,To the Student
Welcome to the fascinating world of organic chemistry. You are about to embark on an exciting
journey. This book has been written with students like you in mind—those who are encountering
the subject for the first time. The book’s central goal is to make this journey through organic
chemistry both stimulating and enjoyable by helping you understand central principles and asking
you to apply them as you progress through the pages. You will be reminded about these principles
at frequent intervals in references back to sections you have already mastered.
You should start by familiarizing yourself with the book. Inside the back cover is information
you may want to refer to often during the course. The list of Some Important Things to Remember
and the Reaction Summary at each chapter’s end provide helpful checklists of the concepts you
should understand after studying the chapter. The Glossary at the end of the book can also be a useful
study aid, as can the Appendices, which consolidate useful categories of information. The molecular
models and electrostatic potential maps that you will find throughout the book are provided to give
you an appreciation of what molecules look like in three dimensions and to show how charge is
distributed within a molecule. Think of the margin notes as the author’s opportunity to inject personal
reminders of ideas and facts that are important to remember. Be sure to read them.
Work all the problems within each chapter. These are drill problems that you will find at the end of
each section that allow you to check whether you have mastered the skills and concepts the particular
section is teaching before you go on to the next section. Some of these problems are solved for you in
the text. Short answers to some of the others—those marked with a diamond—are provided at the end
of the book. Do not overlook the “Problem-Solving Strategies” that are also sprinkled throughout the
text; they provide practical suggestions on the best way to approach important types of problems.
In addition to the within-chapter problems, work as many end-of-chapter problems as you
can. The more problems you work, the more comfortable you will be with the subject matter and
the better prepared you will be for the material in subsequent chapters. Do not let any problem
frustrate you. If you cannot figure out the answer in a reasonable amount of time, turn to the Study
Guide and Solutions Manual to learn how you should have approached the problem. Later on, go
back and try to work the problem on your own again. Be sure to visit www.MasteringChemistry.
com, where you can explore study tools including Exercise Sets, an Interactive Molecular Gallery,
Biographical Sketches of historically important chemists, and where you can access content on
many important topics.
The most important advice to remember (and follow) in studying organic chemistry is DO
NOT FALL BEHIND! The individual steps to learning organic chemistry are quite simple; each
by itself is relatively easy to master. But they are numerous, and the subject can quickly become
overwhelming if you do not keep up.
Before many of the theories and mechanisms were figured out, organic chemistry was a
discipline that could be mastered only through memorization. Fortunately, that is no longer true.
You will find many unifying ideas that allow you to use what you have learned in one situation to
predict what will happen in other situations. So, as you read the book and study your notes, always
making sure that you understand why each chemical event or behavior happens. For example,
when the reasons behind reactivity are understood, most reactions can be predicted. Approaching
the course with the misconception that to succeed you must memorize hundreds of unrelated
reactions could be your downfall. There is simply too much material to memorize. Understanding
and reasoning, not memorization, provide the necessary foundation on which to lay subsequent
learning. Nevertheless, from time to time some memorization will be required: some fundamental
rules will have to be memorized, and you will need to learn the common names of a number of
organic compounds. But that should not be a problem; after all, your friends have common names
that you have been able to learn and remember.
Students who study organic chemistry to gain entrance into medical school sometimes wonder
why medical schools pay so much attention to this topic. The importance of organic chemistry is not
in the subject matter alone, however. Mastering organic chemistry requires a thorough understanding
of certain fundamental principles and the ability to use those fundamentals to analyze, classify, and
predict. The study of medicine makes similar demands: a physician uses an understanding of certain
fundamental principles to analyze, classify, and diagnose.
Good luck in your study. I hope you will enjoy studying organic chemistry and learn to appreciate
the logic of this fascinating discipline. If you have any comments about the book or any suggestions
for improving it, I would love to hear from you. Remember, positive comments are the most fun, but
negative comments are the most useful.
