Organic Chemistry Demystified Daniel Bloch, 2006

Organic Chemistry
Demystified


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Organic Chemistry
Demystified

DANIEL R. BLOCH

McGRAW-HILL
New York

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DOI: 10.1036/0071459200


To Nan for her assistance, patience, and helpful comments.

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CONTENTS

Preface

xvii

Acknowledgments

xix

CHAPTER 1

Structure and Bonding
Atomic Structure
Atomic Number and Atomic Mass (Weight)
Electron Energy Levels
The Octet Rule
Valences
Lewis Structures
Orbital Shapes
Quantum Mechanics
Bond Formation
Valence Bond Theory
Molecular Orbitals
Bonding and Antibonding MOs

Bonding and 3-D Molecular Shape
Curved Arrows
Electronegativity and Bond Polarity
Dipole Moments
Formal Charges
Resonance Structures
Intermolecular Forces
Quiz

1
1
3
4
7
8
9
15
15
18
20
21
21
23
30
31
33
34
36
37
39

CHAPTER 2

Families and Functional Groups

43
vii


CONTENTS

viii

CHAPTER 3

Acids and Bases
Introduction
Arrhenius Definition
Brønsted-Lowry Definition
Conjugate Acids and Bases
Equilibrium Reactions
Weak Hydrocarbon Acids
Lewis Acids and Bases
Quiz

46
46
47
47
47

49
53
54
56

CHAPTER 4

Alkanes and Cycloalkanes
Introduction
Sources of Alkanes
Acyclic and Cyclic Alkanes
Nomenclature
Formulas
Structures
Constitutional Isomers
Cycloalkanes
Alkyl Groups
Nomenclature—Naming Compounds
by the IUPAC System
Physical Properties
Chemical Properties
Conformations of Alkanes
Conformations of Cylcoalkanes
Quiz

59
59
60
60
61

62
62
64
66
67

CHAPTER 5

Stereochemistry
Isomers
Chiral Compounds
Stereocenters
Chirality Centers
Enantiomers
Racemic Mixtures

70
74
75
76
84
94
99
99
100
101
102
105
109

CONTENTS

ix

The R/S System
When the Lowest Priority Group Is Not
in the Back
Molecules with Multiple Asymmetric
Centers
Enantiomers
Diastereomers
Meso Compounds
Fisher Projections
Rotating Fisher Projections/Structures
Cyclic Stereoisomers
Naming Cyclic Stereoisomers
Prochiral Carbons (Wanabees)
Quiz

110

115
116
116
117
119
120
122
125

126
126

CHAPTER 6

Structure and Properties of Alkenes
Introduction
Structure
Naming Alkenes
Common Names
Cis and Trans Isomers
The E/Z (Easy) System
Degrees of Unsaturation
Stability of Alkenes
Physical Properties of Alkenes
Chemical Properties
The Curved Arrow
Quiz

129
129
130
132
134
134
135
136
140
141
141

142
142

CHAPTER 7

Reaction Mechanisms
Introduction
Thermodynamics
Kinetics
Carbocations
Stereochemistry

145
145
145
148
150
151

113


CONTENTS

x

CHAPTER 8

CHAPTER 9

The Hammond Postulate
Regiochemical Reactions
The Markovnikov Rule
Stereochemistry
Rearrangement Reactions of Carbocations
Quiz

152
154
155
156
157
159

Reactions of Alkenes
Reaction with Hydrogen Halides in Inert
Solvents
Reaction with Hydrogen Halides in Protic
Solvents
Oxymercuration-Demercuration Reactions
Hydroboration-Reduction
Halogenation in Inert Solvents
Stereochemistry Halogenation
Halogenation in Reactive Solvents
Radical Bromination
Formation of Diols
Double Bond Cleavage
Hydrogenation
Epoxides
Cyclopropanes

Quiz

161

Alkynes
Introduction
Structure
Nomenclature
Physical Properties
Chemical Properties
Reactions with Brønsted-Lowry Acids

