Organic Chemistry

2017·57.17 MB·English

by  Paula Yurkanis Bruice

Organic Chemistry Page: i
Brief Table of Contents Page: iv
Complete List of In-Chapter Connection Features Page: vi
Contents Page: viii
Preface Page: xxii
Preparing Students for Future Study in a Variety of Scientific Disciplines Page: xxii
The Organization Ties Together Reactivity and Synthesis Page: xxii
Helping Students Learn and Study Organic Chemistry Page: xxiii
Organizational Changes Page: xxiii
Modularity/Spectroscopy Page: xxiv
An Early and Consistent Emphasis on Organic Synthesis Page: xxiv
Problems, Solved Problems, and Problem-Solving Strategies Page: xxiv
Powerpoint Page: xxv
Students Interested in The Biological Sciences and Mcat2015 Page: xxv
The Bioorganic Bridge Page: xxvi
Engaging Mixed Science Majors in Organic Chemistry Page: xxvi
Guided Approach to Problem Solving Page: xxvii
Dynamic Study Modules Page: xxx
Resources in Print and Online Page: xxx
Organic Chemistry Page: xxxiv
PART ONEAn Introduction to the Study of Organic Chemistry Page: 1
1 Remembering General Chemistry: Electronic Structure and Bonding Page: 2
1.1 The Structure of an Atom Page: 4
Problem 1 ♦ Page: 4
Problem 2 ♦ Page: 5
Problem 3 ♦ Page: 5
1.2 How the Electrons in an Atom are Distributed Page: 5
Ground-State Electronic Configuration Page: 5
Valence and Core Electrons Page: 7
Problem 4 ♦ Page: 7
Problem 5 ♦ Page: 7
Problem 6 Page: 7
1.3 Covalent Bonds Page: 7
Achieving a Filled Outer Shell by Losing or Gaining Electrons Page: 7
Problem 7 ♦ Page: 8
Achieving a Filled Outer Shell by Sharing Electrons Page: 8
Nonpolar and Polar Covalent Bonds Page: 9
Problem 8 ♦ Page: 11
Problem 9 ♦ Page: 11
Dipole Moments of Bonds Page: 11
Problem 10 Solved Page: 11
Problem 11 ♦ Page: 12
Problem 12 Solved Page: 12
Solution Page: 12
Problem 13 Page: 12
Electrostatic Potential Maps Page: 12
Problem 14 ♦ Page: 13
1.4 How the Structure of a Compound is Represented Page: 13
Lewis Structures Page: 13
Lone-Pair Electrons Page: 13
Formal Charge Page: 13
Problem 15 ♦ Page: 14
Drawing Lewis Structures Page: 14
Problem 16 Page: 14
Problem-Solving Strategy Drawing Lewis Structures Page: 15
Problem 17 Solved Page: 16
Solution to 17 a. Page: 16
Solution to 17 b. Page: 17
Problem 18 ♦ Page: 17
Kekulé Structures Page: 17
Condensed Structures Page: 17
Problem 19 ♦ Page: 17
Problem 20 ♦ Page: 18
Problem 21 ♦ Page: 19
Problem 22 Page: 19
Skeletal Structures Page: 19
Problem 23 Page: 19
1.5 Atomic Orbitals Page: 19
s Atomic Orbitals Page: 19
p Atomic Orbitals Page: 20
Problem 24 Page: 21
1.6 An Introduction to Molecular Orbital Theory Page: 21
Forming a sigma (σ) Bond Page: 21
Bonding and Antibonding Molecular Orbitals Page: 22
Problem 25 ♦ Page: 24
Forming a pi (π) Bond Page: 24
The VSEPR Model Page: 24
Problem 26 ♦ Page: 25
1.7 How Single Bonds are Formed in Organic Compounds Page: 25
The Bonds in Methane Page: 25
Hybrid Orbitals Page: 26
Tetrahedral Carbon; Tetrahedral Bond Angle Page: 27