Paula Yurkanis Bruice
,Medical Applications Biological Applications Measuring Toxicity (19.0)
Incipient Primary Carbocations (19.8)
Fosamax Prevents Bones from Being Nibbled Poisonous Amines (2.3) Synthetic Polymers (16.21)
Away (2.8) Cell Membranes (3.9) Olestra: Nonfat with Flavor (21.11)
Aspirin Must Be in its Basic Form to be Pheromones (5.0) Hair: Straight or Curly? (22.8)
Physiologically Active (2.10) Trans Fats (6.12) Right-Handed and Left-Handed Helices (22.14)
Blood: A Buffered Solution (2.11) How a Banana Slug Knows What to Eat (7.2) b-Peptides: An Attempt to Improve
Drugs Bind to Their Receptors (3.9) Electron Delocalization Affects the Three- on Nature (22.14)
Cholesterol and Heart Disease (3.15) Dimensional Shape of Proteins (8.5) Too Much Broccoli (24.8)
How High Cholesterol is Clinically Treated (3.15) DDT: A Synthetic Organohalide That Kills Why Did Nature Choose Phosphates? (25.1)
The Enantiomers of Thalidomide (6.17) Disease-Spreading Insects (9.0) Protein Prenylation (25.17)
Synthetic Alkynes Are Used to Treat Parkinson’s Naturally Occurring Organohalides That Defend Natural Products That Modify DNA (26.6)
Disease (7.0) Against Predators (10.0) Resisting Herbicides (26.14)
Synthetic Alkynes Are Used for Birth Control (7.1) Biological Dehydrations (11.4) Designing a Polymer (27.8)
S-Adenosylimethionine: A Natural Antidepressant (9.9) Alkaloids (11.9) Luminescence (29.6)
The Inability to Perform an SN2 Reaction Causes a Whales and Echolocation (16.13) A Biological Reaction That Involves an
Severe Clinical Disorder (11.3) Snake Venom (16.13) Electrocyclic Reaction Followed by a
Treating Alcoholism with Antabuse (11.5) Phosphoglycerides Are Components of Sigmatropic Rearrangement (29.6)
Methanol Poisoning (11.5) Membranes (16.13)
Anesthetics (11.6) A Semisynthetic Penicillin (16.15)
Benzo[a]pyrene and Cancer (11.8) Dalmatians: Do Not Fool with Mother General Applications
Chimney Sweeps and Cancer (11.8) Nature (16.16) Derivation of the Henderson-Hasselbalch
Lead Compounds for the Development Preserving Biological Specimens (17.11) Equation (2.10)
of Drugs (11.9) A Biological Friedel-Crafts Alkylation (19.8) How is the Octane Number of Gasoline
Alkylating Agents as Cancer Drugs (11.11) Controlling Fleas (21.16) Determined? (3.2)
Is Chocolate a Health Food? (13.11) Primary Structure and Taxonomic Relationship A Few Words About Curved Arrows (5.6)
Artificial Blood (13.12) (22.12) Calculating Kinetic Parameters (End of Ch 05)
Nature’s Sleeping Pill (16.1) Competitive Inhibitors (24.7) Which are More Harmful, Natural Pesticides or
Aspirin, NSAIDs, and Cox-2 Inhibitors (16.11) There Are More Than Four Bases in DNA (26.7) Synthetic Pesticides? (6.18)
The Discovery of Penicillin (16.15) Why Are Drugs so Expensive? (7.0)
Penicillin and Drug Resistance (16.15) Kekule’s Dream (8.1)
Penicillins in Clinical Use (16.15) Chemical Applications Environmental Adaptation (9.7)
Dissolving Sutures (16.21) Natural Organic Compounds versus Synthetic Organic The Nobel Prize (10.8)
Serendipity in Drug Development (17.10) Compounds (1.0) Grain Alcohol and Wood Alcohol (11.1)
Cancer Chemotherapy (17.18) Diamond, Graphite, Graphene, and Fullerenes: Blood Alcohol Content (11.5)
Breast Cancer and Aromatase Inhibitors (18.12) Substances Containing Only Carbon Atoms (1.8) Natural Gas and Petroleum (13.1)
Discovery of the First Antibiotic (19.22) Water—A Unique Compound (1.12) Fossil Fuels: A Problematic Energy Source (13.1)
Drug Safety (19.22) Acid Rain (2.2) Why Radicals No Longer Have to Be Called Free
Nitrosamines and Cancer (19.23) Bad Smelling Compounds (3.7) Radicals (13.2)
Thyroxine (19.5) Von Baeyer, Barbituric Acid, and Blue Jeans (3.11) Decaffinated Coffee and the Cancer Scare (13.11)