185
185
185
186
188
188
189

161
162
165
167
171
173
174
175
177
178

180
180
181
182


CONTENTS

xi

Reactions with HBr and Peroxides
Reaction with Halogens
Hydration Reactions
Hydroboration-Oxidation Reactions
Hydrogenation/Reduction Reactions
Oxidation Reactions
Acidity of Alkynes
Alkylation Reactions
Preparation of Alkynes
Quiz

193
195
195
198
199
200
201
202
204

204

CHAPTER 10

Characterization
Introduction
Chromatography
Spectroscopy
UV Spectroscopy
Nuclear Magnetic Resonance Spectroscopy
Nuclear Properties
NMR Spectrometers
1 H NMR Spectroscopy
13 C NMR Spectroscopy
Mass Spectrometry
Quiz

207
207
207
212
222
226
226
228
230
243
246
251

CHAPTER 11

Organohalides
Introduction
Nomenclature
Properties
Preparation of Halides
Radical Halogenation
Isomeric Products
Allylic Halogenation
Reactions of Organohalides
Quiz

256
256
256
257
258
258
260
263
265
266


CONTENTS

xii

CHAPTER 12

CHAPTER 13

Nucleophilic Substitution and
Elimination Reactions
Introduction
Properties of Nucleophiles
Properties of Bases
Properties of Substrates/Electrophiles
Properties of Leaving Groups
Properties of Solvents
Second-Order Nucleophilic Substitution
(SN 2) Reactions
First-Order Nucleophilic Substitution
(SN 1) Reactions
Summary of SN 1 and SN 2 Reactions
Second-Order Elimination (E2)
Reactions
First-Order Elimination (E1) Reactions
Summary of E1 and E2 Reactions
Competition between Substitution and
Elimination Reactions
Quiz
Alcohols
Introduction
Properties of Alcohols
Nomenclature
Acidity and Basicity of Alcohols
Reactions with Active Metals
Preparation of Alcohols

Organometallic Compounds
Preparation of Alcohols Using
Organometallic Reagents
Reactions of Alcohols
Conversion of Alcohols to Alkyl Halides
Dehydration Reactions
Quiz

269
269
270
271
272
272
273
276
279
284
284
289
291
291
292
295
295
296
297
299
301
301

306
307
310
311
313
313


CONTENTS

xiii

CHAPTER 14

Ethers
Introduction
Nomenclature
Properties
Preparation of Ethers
Reactions of Ethers
Three-Membered Ether Rings
Quiz

317
317
317
318
319
321
323

327

CHAPTER 15

Sulfur Compounds
Nomenclature
Properties
Reactions of Sulfur Compounds
Quiz

330
330
331
333
335

CHAPTER 16

Conjugated Systems
Introduction
Stability of Dienes
Electrophilic Addition to Conjugated Dienes
Allylic Cations, Radicals, and Anions
Diels-Alder Reactions
Quiz

337
337
337
344

347
349
355

CHAPTER 17

Aromatic Compounds
358
Introduction
358
Reactivity of Aromatic Compounds
358
Nomenclature
359
Kekul´e Structures
361
Stability of Benzene
362
The Resonance Model
364
Molecular Orbital Description of Aromaticity 365
Properties of Aromatic, Nonaromatic, and
Antiaromatic Compounds
369
H¨uckel’s Rule
370
Heterocyclic Compounds
371

CONTENTS

xiv

Aromatic Ions
Polycyclic Aromatic Compounds
Quiz

372
374
375

CHAPTER 18

Reactions of Benzene and other
Aromatic Compounds
378
Introduction
378
Electrophilic Aromatic Substitution
379
Nucleophilic Aromatic Substitution
386
More Derivatives of Benzene
388
Multiple Substitution Reactions
392
Electrophilic Substitution in Disubstituted
Benzenes
399