The Bonds in Ethane Page: 27
Problem 27 ♦ Page: 28
Problem 28 Page: 28
1.8 How a Double Bond is Formed: The Bonds in Ethene Page: 29
Problem 29 Solved Page: 30
Solution Page: 31
1.9 How a Triple Bond is Formed: The Bonds in Ethyne Page: 31
Problem 30 Page: 32
Problem 31 Solved Page: 33
Solution to 31 a. Page: 33
Solution to 31 b. Page: 33
Problem 32 Page: 33
1.10 The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion Page: 33
The Methyl Cation (C+H3) Page: 33
The Methyl Radical (⋅CH3) Page: 33
The Methyl Anion (:¯CH3) Page: 34
1.11 The Bonds in Ammonia and in the Ammonium Ion Page: 35
Problem 33 ♦ Page: 36
Problem 34 ♦ Page: 36
1.12 The Bonds in Water Page: 36
Problem 35 ♦ Page: 37
Problem 36 Solved Page: 37
Solution Page: 37
1.13 The Bond in a Hydrogen Halide Page: 38
Problem 37 ♦ Page: 39
Problem 38 Page: 39
1.14 Hybridization and Molecular Geometry Page: 39
Problem-Solving Strategy Predicting the Orbitals and Bond Angles Used in Bonding Page: 39
Problem 39 Page: 40
1.15 Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles Page: 40
Bond Order Page: 40
Hybridization Page: 41
Problem 40 Solved Page: 41
Solution Page: 41
Bond Length and Bond Strength Page: 41
Hybridization Affects Bond Length and Bond Strength Page: 42
Hybridization Affects Bond Angles Page: 43
Problem 41 ♦ Page: 43
Problem 42 ♦ Page: 43
Problem 43 Page: 43
Problem 44 Page: 43
Problem-Solving Strategy Predicting Bond Angles Page: 44
Problem 45 ♦ Page: 44
1.16 Dipole Moments of Molecules Page: 44
Problem 46 ♦ Page: 45
Problem 47 Page: 45
Problem 48 ♦ Page: 45
Essential Concepts Page: 46
Glossary Page: 47
Problems Page: 47
2 Acids and Bases: Central to Understanding Organic Chemistry Page: 50
2.1 An Introduction to Acids and Bases Page: 50
Problem 1 ♦ Page: 52
Problem 2 ♦ Page: 52
Problem 3 ♦ Page: 52
Problem 4 ♦ Page: 52
2.2 pKa and pH Page: 52
Defining Keq Page: 52
Defining Ka Page: 52
Defining pKa Page: 53
Defining pH Page: 53
Problem 5 ♦ Page: 53
Problem 6 ♦ Page: 54
Problem-Solving Strategy Page: 54
Problem 7 Page: 54
Problem 8 Page: 54
Problem 9 ♦ Page: 54
2.3 Organic Acids and Bases Page: 55
Carboxylic Acids Page: 55
Alcohols Page: 55
Amines Page: 55
Protonated Compounds Page: 55
Alcohols, Carboxylic Acids, and Amines are Acids and Bases Page: 55
Problem 10 ♦ Page: 57
Problem 11 Page: 57
Problem 12 ♦ Page: 57
Problem-Solving Strategy Determining the Most Basic Atom in a Compound Page: 57
Problem 13 ♦ Page: 58
Problem 14 ♦ Page: 58
2.4 How to Predict the Outcome of an Acid–Base Reaction Page: 58
2.5 How to Determine the Position of Equilibrium Page: 59
Problem 16 Page: 59
Problem 17 Page: 59
Problem 18 ♦ Page: 59
Problem 19 ♦ Page: 59
2.6 How the Structure of an Acid Affects its pKa Value Page: 60
Electronegativity Page: 60
Problem 20 ♦ Page: 61
Hybridization Page: 61
Problem 21 ♦ Page: 61
Problem 22 ♦ Page: 61
Problem 23 Page: 61
Problem 24 Page: 62
Size Page: 62
Problem 25 ♦ Page: 63
Problem 26 ♦ Page: 63
