Petroleum ether 30–60 0.63 1-Propanol 98 0.80 2-Propanol 82 0.79 Pyridine 115 0.98 Tetrahydrofuran (THF) 65 0.99 Toluene 111 0.87

Xylenes 137–144 0.86

Solvents indicated in boldface type are flammable. *Suspected carcinogen.

1 2

3 4

5 6

7 8

9 10

11 12

13 14

15 16

17 18

19 2 0

21 22

23 2 4


06524_IFC_ptg01.indd 106 12/22/11 9:24:15 AM

Atomic Mass Values for Selected Elements

Aluminum 26.98 Boron 10.81 Bromine 79.90 Carbon 12.01 Chlorine 35.45 Fluorine 18.99 Hydrogen 1.008 Iodine 126.9 Lithium 6.941 Magnesium 24.30 Nitrogen 14.01 Oxygen 15.99 Phosphorus 30.97 Potassium 39.09 Silicon 28.09 Sodium 22.99 Sulfur 32.07

Concentrated Acids and Bases


Density (g/mL) 1.18 1.41 1.84 1.20 1.06 0.90 % Acid or base (by weight) 37.3 70.0 96.5 90.0 99.7 29.0

Molecular weight 36.47 63.02 98.08 46.03 60.05 17.03

Molarity of concentrated acid or base 12 16 18 23.4 17.5 15.3

Normality of concentrated acid or base 12 16 36 23.4 17.5 15.3

Volume of concentrated reagent required to prepare 1 L of 1 M solution (ml) 83 64 56 42 58 65 Volume of concentrated reagent required to prepare 1 L of 10% solution (ml)* 227 101 56 93 95 384 Molarity of a 10% solution* 2.74 1.59 1.02 2.17 1.67 5.87

*Percent solutions by weight.

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A Microscale Approach


Organic Laboratory Techniques

FiFth Edition

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This is an electronic version of the print textbook. Due to electronic rights restrictions, some third party content may be suppressed. Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. The publisher reserves the right to remove content from this title at any time if subsequent rights restrictions require it. For valuable information on pricing, previous editions, changes to current editions, and alternate formats, please visit www.cengage.com/highered to search by ISBN#, author, title, or keyword for materials in your areas of interest.

A Microscale Approach


Organic Laboratory Techniques

FiFth Edition

Donald L. Pavia Gary M. Lampman

George S. Kriz Western Washington University

Bellingham, Washington

Randall G. Engel North Seattle Community College

Seattle, Washington

Australia • Brazil • Japan • Korea • Mexico • Singapore • Spain • United Kingdom • United States

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A Microscale Approach to Organic Laboratory Techniques, Fifth Edition Donald L. Pavia, Gary M. Lampman, George S. Kriz, Randall G. Engel

Publisher/Executive Editor: Mary Finch

Acquisitions Editor: Christopher D. Simpson

Developmental Editor: Peter McGahey

Assistant Editor: Krista M. Mastroianni

Editorial Assistant: Alicia B. Landsberg

Media Editor: Stephanie Van Camp

Executive Marketing Manager: Nicole Hamm

Marketing Communications Manager: Darlene Macanan

Production Management and Composition: PreMediaGlobal

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Design Director: Rob Hugel

Art Director: Maria Epes

Text Researcher: Pablo D’Stair

Cover Designer: John Walker

Cover Image: © Alexmax | Dreamstime.com and Artwork by Pat Harman

© 2013, 2007, 1999 Brooks/Cole, Cengage Learning

ALL RIGHTS RESERVED. No part of this work covered by the copyright herein may be reproduced, transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited to photocopying, recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and retrieval systems, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the publisher.