Searching for Drugs: An Antihistamine, a Starch and Cellulose—Axial and Equatorial (3.13) Food Preservatives (13.11)
Nonsedating Antihistamine, and a Cis-Trans Interconversion in Vision (4.1) Mass Spectrometry in Forensics (14.8)
Drug for Ulcers (20.7) The Difference Between ∆G‡ and Ea (5.9) The Originator of Hooke’s Law (14.13)
Porphyrin, Bilirubin, and Jaundice (20.7) Borane and Diborane (6.8) Ultraviolet Light and Sunscreens (14.18)
Measuring the Blood Glucose Levels in Cyclic Alkenes (6.15) Nikola Tesla (15.1)
Diabetes (21.8) Chiral Catalysts (6.16) Structural Databases (15.24)
Lactose Intolerance (21.15) Chiral Drugs (4.15) Soaps and Micelles (16.13)
Galactosemia (21.15) Sodium Amide and Sodium in Ammonia (7.10) What Drug-Enforcement Dogs Are Really
Why the Dentist is Right (21.16) Green Chemistry: Aiming for Sustainability (7.12) Detecting (16.20)
Bacterial Resistance (21.17) Buckyballs (8.9) Butanedione: An Unpleasant Compound (17.1)
Heparin–A Natural Anticoagulant (21.17) Organic Compounds That Conduct Electricity (8.13) The Toxicity of Benzene (19.1)
Vitamin C (21.17) Why Are Living Organisms Composed of Carbon Glucose/Dextrose (21.9)
Amino Acids and Disease (22.2) Instead of Silicon? (9.2) Acceptable Daily Intake (21.19)
A Peptide Antibiotic (22.2) Solvation Effects (9.7) Proteins and Nutrition (22.1)
Diabetes (22.8) Eradicating Termites (9.7) Water Softeners: Examples of Cation-Exchange
Diseases Caused by a Misfolded Protein (22.15) The Lucas Test (11.1) Chromatography (22.3)
How Tamiflu Works (23.10) Crown Ethers: Another Example of Molecular Vitamin B1 (24.0)
Niacin Deficiency (24.1) Recognition (11.7) Curing A Hangover with Vitamin B1 (24.3)
Assessing the Damage After a Heart Attack (24.5) Crown Ethers Can be Used to Catalyze SN2 Differences in Metabolism (25.0)
The First Antibiotics (24.7) Reactions (11.7) The Structure of DNA: Watson, Crick, Franklin, and
Cancer Drugs and Side Effects (24.7) Mustard–A Chemical Warfare Agent (11.11) Wilkins (26.1)
Anticoagulants (24.8) Cyclopropane (13.9) DNA Fingerprinting (26.13)
Phenylketonuria (PKU): An Inborn Error of What Makes Blueberries Blue and Strawberries Teflon: An Accidental Discovery (27.2)
Metabolism (25.9) Red? (14.21) Recycling Symbols (27.2)
Alcaptonuria (25.9) Omega Fatty Acids (16.4)
Basal Metabolic Rate (25.11) Waxes Are Esters That Have High-Molecular
How Statins Lower Cholesterol Levels (25.17) Weights (16.9)
Sickle Cell Anemia (26.9) Synthetic Polymers (16.21)
Antibiotics That Act by Inhibiting Translation (26.9) Nerve Impulses, Paralysis, and Insecticides (16.23)
Three Different Antibiotics Act by a Common Enzyme-Catalyzed Carbonyl Additions (17.14)
Mechanism (26.10) Carbohydrates (17.12)
Influenza Pandemics (26.11) b-Carotene (17.16)
The X Prize (26.12) Synthesizing Organic Compounds (17.17)
Nanocontainers (27.5) Semisynthetic Drugs (17.17)
Melamine Poisoning (27.8) Enzyme-Catalyzed Cis-Trans
Health Concerns: Bisphenol A and Phthalates (27.8) Interconversion (17.18)
The Sunshine Vitamin (29.6) The Synthesis of Aspirin (18.7)
, Organic Chemistry
Welcome to the fascinating world of organic chemistry. You are about to embark on an exciting
journey. This book has been written with students like you in mind—those who are encountering
the subject for the first time. The book’s central goal is to make this journey through organic
chemistry both stimulating and enjoyable by helping you understand central principles and asking
you to apply them as you progress through the pages. You will be reminded about these principles
at frequent intervals in references back to sections you have already mastered.