Problem 27 ♦ Page: 63
Problem 28 ♦ Page: 63
Problem 29 ♦ Page: 63
2.7 How Substituents Affect the Strength of an Acid Page: 64
Problem-Solving Strategy Determining Relative Acid Strength Page: 64
Problem 30 ♦ Page: 65
Problem 31 ♦ Page: 65
Problem 32 ♦ Page: 65
Problem 33 Solved Page: 65
Solution Page: 65
2.8 An Introduction to Delocalized Electrons Page: 66
Inductive Electron Withdrawal Page: 66
Delocalized Electrons Page: 66
Problem-Solving Strategy Determining the Site of Protonation in a Compound with Delocalized Electrons Page: 67
Problem 34 Page: 68
Problem 35 ♦ Page: 68
Problem 36 ♦ Page: 68
Problem 37 Page: 68
2.9 A Summary of the Factors that Determine Acid Strength Page: 69
Problem 38 ♦ Page: 70
2.10 How pH Affects the Structure of an Organic Compound Page: 70
Problem-Solving Strategy Determining the Structure at a Particular pH Page: 70
Problem 39 ♦ Page: 71
Problem 40 ♦ Page: 71
Problem 41 Solved Page: 71
Solution Page: 71
Problem 42 ♦ Page: 71
Problem 43 Page: 71
Problem 44 Solved Page: 72
Solution 44 a. Page: 73
Solution 44 b. Page: 73
Problem 45 ♦ Page: 73
Problem 46 ♦ Page: 73
Problem 47 Solved Page: 73
Solution Page: 74
Problem 48 ♦ Page: 74
2.11 Buffer Solutions Page: 74
Problem 49 ♦ Page: 75
Problem 50 Solved Page: 75
Solution Page: 75
2.12 Lewis Acids and Bases Page: 76
Problem 51 Page: 76
Problem 52 Page: 76
Essential concepts Page: 77
Problems Page: 77
3 An Introduction to Organic Compounds Nomenclature, Physical Properties, and Structure Page: 88
3.1 Alkyl Groups Page: 92
Problem 3 ♦ Page: 92
3.2 The Nomenclature of Alkanes Page: 95
Problem 9 ♦ Page: 98
Problem 10 Solved Page: 98
Solution Page: 99
Problem 11 ♦ Page: 99
Problem 12 Solved Page: 99
Solution to 12 a. Page: 99
Problem 13 Page: 99
Problem 14 ♦ Page: 99
3.3 The Nomenclature of Cycloalkanes Page: 99
Problem 15 ♦ Page: 100
Problem-Solving Strategy Interpreting a Skeletal Structure Page: 100
Problem 16 Page: 101
Problem 17 ♦ Page: 101
Problem 18 Page: 101
Problem 19 Page: 101
3.4 The Nomenclature of Alkyl Halides Page: 101
3.5 The Nomenclature of Ethers Page: 103
3.6 The Nomenclature of Alcohols Page: 104
Common Names Page: 104
Systematic Names Page: 104
Problem 23 ♦ Page: 105
Problem 24 Page: 106
Problem 25 ♦ Page: 106
Problem 26 ♦ Page: 106
3.7 The Nomenclature of Amines Page: 106
3.8 The Structures of Alkyl Halides, Alcohols, Ethers, and Amines Page: 109
3.9 Noncovalent Interactions Page: 110
Boiling Points Page: 110
London Dispersion Forces Page: 111
Problem 32 ♦ Page: 111
Dipole–Dipole Interactions Page: 111
Hydrogen Bonds Page: 112
Problem-Solving Strategy Predicting Hydrogen Bonding Page: 114
Problem 33 ♦ Page: 114
Problem 34 Page: 114
Problem 35 ♦ Page: 114
Problem 36 Page: 114
Melting Points Page: 115
3.10  The Solubility of Organic Compounds Page: 116
3.11 Rotation Occurs about Carbon–Carbon Single Bonds Page: 118
3.12 Some Cycloalkanes Have Angle Strain Page: 122
Problem 43 ♦ Page: 122