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Library of Congress Control Number: 2011943582

ISBN-13: 978-1-133-10652-4

ISBN-10: 1-133-10652-8

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Printed in the United States of America 1 2 3 4 5 6 7 16 15 14 13 12

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This book is dedicated to our organic chemistry laboratory students

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the purpose of this current edition of the microscale lab book is to teach students the techniques of organic chemistry. We desire to share our joy and love of the organic chemistry lab with our students! in this edition, we include many new up-to-date experiments that will demonstrate how organic chemistry is evolving. For example, there are new experiments involving nanotechnology and biofuels. We also include several new experiments based on nobel Prize awards, such as using organome- tallic catalysts for synthesis (Sonogashira Coupling of iodosubstituted Aromatic Compounds with Alkynes Using a Palladium Catalyst and Grubbs- Catalyzed Metathesis of Eugenol with 1,4-Butendiol to Prepare a natural Product). Also included is a synthesis of the pharmaceutical drug Aleve® (naproxen) in a project- based experiment. this experiment includes a resolution step and makes extensive use of nMR spectroscopy. there are several new Green Chemistry experiments, and the “green” aspects of experiments from our previous book have been improved. We think that you will be enthusiastic about this new edition. Many of the new experiments will not be found in other laboratory manuals, but we have been care- ful to retain all of the standard reactions and techniques, such as the Friedel-Crafts reaction, the aldol condensation, Grignard synthesis, and basic experiments de- signed to teach crystallization, chromatography, and distillation.

S C A L E I N T H E O R G A N I C L A B O R A T O R Y Experiments in organic chemistry can be conducted at different scales using vary- ing amounts of chemicals and different styles of glassware. We have two versions of our laboratory textbooks that teach organic laboratory techniques. this microscale book (A Microscale Approach to Organic Laboratory Techniques, Fifth Edition) makes use of ts 14/10 standard-tapered glassware. our version of a “macroscale” textbook (A Small Scale Approach to Organic Laboratory Techniques) uses the traditional larger scale ts 19/22 standard-tapered glassware. the third edition of our small scale book was published in 2011.

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viii Preface

over the years that we have been involved with developing experiments, we have learned that students can easily adjust to working with small laboratory equipment. Perhaps we can thank our colleagues who teach analytical techniques in general chemistry for demonstrating that students can learn to be meticulous and work with small amounts of material in many traditional experiments. As stu- dents and faculty learn to appreciate the impact of laboratory experiments on the environment, they become more aware that it is not necessary to consume large quantities of chemicals. Students come to appreciate the importance of reducing waste generated in the organic laboratory. All of us, students and faculty alike, are becoming more “green.”


organic chemistry significantly impacts our lives in the real world. organic chem- istry plays a major role in industry, medicine, and consumer products. Composite plastics are increasingly used in cars and airplanes to cut weight while increasing strength. Biodiesel is a hot topic today as we try to find ways of reducing our need for petroleum, and replacing it with materials that are renewable. We need to replace the resources that we consume.

A number of experiments are linked together to create multistep syntheses. the advantage of this approach is that you will be doing something different from your neighbor in the laboratory. Wouldn’t you like to be doing something different from your neighbor? You may be synthesizing a new compound that hasn’t been reported in the chemical literature! You will not be all doing the same reaction on the same compounds: an example of this is the chalcone reaction, followed by the green epoxidation and cyclopropanation of the resulting chalcones.

N E W T O T H I S E D I T I O N Since the fourth edition of our microscale textbook appeared in 2007, there have been new developments in the teaching of organic chemistry laboratory. this fifth edition includes many new experiments that reflect these new developments and includes significant updating of the essays and techniques chapters.

new experiments added for this edition include:

Experiment 1 Solubility: Part F nanotechnology demonstration Experiment 27 Biodiesel Experiment 31 Borneol oxidation to camphor, new procedure Experiment 34 Sonogashira Coupling of iodoaromatic Compounds with

Alkynes Experiment 35 Grubb’s-Catalyzed Metathesis of Eugenol with cis-1,4-

Butenediol Experiment 44 n,n-diethyl-m-toluamide (oFF), new procedure Experiment 48 diels-Alder Reaction with Anthracene-9-methanol Experiment 52 identification of Unknowns, revised procedure Experiment 55 Competing nucleophiles in Sn1 and Sn2 Reactions: investi-

gations Using 2-Pentanol and 3-Pentanol Experiment 56 Friedel-Crafts, more substrates added Experiment 58 Aqueous-Based organozinc Reactions

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Preface ix

Experiment 59 Synthesis of naproxen (Aleve®) by palladium catalysis Experiment 62 Green Epoxidation of Chalcones Experiment 63 Cyclopropanation of Chalcones

We have included a new essay “Biofuels.” Substantial revisions were made to the “Petroleum and Fossil Fuels”essay and “the Chemistry of Sweeteners”essay. other essays have been updated as well.

