Table Of ContentOrganicChemistry
Demystified
DANIEL R. BLOCH
McGRAW-HILL
NewYork Chicago SanFrancisco Lisbon London
Madrid MexicoCity Milan NewDelhi
SanJuan Seoul Singapore Sydney Toronto
Copyright © 2006 by The McGraw-Hill Companies, Inc. Inc. All rights reserved. Manufactured in the United States of America.
Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in
any form or by any means, or stored in a database or retrieval system, without the prior written permission of the publisher.
0-07-148710-7
The material in this eBook also appears in the print version of this title: 0-07-145920-0.
All trademarks are trademarks of their respective owners. Rather than put a trademark symbol after every occurrence of a trade-
marked name, we use names in an editorial fashion only, and to the benefit of the trademark owner, with no intention of infringe-
ment of the trademark. Where such designations appear in this book, they have been printed with initial caps.
McGraw-Hill eBooks are available at special quantity discounts to use as premiums and sales promotions, or for use in corporate
training programs. For more information, please contact George Hoare, Special Sales, at [email protected] or (212)
904-4069.
TERMS OF USE
This is a copyrighted work and The McGraw-Hill Companies, Inc. (“McGraw-Hill”) and its licensors reserve all rights in and to the
work. Use of this work is subject to these terms. Except as permitted under the Copyright Act of 1976 and the right to store and
retrieve one copy of the work, you may not decompile, disassemble, reverse engineer, reproduce, modify, create derivative works
based upon, transmit, distribute, disseminate, sell, publish or sublicense the work or any part of it without McGraw-Hill’s prior con-
sent. You may use the work for your own noncommercial and personal use; any other use of the work is strictly prohibited. Your
right to use the work may be terminated if you fail to comply with these terms.
THE WORK IS PROVIDED “AS IS.” McGRAW-HILL AND ITS LICENSORS MAKE NO GUARANTEES OR WARRANTIES
AS TO THE ACCURACY, ADEQUACY OR COMPLETENESS OF OR RESULTS TO BE OBTAINED FROM USING THE
WORK, INCLUDING ANY INFORMATION THAT CAN BE ACCESSED THROUGH THE WORK VIA HYPERLINK OR
OTHERWISE, AND EXPRESSLY DISCLAIM ANY WARRANTY, EXPRESS OR IMPLIED, INCLUDING BUT NOT LIMIT-
ED TO IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. McGraw-Hill and
its licensors do not warrant or guarantee that the functions contained in the work will meet your requirements or that its operation
will be uninterrupted or error free. Neither McGraw-Hill nor its licensors shall be liable to you or anyone else for any inaccuracy,
error or omission, regardless of cause, in the work or for any damages resulting therefrom. McGraw-Hill has no responsibility for
the content of any information accessed through the work. Under no circumstances shall McGraw-Hill and/or its licensors be liable
for any indirect, incidental, special, punitive, consequential or similar damages that result from the use of or inability to use the
work, even if any of them has been advised of the possibility of such damages. This limitation of liability shall apply to any claim
or cause whatsoever whether such claim or cause arises in contract, tort or otherwise.
DOI: 10.1036/0071459200
For more information about this title, click here
CONTENTS
Preface xvii
Acknowledgments xix
CHAPTER 1 Structure and Bonding 1
Atomic Structure 1
Atomic Number and Atomic Mass (Weight) 3
Electron Energy Levels 4
The Octet Rule 7
Valences 8
Lewis Structures 9
Orbital Shapes 15
Quantum Mechanics 15
Bond Formation 18
Valence Bond Theory 20
Molecular Orbitals 21
Bonding and Antibonding MOs 21
Bonding and 3-D Molecular Shape 23
Curved Arrows 30
Electronegativity and Bond Polarity 31
Dipole Moments 33
Formal Charges 34
Resonance Structures 36
Intermolecular Forces 37
Quiz 39
CHAPTER 2 Families and Functional Groups 43
vii
CONTENTS
viii
CHAPTER 3 Acids and Bases 46
Introduction 46
Arrhenius Definition 47
Brønsted-Lowry Definition 47
Conjugate Acids and Bases 47
Equilibrium Reactions 49
Weak Hydrocarbon Acids 53
Lewis Acids and Bases 54
Quiz 56
CHAPTER 4 Alkanes and Cycloalkanes 59
Introduction 59
Sources of Alkanes 60
Acyclic and Cyclic Alkanes 60
Nomenclature 61
Formulas 62
Structures 62
Constitutional Isomers 64
Cycloalkanes 66
Alkyl Groups 67
Nomenclature—Naming Compounds
by the IUPAC System 70
Physical Properties 74
Chemical Properties 75
Conformations of Alkanes 76
Conformations of Cylcoalkanes 84
Quiz 94
CHAPTER 5 Stereochemistry 99
Isomers 99
Chiral Compounds 100
Stereocenters 101
Chirality Centers 102
Enantiomers 105
Racemic Mixtures 109
CONTENTS
ix
The R/S System 110