Problem-Solving Strategy Calculating the Strain Energy of a Cycloalkane Page: 123
Problem 44 Page: 124
3.13 Conformers of Cyclohexane Page: 124
3.14 Conformers of Monosubstituted Cyclohexanes Page: 127
Problem 46 ♦ Page: 129
Problem 47 ♦ Page: 129
3.15 Conformers of Disubstituted Cyclohexanes Page: 129
Geometric Isomers Page: 129
Problem-Solving Strategy Differentiating Cis–Trans Isomers Page: 130
Problem 48 ♦ Page: 130
3.16 Fused Cyclohexane Rings Page: 134
Essential Concepts Page: 135
Problems Page: 136
Part Two Electrophilic Addition Reactions, Stereochemistry, and Electron Delocalization Page: 141
4 Isomers: The Arrangement of Atoms in Space Page: 143
4.1 Cis–Trans Isomers Result from Restricted Rotation Page: 145
4.2 Using the E,Z System to Distinguish Isomers Page: 147
4.3 A Chiral Object Has a Nonsuperimposable Mirror Image Page: 150
Problem 13 ♦ Page: 151
4.4 An Asymmetric Center is a Cause of Chirality in a Molecule Page: 151
Problem 14 ♦ Page: 151
4.5 Isomers with One Asymmetric Center Page: 152
Problem 16 ♦ Page: 152
4.6 Asymmetric Centers and Stereocenters Page: 153
Problem 17 ♦ Page: 153
4.7 How to Draw Enantiomers Page: 153
Problem 18 Page: 154
Problem 19 Solved Page: 154
Solution Page: 154
4.8 Naming Enantiomers by the R,S System Page: 154
4.9 Chiral Compounds Are Optically Active Page: 159
Problem 28 ♦ Page: 160
Problem 29 Solved Page: 160
Solution Page: 160
Problem 30 ♦ Page: 161
Problem 31 Solved Page: 161
Solution Page: 161
Problem 32 ♦ Page: 161
4.10 How Specific Rotation Is Measured Page: 161
Problem 33 ♦ Page: 162
Problem 34 ♦ Page: 163
4.11 Enantiomeric Excess Page: 163
Problem 35 ♦ Page: 164
Problem 36 ♦ Page: 164
Problem 37 Solved Page: 164
Solution Page: 164
4.12 Compounds with More than One Asymmetric Center Page: 164
4.13 Stereoisomers of Cyclic Compounds Page: 166
Problem 42 Page: 166
Problem 43 ♦ Page: 167
Problem 44 Page: 167
Problem 45 Page: 168
Problem 46 ♦ Page: 168
Problem-Solving Strategy Page: 168
Problem 47 Page: 168
Problem 48 ♦ Page: 168
4.14 Meso Compounds Have Asymmetric Centers but Are Optically Inactive Page: 169
Problem-Solving Strategy Page: 171
Problem 49 ♦ Page: 171
Problem 50 Solved Page: 172
Solution Page: 172
Problem 51 Page: 172
4.15 How to Name Isomers with More than One Asymmetric Center Page: 172
4.16 Nitrogen and Phosphorus Atoms Can Be Asymmetric Centers Page: 177
Problem 63 Page: 178
4.17 Receptors Page: 178
Problem 64 ♦ Page: 178
4.18 How Enantiomers Can Be Separated Page: 179
Essential Concepts Page: 181
Problems Page: 181
5 Alkenes Structure, Nomenclature, and an Introduction to Reactivity Thermodynamics and Kinetics Page: 190
5.1 Molecular Formulas and the Degree of Unsaturation Page: 191
Problem 1 SOLVED Page: 191
Solution Page: 191
Problem 2 ♦ Page: 191
Problem 3 SOLVED Page: 192
Solution Page: 192
Problem 4 ♦ Page: 192
Problem 5 Page: 192
Problem 6 ♦ Page: 192
5.2 The Nomenclature of Alkenes Page: 192
Problem 7 ♦ Page: 194
Problem 8 ♦ Page: 195