We have made a number of improvements in this edition that significantly improve safety in the laboratory. We have added several new experiments that incorporate the principles of Green Chemistry. the Green Chemistry experiments decrease the need for hazardous waste disposal, leading to reduced contami- nation of the environment. these experiments involve techniques such as solid phase extraction and the use of a microwave reactor. other experiments have been modified to reduce their use of hazardous solvents. the “Green Chemistry” essayhas been revised. in our view, it is most timely that students begin to think about how to conduct chemical experiments in a more environmentally benign manner. Many other experiments have been modified to improve their reliability and safety.

in keeping with the Green Chemistry approach, we have suggested an alternative way of approaching qualitative organic analysis. this approach makes extensive use of spectroscopy to solve the structure of organic unknowns. in this approach, some of the traditional tests have been retained, but the main empha- sis is on using spectroscopy. in this way, we have attempted to show students how to solve structures in a more modern way, similar to that used in a research laboratory. the added advantage to this approach is that waste is considerably reduced.

new techniques have been introduced in this edition. Chiral gas chromatogra- phy has been included in the analysis of the products obtained from the resolution of a-phenylethylamine (Experiment 30) and the products from the chiral reduction of ethyl acetoacetate (Experiment 28). A new method of obtaining boiling points using a temperature probe with a Vernier LabPro interface or digital thermometer has been introduced.

Many of the techniques chapters have been updated. new problems have been added to the chapters on infrared and nMR spectroscopy (techniques 25, 26, and 27). Many of the old 60 Mhz nMR spectra have been replaced by more modern 300 Mhz spectra. As in previous editions, the techniques chapters include both microscale and macroscale methods.

A L T E R N A T E V E R S I O N S eBooks

Cengage Learning textbooks are sold in many eBook formats. offerings vary over time, so be sure to check your favorite eBook retailer if you are interested in a digi- tal version of this textbook.

Cengage Learning Custom Solutions

Because we realize that the traditional, comprehensive laboratory textbook may not fit every classroom’s needs or every student’s budget, we offer the opportunity to create personalized course materials. this book can be purchased in customized formats that may exclude unneeded experiments, include your local material, and,

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x Preface

if desired, incorporate additional content from other Cengage Learning products. For more information on custom possibilities, visit www.cengage.com/custom or contact your local Cengage Learning custom editor using the “Find Your Custom Editor” link at the top of the page.

I N S T R U C T O R R E S O U R C E S Instructor’s Manual

We would like to call your attention to the instructor’s Manual that accompanies our textbook and is available as a digital download for qualified instructors. the manual contains complete instructions for the preparation of reagents and equip- ment for each experiment, as well as answers to each of the questions in this text- book. in some cases, additional optional experiments are included. instructors will also find helpful the estimated time to complete each experiment and notes regard- ing special equipment or reagent handling. We strongly recommend that qualified adopters obtain a copy of this manual at login.cengage.com by searching for this book using the iSBn on the back cover. You may also contact your local Cengage Learning, Brooks/Cole representative for assistance. Contact information for your representative is available at www.cengagelearning.com through the “Find Your Rep” link at the top of the page.

Image Library

new for this edition, digital files for most text art are available for download by qualified instructors from the faculty companion Web site. these files can be used to print transparencies, create your own presentation slides, and supplement your lectures. Go to login.cengage.com and search for this book using the iSBn on the back cover for details on downloading these files.