Quiz
400

CHAPTER 19

Aldehydes and Ketones
Introduction
Nomenclature
Physical Properties
Chemical Properties
Preparation of Aldehydes and Ketones
Hydration of Alkynes
Reduction of Acid Chlorides
Reactions of Aldehydes and Ketones with
Nucleophiles
Wittig Reactions
Oxidation and Reduction Reactions
Quiz

404
404
405
408
408
410
412
414

Carboxylic Acids
Introduction

Nomenclature
Three-Dimensional Structure
Molecular Orbital (MO) Description
Physical Properties

430
430
431
434
434
435

CHAPTER 20

418
424
425
427


CONTENTS

xv

Acidity of Carboxylic Acids
Preparation of Carboxylic Acids
Derivatives of Carboxylic Acids
Quiz

437

439
444
444

CHAPTER 21

Derivatives of Carboxylic Acids
Introduction
Carboxylic Acid Halides
Carboxylic Acid Anhydrides
Carboxylic Esters
Amides
Cyclic Amides
Imides
Nitriles
Quiz

447
447
450
454
458
463
466
467
468
470

CHAPTER 22

Alpha-Substitution Reactions in
Carbonyl Compounds
Introduction
Enol and Enolate Anions
Alpha Monohalogenation of Aldehydes
and Ketones
α,β Unsaturated Ketones
α-Bromination of Carboxylic Acids
Acidity of α-Hydrogen Atoms
Malonic Ester Synthesis
Acetoacetic Ester Synthesis
Additional Condensation Reactions
Quiz

CHAPTER 23

Carbonyl Condensation Reactions
Introduction
Aldol Reactions
Dehydration of Aldol Compounds
Mixed or Crossed Aldol Reactions

474
474
475
477
479
479
479
483

485
486
488
490
490
491
492
493


CONTENTS

xvi

Intramolecular Aldol Reactions
Claisen Condensation Reactions
α-Substitution Reactions
Quiz

494
495
499
502

Final Exam

504

Quiz and Exam Solutions

531

Appendix A / Periodic Table
of the Elements

537

Bibliography

539

Index

541


PREFACE

Organic chemistry is the chemistry of carbon-containing compounds. Every
living organism, plant and animal, is composed of organic compounds. Anyone
with an interest in life and living things needs to have a basic understanding of
organic chemistry.
Articles continue to appear in newspapers and magazines describing the
development of new medicines and diagnostic tests. These new products and
technologies are results of a better understanding of the structure and function
of DNA, proteins, and other organic biological molecules. The reactions and
interactions of these complex molecules are the same reactions and interactions
that occur in more simple organic molecules.
This text was written to help those who are intimidated by the words organic
chemistry. Those who have never had a formal course in organic chemistry and

students currently taking or planning to take a formal course will find this text
an easy-to-read introduction and supplement to other texts.
The chapters are written in the same general order as found in most college
textbooks. It would be helpful, but not necessary, if the reader had a course in
introductory chemistry. The first three chapters cover the background material
typically covered in general chemistry courses. It is not necessary that chapters
be read sequentially, but since material tends to build on previous concepts it will
be easier to understand the material if the chapters are read in sequential order.
Key terms and concepts are italicized. Be sure you understand these concepts
as they will continue to appear in other sections of this book. Questions (and
answers) are given within each chapter to help you measure your understanding.
Each chapter ends with a quiz covering the material presented. Use each quiz
to check your comprehension and progress. The answers to quizzes are given
in the back of the text. Review those problems (immediately) you did not get
correct. Be sure you understand the concepts before going to the next chapter
as new material often builds upon previous concepts.

xvii
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xviii

PREFACE
As you read each chapter, take frequent breaks (you can munch on the extra
gum drops used to make models in Chapter 5). The book contains a lot of figures
and diagrams. Follow these as you read the text. It is often easier to understand
a reaction mechanism in a diagram than to describe it in words.
Yes, there is some memorization. New terms will appear that you probably
have never heard before. For a series of terms I recommend making a mnemonic

and I suggested a few. Reaction mechanisms are not as difficult as they may
appear. You can predict most reactions in that negative species will be attracted
to positive species (opposites attract). Atoms with electrons to share will be
attracted to species that want more electrons—it is just that simple.
There is a multiple-choice final exam at the end of the text. The final exam
has more general, but similar, questions than those in the quizzes. Answers are
given in the back of the book. If you are able to answer 80% of the final exam
questions correctly (the first time), you will have a good understanding of the
material.
I hope you will enjoy reading about organic chemistry as much as I have
enjoyed writing about it.
Daniel R. Bloch