You should start by familiarizing yourself with the book. Inside the back cover is information
you may want to refer to often during the course. The list of Some Important Things to Remember
and the Reaction Summary at each chapter’s end provide helpful checklists of the concepts you
should understand after studying the chapter. The Glossary at the end of the book can also be a useful
study aid, as can the Appendices, which consolidate useful categories of information. The molecular
models and electrostatic potential maps that you will find throughout the book are provided to give
you an appreciation of what molecules look like in three dimensions and to show how charge is
distributed within a molecule. Think of the margin notes as the author’s opportunity to inject personal
reminders of ideas and facts that are important to remember. Be sure to read them.
Work all the problems within each chapter. These are drill problems that you will find at the end of
each section that allow you to check whether you have mastered the skills and concepts the particular
section is teaching before you go on to the next section. Some of these problems are solved for you in
the text. Short answers to some of the others—those marked with a diamond—are provided at the end
of the book. Do not overlook the “Problem-Solving Strategies” that are also sprinkled throughout the
text; they provide practical suggestions on the best way to approach important types of problems.
In addition to the within-chapter problems, work as many end-of-chapter problems as you
can. The more problems you work, the more comfortable you will be with the subject matter and
the better prepared you will be for the material in subsequent chapters. Do not let any problem
frustrate you. If you cannot figure out the answer in a reasonable amount of time, turn to the Study
Guide and Solutions Manual to learn how you should have approached the problem. Later on, go
back and try to work the problem on your own again. Be sure to visit www.MasteringChemistry.
com, where you can explore study tools including Exercise Sets, an Interactive Molecular Gallery,
Biographical Sketches of historically important chemists, and where you can access content on
many important topics.
The most important advice to remember (and follow) in studying organic chemistry is DO
NOT FALL BEHIND! The individual steps to learning organic chemistry are quite simple; each
by itself is relatively easy to master. But they are numerous, and the subject can quickly become
overwhelming if you do not keep up.
Before many of the theories and mechanisms were figured out, organic chemistry was a
discipline that could be mastered only through memorization. Fortunately, that is no longer true.
You will find many unifying ideas that allow you to use what you have learned in one situation to
predict what will happen in other situations. So, as you read the book and study your notes, always
making sure that you understand why each chemical event or behavior happens. For example,
when the reasons behind reactivity are understood, most reactions can be predicted. Approaching
the course with the misconception that to succeed you must memorize hundreds of unrelated
reactions could be your downfall. There is simply too much material to memorize. Understanding
and reasoning, not memorization, provide the necessary foundation on which to lay subsequent
learning. Nevertheless, from time to time some memorization will be required: some fundamental
rules will have to be memorized, and you will need to learn the common names of a number of
organic compounds. But that should not be a problem; after all, your friends have common names
that you have been able to learn and remember.
Students who study organic chemistry to gain entrance into medical school sometimes wonder
why medical schools pay so much attention to this topic. The importance of organic chemistry is not
in the subject matter alone, however. Mastering organic chemistry requires a thorough understanding
of certain fundamental principles and the ability to use those fundamentals to analyze, classify, and
predict. The study of medicine makes similar demands: a physician uses an understanding of certain
fundamental principles to analyze, classify, and diagnose.
Good luck in your study. I hope you will enjoy studying organic chemistry and learn to appreciate
the logic of this fascinating discipline. If you have any comments about the book or any suggestions
for improving it, I would love to hear from you. Remember, positive comments are the most fun, but
negative comments are the most useful.