A C K N O W L E D G M E N T S We owe our sincere thanks to the many colleagues who have used our textbooks and who have offered their suggestions for changes and improvements in our laboratory procedures or discussions. Although we cannot mention everyone who has made important contributions, we must make special mention of Albert Burns (north Seattle Community College), Amanda Murphy (Western Washington University), Charles Wandler (Western Washington University), Emily Borda ( Western Washington University), Frank deering (north Seattle Community College), Gregory o’neil (Western Washington University), James Patterson (north Seattle Community College), James Vyvyan (Western Washington University), nadine Fattaleh (Clark College), Scott Clary (north Seattle Community College), and timothy Clark (University of San diego).

in preparing this new edition, we have also attempted to incorporate the many improvements and suggestions that have been forwarded to us by the many instructors who have used our materials over the past several years.

We thank all who contributed, with special thanks to our developmental editor, Peter McGahey; acquiring sponsoring editor, Christopher Simpson; assistant edi- tor, Krista Mastroianni; editorial assistant, Alicia Landsberg; senior content project manager, Matthew Ballantyne; and associate media editor, Stephanie Van Camp.

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Preface xi

We are especially grateful to the students and friends who have volunteered to par- ticipate in the development of experiments or who offered their help and criticism. We thank heather Brogan, Courtney Engels, Erin Gilmore, Peter Lechner, Sherri Phillips, Sean Rumberger, Lance Visser, and Jonathan Pittman.

Finally, we wish to thank our families and special friends, especially neva-Jean Pavia, Marian Lampman, Carolyn Kriz, and Karin Granstrom, for their encouragement, support, and patience.

Donald L. Pavia (pavia@comcast.net) Gary M. Lampman (lampman@chem.wwu.edu) George S. Kriz (George.Kriz@wwu.edu) Randall G. Engel (rengel@sccd.ctc.edu)

November 2011

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O V E R A L L S T R U C T U R E O F T H E B O O K this textbook is divided into two major sections (see table of Contents). the first section, which includes Part one through Part Five, contains all of the experiments in this book. the second major section includes only Part Six, which contains all of the important techniques you will use in performing the experiments in this book. interspersed among the experiments in Part one through Part three is a series of essays. the essays provide a context for many of the experiments and often relate the experiment to real world applications. When your instructor assigns an experiment, he or she will often assign an essay and/or several techniques chapters along with the experiment. Before you come to lab, you should read all of these. in addition, it is likely that you will need to prepare some sections in your laboratory notebook (see technique 2) before you come to the lab.

S T R U C T U R E O F T H E E X P E R I M E N T S in this section we discuss how each experiment is organized in the textbook. to follow this discussion, you may want to refer to a specific experiment, such as Experiment 13.

Multiple Parts Experiments

Some experiments, such as Experiment 13, are divided into two or more indi- vidual parts that are designated by the experiment number and the letters A, B, etc. in some experiments, like Experiment 13, each part is a separate but related experiment, and you will most likely perform only one part. in Experiment 13, you would do Experiment 13A (isolation of Caffeine from tea Leaves) or Experi- ment 13B (isolation of Caffeine from a tea Bag). in other experiments, for example Experiment 32, the various parts can be linked together to form a multistep synthe- sis. in a few experiments, such as Experiment 22, the last part describes how you should analyze your final product.

Featured Topics and Techniques Lists

directly under the title of each experiment (see Experiment 13), there will be a list of topics. these topics may explain what kind of experiment it is, such as isola- tion of a natural product or Green Chemistry. the topics may also include major techniques that are required to perform the experiment, such as crystallization or extraction.

How To Use This Book

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xiv How To Use This Book

Required Reading

in the introduction to each experiment, there will be a section labeled Required Reading. Within this section, some of the required readings are labeled Review and some are labeled new. You should always read the chapters listed in the new section. Sometimes it will also be helpful to do the readings in the Review section.

Special Instructions

You should always read this section since it may include instructions that are es- sential to the success of the experiment.

Suggested Waste Disposal

this very important section gives instructions on how to dispose of the waste gen- erated in an experiment. often your instructor will provide you with additional instructions on how to handle the waste.