ACKNOWLEDGMENTS

The author expresses his appreciation to Nan for her assistance, patience, and
helpful comments during the preparation of this book.
The following individuals were kind enough to review various chapters in
this book:
Vaughn Ausman, Marquette University
Kate Bichler, University of Wisconsin Center—Manitowoc
Peter Conigliaro (retired), S.C. Johnson
Sheldon Cramer (emeritus), Marquette University
Timothy Eckert, Carthage College
Sharbil Firson, Sigma-Aldrich
Kevin Glaeske, Wisconsin Lutheran College
Bruce Holman
Shashi Jasti, Sigma-Aldrich
Steven Levsen, Mount Mary College

Julie Lukesh, University of Wisconsin—Green Bay
Kevin Morris, Carthage College
Patt Nylen, University of Wisconsin—Milwaukee
Stephen Templin, Cardinal Stritch University
A special thanks to Priyanka Negi and Judy Bass who assisted with the
technical editing of this book.

xix
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Organic Chemistry
Demystified

xxi
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1

CHAPTER

Structure and
Bonding

Introduction
The study of organic chemistry involves the reactions and interactions of
molecules. Since molecules are composed of atoms, it is necessary to review
the structure of atoms and how they contribute to the properties of molecules.

Atomic Structure
Atoms are composed of a nucleus surrounded by electrons, as shown in Fig. 1-1.
The nucleus consists of positively charged protons and neutral neutrons. Although the nucleus consists of other subatomic particles, the proton, neutron,
and electron are the only subatomic particles that will be discussed in this text.

1
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CHAPTER 1

2

Structure and Bonding

Nucleus contains
protons and neutrons and is
about 0.0001 angstrom in diameter

Electron cloud

1Å
diameter

Fig. 1-1. Structure of an atom.

The atom is extremely small. It has a diameter of about 10−10 m
(0.000,000,000,1 m or 0.000,000,004 in.). These small dimensions are usu˚ where 1 A
˚ equals 1 ×10−10 m, or pm where
ally expressed in angstroms (A),
−12
1 pm equals 1 × 10
m. The nucleus is about 1/10,000th the diameter of the
−4 ˚
atom, or about 10 A. A key point: most of the volume of an atom is occupied
by the electrons. To put this in terms that are easier to understand, if the atom
was magnified so that the nucleus was the size of a marble, the area occupied by
the electrons would be the size of a football stadium. Take a minute to visualize
that. The area occupied by electrons is huge relative to that of the nucleus. The
area occupied by electrons is referred to as the electron cloud.

MASSES OF ATOMS
The mass of an atom is concentrated in the nucleus. A proton and a neutron
each have a mass of about 1.66 × 10−24 g. An electron has a mass of 1/1800th
that of a proton. Since these are such very small numbers, it is more convenient
to give the mass of a proton and a neutron in atomic mass units (amu). One
amu is equal to 1.66 × 10−24 g. The mass of individual atoms is also given in
a.m.u. The mass of 1 mole of atoms (a mole is a specific number, approximately
6.022 × 1023 ) is the atomic mass, which we usually call the atomic weight, of
an element. The atomic weight is expressed in grams/mol.

ELECTRON CLOUDS
Structures of molecules are usually written as shown in Fig. 1-2. Structure 1-2a
implies that atoms are quite far apart, relative to their size. This is certainly true

for the nuclei, but not for the electron clouds. The distance between a hydrogen
˚ The
nucleus and a carbon nucleus in a carbon-hydrogen bond is about 1.14 A.