Paula Yurkanis Bruice
,Medical Applications Biological Applications Measuring Toxicity (19.0)
Incipient Primary Carbocations (19.8)
Fosamax Prevents Bones from Being Nibbled Poisonous Amines (2.3) Synthetic Polymers (16.21)
Away (2.8) Cell Membranes (3.9) Olestra: Nonfat with Flavor (21.11)
Aspirin Must Be in its Basic Form to be Pheromones (5.0) Hair: Straight or Curly? (22.8)
Physiologically Active (2.10) Trans Fats (6.12) Right-Handed and Left-Handed Helices (22.14)
Blood: A Buffered Solution (2.11) How a Banana Slug Knows What to Eat (7.2) b-Peptides: An Attempt to Improve
Drugs Bind to Their Receptors (3.9) Electron Delocalization Affects the Three- on Nature (22.14)
Cholesterol and Heart Disease (3.15) Dimensional Shape of Proteins (8.5) Too Much Broccoli (24.8)
How High Cholesterol is Clinically Treated (3.15) DDT: A Synthetic Organohalide That Kills Why Did Nature Choose Phosphates? (25.1)
The Enantiomers of Thalidomide (6.17) Disease-Spreading Insects (9.0) Protein Prenylation (25.17)
Synthetic Alkynes Are Used to Treat Parkinson’s Naturally Occurring Organohalides That Defend Natural Products That Modify DNA (26.6)
Disease (7.0) Against Predators (10.0) Resisting Herbicides (26.14)
Synthetic Alkynes Are Used for Birth Control (7.1) Biological Dehydrations (11.4) Designing a Polymer (27.8)
S-Adenosylimethionine: A Natural Antidepressant (9.9) Alkaloids (11.9) Luminescence (29.6)
The Inability to Perform an SN2 Reaction Causes a Whales and Echolocation (16.13) A Biological Reaction That Involves an
Severe Clinical Disorder (11.3) Snake Venom (16.13) Electrocyclic Reaction Followed by a
Treating Alcoholism with Antabuse (11.5) Phosphoglycerides Are Components of Sigmatropic Rearrangement (29.6)
Methanol Poisoning (11.5) Membranes (16.13)
Anesthetics (11.6) A Semisynthetic Penicillin (16.15)
Benzo[a]pyrene and Cancer (11.8) Dalmatians: Do Not Fool with Mother General Applications
Chimney Sweeps and Cancer (11.8) Nature (16.16) Derivation of the Henderson-Hasselbalch
Lead Compounds for the Development Preserving Biological Specimens (17.11) Equation (2.10)
of Drugs (11.9) A Biological Friedel-Crafts Alkylation (19.8) How is the Octane Number of Gasoline
Alkylating Agents as Cancer Drugs (11.11) Controlling Fleas (21.16) Determined? (3.2)
Is Chocolate a Health Food? (13.11) Primary Structure and Taxonomic Relationship A Few Words About Curved Arrows (5.6)
Artificial Blood (13.12) (22.12) Calculating Kinetic Parameters (End of Ch 05)
Nature’s Sleeping Pill (16.1) Competitive Inhibitors (24.7) Which are More Harmful, Natural Pesticides or
Aspirin, NSAIDs, and Cox-2 Inhibitors (16.11) There Are More Than Four Bases in DNA (26.7) Synthetic Pesticides? (6.18)
The Discovery of Penicillin (16.15) Why Are Drugs so Expensive? (7.0)
Penicillin and Drug Resistance (16.15) Kekule’s Dream (8.1)
Penicillins in Clinical Use (16.15) Chemical Applications Environmental Adaptation (9.7)
Dissolving Sutures (16.21) Natural Organic Compounds versus Synthetic Organic The Nobel Prize (10.8)
Serendipity in Drug Development (17.10) Compounds (1.0) Grain Alcohol and Wood Alcohol (11.1)
Cancer Chemotherapy (17.18) Diamond, Graphite, Graphene, and Fullerenes: Blood Alcohol Content (11.5)
Breast Cancer and Aromatase Inhibitors (18.12) Substances Containing Only Carbon Atoms (1.8) Natural Gas and Petroleum (13.1)
Discovery of the First Antibiotic (19.22) Water—A Unique Compound (1.12) Fossil Fuels: A Problematic Energy Source (13.1)