Notes to Instructor

it will usually not be necessary to read this section. this section provides special advice for the instructor that will help to make the experiment successful.


this section provides detailed instructions on how to carry out the experiments. Within the procedure, there will be many references to the techniques chapters, which you may need to consult in order to perform an experiment.


in some experiments, specific suggestions for what should be included in the labo- ratory report will be given. Your instructor may refer to these recommendations or may have other directions for you to follow.


At the end of most experiments will be a list of questions related to the experiment. it is likely that your instructor will assign at least some of these questions along with the laboratory report.

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Preface vii

PART 1 Introduction to Basic Laboratory Techniques 1 1 introduction to Microscale Laboratory 2 2 Solubility 12 3 Crystallization 22

3A Semimicroscale Crystallization—Erlenmeyer Flask and hirsch Funnel 23 3B Microscale Crystallization—Craig tube 26 3C Selecting a Solvent to Crystallize a Substance 28 3d Mixture Melting Points 29 3E Critical thinking Application 30

4 Extraction 34 4A Extraction of Caffeine 35 4B distribution of a Solute between two immiscible Solvents 37 4C how do You determine Which one is the organic Layer? 38 4d Use of Extraction to isolate a neutral Compound from a Mixture

Containing an Acid or Base impurity 39 4E Critical thinking Application 41

5 A Separation and Purification Scheme 44 6 Chromatography 47

6A thin-Layer Chromatography 48 6B Selecting the Correct Solvent for thin-Layer Chromatography 50 6C Monitoring a Reaction with thin-Layer Chromatography 51 6d Column Chromatography 52

7 Simple and Fractional distillation 56 7A Simple and Fractional distillation (Semimicroscale Procedure) 58 7B Simple and Fractional distillation (Microscale Procedure) 62

8 infrared Spectroscopy and Boiling-Point determination 64

Essay Aspirin 68

9 Acetylsalicylic Acid 71

Essay Analgesics 75

10 isolation of the Active ingredient in an Analgesic drug 79 11 Acetaminophen 83

11A Acetaminophen (Microscale Procedure) 84 11B Acetaminophen (Semimicroscale Procedure) 86

Essay Identification of Drugs 89

12 tLC Analysis of Analgesic drugs 91


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xvi Contents

Essay Caffeine 96

13 isolation of Caffeine from tea or Coffee 100 13A Extraction of Caffeine from tea with Methylene Chloride 103 13B Extraction of Caffeine from tea or Coffee Using Solid Phase Extraction

(SPE) 105

Essay Esters—Flavors and Fragrances 109

14 isopentyl Acetate (Banana oil) 112 14A isopentyl Acetate (Microscale Procedure) 113 14B isopentyl Acetate (Semimicroscale Procedure) 115

Essay Terpenes and Phenylpropanoids 118

15 Essential oils: Extraction of oil of Cloves by Steam distillation 122 15A oil of Cloves (Microscale Procedure) 123 15B oil of Cloves (Semimicroscale Procedure) 125

Essay Stereochemical Theory of Odor 127

16 Spearmint and Caraway oil: (1)- and (2)-Carvones 131

Essay The Chemistry of Vision 139

17 isolation of Chlorophyll and Carotenoid Pigments from Spinach 144

Essay Ethanol and Fermentation Chemistry 151

18 Ethanol from Sucrose 154

PART 2 Introduction to Molecular Modeling 159 Essay Molecular Modeling and Molecular Mechanics 160

19 An introduction to Molecular Modeling 165 19A the Conformations of n-Butane: Local Minima 166 19B Cyclohexane Chair and Boat Conformations 167 19C Substituted Cyclohexane Rings (Critical thinking Exercises) 168 19d cis- and trans-2-Butene168

Essay Computational Chemistry—ab Initio and Semiempirical Methods 170

20 Computational Chemistry 178 20A heats of Formation: isomerism, tautomerism, and Regioselectivity 179 20B heats of Reaction: Sn1 Reaction Rates 180 20C density–Electrostatic Potential Maps: Acidities of Carboxylic Acids 181 20d density–Electrostatic Potential Maps: Carbocations 182 20E density–LUMo Maps: Reactivities of Carbonyl Groups 182

