A microscale approach to organic laboratory techniques

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METRIC 1

2
Common Organic Solvents

3
Solvent

4
5
6
7
8
9
10
11
12
13
14
15

Acetic acid
Acetic anhydride
Acetone
Benzene*
Carbon tetrachloride*
Chloroform*
Cyclohexane
Dimethylformamide (DMF)

Dimethyl sulfoxide (DMSO)
Ethanol
Ether (diethyl)
Ethyl acetate
Heptane
Hexane
Ligroin
Methanol
Methylene chloride
Pentane
Petroleum ether
1-Propanol
2-Propanol
Pyridine
Tetrahydrofuran (THF)
Toluene
Xylenes

16

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

Boiling Point (°C)

Density (g/mL)

118
140
56

80
77
61
81
153
189
78
35
77
98
69
60–90
65
40
36
30–60
98
82
115
65
111

1.05
1.08
0.79
0.88
1.59
1.48
0.78
0.94

1.10
0.80
0.71
0.90
0.68
0.66
0.68
0.79
1.32
0.63
0.63
0.80
0.79
0.98
0.99
0.87

137–144

0.86

17
18
19
20
21
22
23
24

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Atomic Mass Values
for Selected Elements
Aluminum
Boron
Bromine
Carbon
Chlorine
Fluorine
Hydrogen
Iodine
Lithium
Magnesium
Nitrogen
Oxygen
Phosphorus
Potassium
Silicon
Sodium
Sulfur

26.98
10.81
79.90
12.01
35.45
18.99
1.008

126.9
6.941
24.30
14.01
15.99
30.97
39.09
28.09
22.99
32.07

Concentrated Acids and Bases
Reagent

HCI

HNO 3

H 2 SO 4

HCOOH

CH 3 COOH

NH 3 (NH 4 OH)

Density (g/mL)
% Acid or base (by weight)

1.18

37.3

1.41
70.0

1.84
96.5

1.20
90.0

1.06
99.7

0.90
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

83

64

56

42

58

65

56
1.02

93
2.17

95
1.67

Volume of concentrated
reagent required to prepare
1 L of 1 M solution (ml)
Volume of concentrated
reagent required to prepare
1 L of 10% solution (ml)*
Molarity of a 10% solution*
*Percent solutions by weight.

227
2.74

101
1.59

384
5.87


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A Microscale
Approach
to

Organic
Laboratory
Techniques
Fifth Edition


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This is an electronic version of the print textbook. Due to electronic rights restrictions,
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A Microscale
Approach
to

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

© 2013, 2007, 1999 Brooks/Cole, Cengage Learning
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This book is dedicated to
our organic chemistry laboratory students


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Preface

STATEMENT OF MISSION AND PURPOSE IN REVISING THE

TEXTBOOK
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 organometallic 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 projectbased 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 careful to retain all of the standard reactions and techniques, such as the ­Friedel-Crafts
­reaction, the aldol condensation, Grignard synthesis, and basic experiments designed to teach crystallization, chromatography, and distillation.

SCALE IN THE ORGANIC LABORATORY
Experiments in organic chemistry can be conducted at different scales using varying 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 T
s 14/10 standard-tapered glassware. Our version of a “macroscale” textbook
(A Small Scale Approach to Organic Laboratory Techniques) uses the traditional larger
scale T
s 19/22 standard-tapered glassware. The third edition of our small scale book
was published in 2011.

vii

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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 students 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.”

MAJOR FEATURES OF THE TEXTBOOK THAT WILL BENEFIT
THE STUDENT
Organic chemistry significantly impacts our lives in the real world. Organic chemistry 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.

NEW TO THIS EDITION
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
Borneol oxidation to camphor, new procedure
Experiment 31
Experiment 34Sonogashira Coupling of Iodoaromatic Compounds with
Alkynes
Experiment 35Grubb’s-Catalyzed Metathesis of Eugenol with cis-1,4Butenediol
Experiment 44N,N-Diethyl-m-toluamide (OFF), new procedure
Experiment 48Diels-Alder Reaction with Anthracene-9-methanol
Experiment 52Identification of Unknowns, revised procedure
Experiment 55Competing Nucleophiles in SN1 and SN2 Reactions: Investigations 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 59Synthesis of Naproxen (Aleve®) by palladium catalysis
Experiment 62
Green Epoxidation of Chalcones
Cyclopropanation of Chalcones
Experiment 63
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 contamination 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”
essay has 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 emphasis 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 chromatography 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 LT E R N AT 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 digital 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.

INSTRUCTOR RESOURCES
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 equipment for each experiment, as well as answers to each of the questions in this textbook. In some cases, additional optional experiments are included. Instructors will
also find helpful the ­estimated time to complete each experiment and notes regarding 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.

ACKNOWLEDGMENTS
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
­U niversity), Charles Wandler (Western Washington ­U niversity), 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 editor, 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 participate 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
Gary M. Lampman
George S. Kriz
Randall G. Engel

()
()
()
()
November 2011


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How To Use This Book

OVERALL STRUCTURE OF THE BOOK
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.

STRUCTURE OF THE EXPERIMENTS
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 individual 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 Experiment 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 synthesis. 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 isolation 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.
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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 essential to the success of the experiment.
Suggested Waste Disposal
This very important section gives instructions on how to dispose of the waste generated 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.
Procedure
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.
Report
In some experiments, specific suggestions for what should be included in the laboratory report will be given. Your instructor may refer to these recommendations or
may have other directions for you to follow.
Questions
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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Contents



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
xv


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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-Butene  168

EssayComputational 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)-3Hydroxybutanoate  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

34Sonogashira 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
54Extraction 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

55Competing 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
58The 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
  1Tables of Unknowns and Derivatives  984
  2 Procedures for Preparing Derivatives  998

  3Index of Spectra  1002



Index  1005


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part

1

Introduction to Basic
Laboratory Techniques

1