Drug Safety (19.22) Acid Rain (2.2) Why Radicals No Longer Have to Be Called Free
Nitrosamines and Cancer (19.23) Bad Smelling Compounds (3.7) Radicals (13.2)
Thyroxine (19.5) Von Baeyer, Barbituric Acid, and Blue Jeans (3.11) Decaffinated Coffee and the Cancer Scare (13.11)
Searching for Drugs: An Antihistamine, a Starch and Cellulose—Axial and Equatorial (3.13) Food Preservatives (13.11)
Nonsedating Antihistamine, and a Cis-Trans Interconversion in Vision (4.1) Mass Spectrometry in Forensics (14.8)
Drug for Ulcers (20.7) The Difference Between ∆G‡ and Ea (5.9) The Originator of Hooke’s Law (14.13)
Porphyrin, Bilirubin, and Jaundice (20.7) Borane and Diborane (6.8) Ultraviolet Light and Sunscreens (14.18)
Measuring the Blood Glucose Levels in Cyclic Alkenes (6.15) Nikola Tesla (15.1)
Diabetes (21.8) Chiral Catalysts (6.16) Structural Databases (15.24)
Lactose Intolerance (21.15) Chiral Drugs (4.15) Soaps and Micelles (16.13)
Galactosemia (21.15) Sodium Amide and Sodium in Ammonia (7.10) What Drug-Enforcement Dogs Are Really
Why the Dentist is Right (21.16) Green Chemistry: Aiming for Sustainability (7.12) Detecting (16.20)
Bacterial Resistance (21.17) Buckyballs (8.9) Butanedione: An Unpleasant Compound (17.1)
Heparin–A Natural Anticoagulant (21.17) Organic Compounds That Conduct Electricity (8.13) The Toxicity of Benzene (19.1)
Vitamin C (21.17) Why Are Living Organisms Composed of Carbon Glucose/Dextrose (21.9)
Amino Acids and Disease (22.2) Instead of Silicon? (9.2) Acceptable Daily Intake (21.19)
A Peptide Antibiotic (22.2) Solvation Effects (9.7) Proteins and Nutrition (22.1)
Diabetes (22.8) Eradicating Termites (9.7) Water Softeners: Examples of Cation-Exchange
Diseases Caused by a Misfolded Protein (22.15) The Lucas Test (11.1) Chromatography (22.3)
How Tamiflu Works (23.10) Crown Ethers: Another Example of Molecular Vitamin B1 (24.0)
Niacin Deficiency (24.1) Recognition (11.7) Curing A Hangover with Vitamin B1 (24.3)
Assessing the Damage After a Heart Attack (24.5) Crown Ethers Can be Used to Catalyze SN2 Differences in Metabolism (25.0)
The First Antibiotics (24.7) Reactions (11.7) The Structure of DNA: Watson, Crick, Franklin, and
Cancer Drugs and Side Effects (24.7) Mustard–A Chemical Warfare Agent (11.11) Wilkins (26.1)
Anticoagulants (24.8) Cyclopropane (13.9) DNA Fingerprinting (26.13)
Phenylketonuria (PKU): An Inborn Error of What Makes Blueberries Blue and Strawberries Teflon: An Accidental Discovery (27.2)
Metabolism (25.9) Red? (14.21) Recycling Symbols (27.2)
Alcaptonuria (25.9) Omega Fatty Acids (16.4)
Basal Metabolic Rate (25.11) Waxes Are Esters That Have High-Molecular
How Statins Lower Cholesterol Levels (25.17) Weights (16.9)
Sickle Cell Anemia (26.9) Synthetic Polymers (16.21)
Antibiotics That Act by Inhibiting Translation (26.9) Nerve Impulses, Paralysis, and Insecticides (16.23)
Three Different Antibiotics Act by a Common Enzyme-Catalyzed Carbonyl Additions (17.14)
Mechanism (26.10) Carbohydrates (17.12)
Influenza Pandemics (26.11) b-Carotene (17.16)
The X Prize (26.12) Synthesizing Organic Compounds (17.17)
Nanocontainers (27.5) Semisynthetic Drugs (17.17)
Melamine Poisoning (27.8) Enzyme-Catalyzed Cis-Trans
Health Concerns: Bisphenol A and Phthalates (27.8) Interconversion (17.18)
The Sunshine Vitamin (29.6) The Synthesis of Aspirin (18.7)
, Organic Chemistry