PART 3 Properties and Reactions of Organic Compounds 185 21 Reactivities of Some Alkyl halides 186 22 nucleophilic Substitution Reactions: Competing nucleophiles 191

22A Competitive nucleophiles with 1-Butanol or 2-Butanol 193 22B Competitive nucleophiles with 2-Methyl-2-Propanol 195 22C Analysis 196

23 Synthesis of n-Butyl Bromide and t-Pentyl Chloride 200 23A n-Butyl Bromide 202 23B n-Butyl Bromide (Semimicroscale Procedure) 204 23C t-Pentyl Chloride (Microscale Procedure) 205 23d t-Pentyl Chloride (Semimicroscale Procedure) 206 23E t-Pentyl Chloride (Macroscale Procedure) 207

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Contents xvii

24 4-Methylcyclohexene 209 24A 4-Methylcyclohexene (Microscale Procedure) 211 24B 4-Methylcyclohexene (Semimicroscale Procedure) 212

Essay Fats and Oils 215

25 Methyl Stearate from Methyl oleate 220

Essay Petroleum and Fossil Fuels 225

26 Gas-Chromatographic Analysis of Gasolines 234

Essay Biofuels 239

27 Biodiesel 243 27A Biodiesel from Coconut oil 245 27B Biodiesel from other oils 246 27C Analysis of Biodiesel 246

Essay Green Chemistry 249

28 Chiral Reduction of Ethyl Acetoacetate; optical Purity determination 255

28A Chiral Reduction of Ethyl Acetoacetate 256 28B nMR determination of the optical Purity of Ethyl (S)-3-

hydroxybutanoate 260 29 nitration of Aromatic Compounds Using a Recyclable Catalyst 265 30 Resolution of (6)-a-Phenylethylamine and determination of optical

Purity 269 30A Resolution of (6)-a-Phenylethylamine 271 30B determination of optical Purity Using nMR and a Chiral Resolving

Agent 275 31 An oxidation–Reduction Scheme: Borneol, Camphor, isoborneol 277 32 Multistep Reaction Sequences: the Conversion of Benzaldehyde to

Benzilic Acid 292 32A Preparation of Benzoin by thiamine Catalysis 293 32B Preparation of Benzil 299 32C Preparation of Benzilic Acid 301

33 triphenylmethanol and Benzoic Acid 305 33A triphenylmethanol 310 33B Benzoic Acid 312

34 Sonogashira Coupling of iodosubstituted Aromatic Compounds with Alkynes using a Palladium Catalyst 316

35 Grubbs-Catalyzed Metathesis of Eugenol with 1,4-Butenediol to Prepare a natural Product 326

36 Aqueous-Based organozinc Reactions 333 37 the Aldol Condensation Reaction: Preparation of Benzalacetophenones

(Chalcones) 337 38 Preparation of an a,b-Unsaturated Ketone via Michael and Aldol

Condensation Reactions 342 39 1,4-diphenyl-1,3-butadiene 347

39A Benzyltriphenylphosphonium Chloride (Wittig Salt) 350 39B Preparation of 1,4-diphenyl-1,3-Butadiene Using Sodium Ethoxide to

Generate the Ylide 350 39C Preparation of 1,4-diphenyl-1,3-Butadiene Using Potassium Phosphate to

Generate the Ylide 352 40 Relative Reactivities of Several Aromatic Compounds 355 41 nitration of Methyl Benzoate 359

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xviii Contents

Essay Local Anesthetics 364

42 Benzocaine 368 43 Methyl Salicylate (oil of Wintergreen) 372

Essay Pheromones: Insect Attractants and Repellents 376

44 N,N-diethyl-m-toluamide:the insect Repellent “oFF” 384

Essay Sulfa Drugs 389

45 Sulfa drugs: Preparation of Sulfanilamide 392

Essay Polymers and Plastics 397

46 Preparation and Properties of Polymers: Polyester, nylon, and Polystyrene 407

46A Polyesters 408 46B Polyamide (nylon) 409 46C Polystyrene 411 46d infrared Spectra of Polymer Samples 412