When the Lowest Priority Group Is Not
in the Back 113
Molecules with Multiple Asymmetric
Centers 115
Enantiomers 116
Diastereomers 116
Meso Compounds 117
Fisher Projections 119
Rotating Fisher Projections/Structures 120
Cyclic Stereoisomers 122
Naming Cyclic Stereoisomers 125
Prochiral Carbons (Wanabees) 126
Quiz 126
CHAPTER 6 Structure and Properties of Alkenes 129
Introduction 129
Structure 130
Naming Alkenes 132
Common Names 134
Cis and Trans Isomers 134
The E/Z (Easy) System 135
Degrees of Unsaturation 136
Stability of Alkenes 140
Physical Properties of Alkenes 141
Chemical Properties 141
The Curved Arrow 142
Quiz 142
CHAPTER 7 Reaction Mechanisms 145
Introduction 145
Thermodynamics 145
Kinetics 148
Carbocations 150
Stereochemistry 151
CONTENTS
x
The Hammond Postulate 152
Regiochemical Reactions 154
The Markovnikov Rule 155
Stereochemistry 156
Rearrangement Reactions of Carbocations 157
Quiz 159
CHAPTER 8 Reactions of Alkenes 161
Reaction with Hydrogen Halides in Inert
Solvents 161
Reaction with Hydrogen Halides in Protic
Solvents 162
Oxymercuration-Demercuration Reactions 165
Hydroboration-Reduction 167
Halogenation in Inert Solvents 171
Stereochemistry Halogenation 173
Halogenation in Reactive Solvents 174
Radical Bromination 175
Formation of Diols 177
Double Bond Cleavage 178
Hydrogenation 180
Epoxides 180
Cyclopropanes 181
Quiz 182
CHAPTER 9 Alkynes 185
Introduction 185
Structure 185
Nomenclature 186
Physical Properties 188
Chemical Properties 188
Reactions with Brønsted-Lowry Acids 189
CONTENTS
xi
Reactions with HBr and Peroxides 193
Reaction with Halogens 195
Hydration Reactions 195
Hydroboration-Oxidation Reactions 198
Hydrogenation/Reduction Reactions 199
Oxidation Reactions 200
Acidity of Alkynes 201
Alkylation Reactions 202
Preparation of Alkynes 204
Quiz 204
CHAPTER 10 Characterization 207
Introduction 207
Chromatography 207
Spectroscopy 212
UV Spectroscopy 222
Nuclear Magnetic Resonance Spectroscopy 226
Nuclear Properties 226
NMR Spectrometers 228
1
H NMR Spectroscopy 230
13
C NMR Spectroscopy 243
Mass Spectrometry 246
Quiz 251
CHAPTER 11 Organohalides 256
Introduction 256
Nomenclature 256
Properties 257
Preparation of Halides 258
Radical Halogenation 258
Isomeric Products 260
Allylic Halogenation 263
Reactions of Organohalides 265
Quiz 266
CONTENTS
xii
CHAPTER 12 Nucleophilic Substitution and
Elimination Reactions 269
Introduction 269
Properties of Nucleophiles 270
Properties of Bases 271
Properties of Substrates/Electrophiles 272
Properties of Leaving Groups 272
Properties of Solvents 273
Second-Order Nucleophilic Substitution
(S 2) Reactions 276
N
First-Order Nucleophilic Substitution
(S 1) Reactions 279
N
Summary of S 1 and S 2 Reactions 284
N N
Second-Order Elimination (E2)
Reactions 284
First-Order Elimination (E1) Reactions 289
Summary of E1 and E2 Reactions 291
Competition between Substitution and
Elimination Reactions 291
Quiz 292
CHAPTER 13 Alcohols 295
Introduction 295
Properties of Alcohols 296
Nomenclature 297
Acidity and Basicity of Alcohols 299
Reactions with Active Metals 301
Preparation of Alcohols 301
Organometallic Compounds 306
Preparation of Alcohols Using
Organometallic Reagents 307
Reactions of Alcohols 310
Conversion of Alcohols to Alkyl Halides 311
Dehydration Reactions 313
Quiz 313
CONTENTS
xiii
CHAPTER 14 Ethers 317
Introduction 317
Nomenclature 317
Properties 318
Preparation of Ethers 319
Reactions of Ethers 321
Three-Membered Ether Rings 323
Quiz 327
CHAPTER 15 Sulfur Compounds 330
Nomenclature 330
Properties 331
Reactions of Sulfur Compounds 333
Quiz 335
CHAPTER 16 Conjugated Systems 337
Introduction 337
Stability of Dienes 337
Electrophilic Addition to Conjugated Dienes 344
Allylic Cations, Radicals, and Anions 347
Diels-Alder Reactions 349
Quiz 355
CHAPTER 17 Aromatic Compounds 358
Introduction 358
Reactivity of Aromatic Compounds 358
Nomenclature 359
Kekule´ Structures 361
Stability of Benzene 362
The Resonance Model 364
Molecular Orbital Description of Aromaticity 365
Properties of Aromatic, Nonaromatic, and
Antiaromatic Compounds 369
Hu¨ckel’s Rule 370
Heterocyclic Compounds 371
CONTENTS
xiv
Aromatic Ions 372
Polycyclic Aromatic Compounds 374
Quiz 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 404
Introduction 404
Nomenclature 405
Physical Properties 408
Chemical Properties 408
Preparation of Aldehydes and Ketones 410
Hydration of Alkynes 412
Reduction of Acid Chlorides 414
Reactions of Aldehydes and Ketones with
Nucleophiles 418
Wittig Reactions 424
Oxidation and Reduction Reactions 425
Quiz 427
CHAPTER 20 Carboxylic Acids 430
Introduction 430
Nomenclature 431
Three-Dimensional Structure 434
Molecular Orbital (MO) Description 434
Physical Properties 435