Essay Diels–Alder Reaction and Insecticides 415

47 the diels—Alder Reaction of Cyclopentadiene with Maleic Anhydride 421

48 the diels–Alder Reaction with Anthracene-9-methanol 425 49 Photoreduction of Benzophenone and Rearrangement of Benzpinacol to

Benzopinacolone 428 49A Photoreduction of Benzophenone 429 49B Synthesis of b-Benzopinacolone: the Acid-Catalyzed Rearrangement of

Benzpinacol 435

Essay Fireflies and Photochemistry 437

50 Luminol 440 Essay The Chemistry of Sweeteners 445 51 Analysis of a diet Soft drink by hPLC 450

PART 4 Identification of Organic Substances 453 52 identification of Unknowns 454

52A Solubility tests 461 52B tests for the Elements (n, S, X) 468 52C tests for Unsaturation 473 52d Aldehydes and Ketones 477 52E Carboxylic Acids 483 52F Phenols 485 52G Amines 488 52h Alcohols 491 52i Esters 496

PART 5 Project-Based Experiments 501 53 Preparation of a C-4 or C-5 Acetate Ester 502 54 Extraction of Essential oils from Caraway, Cinnamon, Cloves, Cumin,

Fennel, or Star Anise by Steam distillation 506 54A isolation of Essential oils by Steam distillation 508 54B identification of the Constituents of Essential oils by Gas

Chromatography–Mass Spectrometry 511 54C investigation of the Essential oils of herbs and Spices—A Mini-Research

Project 512 55 Competing nucleophiles in Sn1 and Sn2 Reactions: investigations Using

2-Pentanol and 3-Pentanol 514

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Contents xix

56 Friedel–Crafts Acylation 519 57 the Analysis of Antihistamine drugs by Gas Chromatography–Mass

Spectrometry 527 58 the Use of organozinc Reagents in Synthesis: An Exercise in Synthesis

and Structure Proof by Spectroscopy 530 59 Synthesis of naproxen by Palladium Catalysis 534 60 Aldehyde disproportionation: A Structure Proof Problem 548 61 Synthesis of Substituted Chalcones: A Guided-inquiry Experience 551 62 Green Epoxidation of Chalcones 556 63 Cyclopropanation of Chalcones 560 64 Michael and Aldol Condensation Reactions 564 65 Esterification Reactions of Vanillin: the Use of nMR to Solve a Structure

Proof Problem 568 66 An oxidation Puzzle 571

PART 6 The Techniques 575 1 Laboratory Safety 576 2 the Laboratory notebook, Calculations, and Laboratory Records 592 3 Laboratory Glassware: Care and Cleaning 599 4 how to Find data for Compounds: handbooks and Catalogs 607 5 Measurement of Volume and Weight 614 6 heating and Cooling Methods 622 7 Reaction Methods 629 8 Filtration 649 9 Physical Constants of Solids: the Melting Point 660 10 Solubility 669 11 Crystallization: Purification of Solids 678 12 Extractions, Separations, and drying Agents 700 13 Physical Constants of Liquids: the Boiling Point and density 727 14 Simple distillation 738 15 Fractional distillation, Azeotropes 750 16 Vacuum distillation, Manometers 767 17 Sublimation 779 18 Steam distillation 784 19 Column Chromatography 790 20 thin-Layer Chromatography 810 21 high-Performance Liquid Chromatography (hPLC) 824 22 Gas Chromatography 829 23 Polarimetry 849 24 Refractometry 857 25 infrared Spectroscopy 862 26 nuclear Magnetic Resonance Spectroscopy (Proton nMR) 896 27 Carbon-13 nuclear Magnetic Resonance Spectroscopy 934 28 Mass Spectrometry 951 29 Guide to the Chemical Literature 969

Appendices 983 1 tables of Unknowns and derivatives 984 2 Procedures for Preparing derivatives 998 3 index of Spectra 1002

Index 1005

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Introduction to Basic Laboratory Techniques

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