Problem 9 ♦ Page: 195
5.3 The Structure of Alkenes Page: 195
Problem 10 SOLVED Page: 196
Solution Page: 196
Problem 11 ♦ Page: 196
Problem-Solving Strategy Page: 196
Problem 12 Page: 196
5.4 How An Organic Compound Reacts Depends on Its Functional Group Page: 197
5.5 How Alkenes React • Curved Arrows Show the Flow of Electrons Page: 198
Electrophiles Page: 198
Nucleophiles Page: 198
Problem 13 ♦ Page: 198
Problem 14 Page: 198
The Mechanism of a Reaction Page: 199
Problem 15 SOLVED Page: 200
Solution to 15 a.  Page: 201
Problem 16 Page: 201
Problem 17 Page: 201
A Reaction Coordinate Diagram Describes the Reaction Pathway Page: 201
5.6 Thermodynamics: How Much Product is Formed? Page: 202
Gibbs Free-Energy Change Page: 203
Problem 18 ♦ Page: 203
Problem 19 SOLVED Page: 204
Solution Page: 204
Problem 20 Page: 204
Enthalpy and Entropy Page: 204
Problem 21 Page: 205
Problem 22 ♦ Page: 205
5.7 Increasing the Amount of Product Formed in a Reaction Page: 205
5.8 Calculating ΔH° Values Page: 206
Problem 23 ♦ Page: 207
5.9 Using ΔH° Values to Determine the Relative Stabilities of Alkenes Page: 207
Catalytic Hydrogenation Page: 207
Problem-Solving Strategy Page: 208
Problem 24 Page: 208
Problem 25 Page: 208
Relative Stabilities of Alkenes Page: 208
Problem 26 ♦ Page: 210
Problem 27 ♦ Page: 210
Problem 28 ♦ Page: 211
5.10 Kinetics: How Fast is the Product Formed? Page: 211
Problem 29 ♦ Page: 212
Problem 30 Page: 212
5.11 The Rate of a Chemical Reaction Page: 213
The Difference Between the Rate of a Reaction and the Rate Constant for a Reaction Page: 213
The Arrhenius Equation Page: 214
Problem 31 SOLVED Page: 214
Solution to 31 a.  Page: 214
Problem 32 ♦ Page: 214
Problem 33 ♦ Page: 215
How Are Rate Constants Related to the Equilibrium Constant? Page: 215
Problem 34 ♦ Page: 215
5.12 A Reaction Coordinate Diagram Describes the Energy Changes That Take Place During a Reaction Page: 215
Reaction Coordinate Diagram Page: 216
Transition States and Intermediates Page: 216
The Rate-Determining Step Page: 217
Problem 35 Page: 217
Problem 36 ♦ Page: 217
Problem 37 ♦ Page: 217
5.13 Catalysis Page: 218
Problem 38 ♦ Page: 218
5.14 Catalysis by Enzymes Page: 219
Essential Concepts Page: 220
Problems Page: 221
6 The Reactions of Alkenes • The Stereochemistry of Addition Reactions Page: 235
6.1 The Addition of a Hydrogen Halide to an Alkene Page: 236
Problem 1 Page: 237
6.2 Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon Page: 237
6.3 What Does the Structure of the Transition State Look Like? Page: 239
Problem 5 ♦ Page: 241
6.4 Electrophilic Addition Reactions Are Regioselective Page: 241
6.5 The Addition of Water to an Alkene Page: 245
Problem 9 ♦ Page: 246
Problem 10 ♦ Page: 246
Problem 11 ♦ Page: 246
6.6 The Addition of an Alcohol to an Alkene Page: 246
Problem 12 Page: 246
Problem 13 Solved Page: 246
Solution Page: 247
Problem 14 Page: 247
Problem 15 Page: 247
6.7 A Carbocation Will Rearrange if It Can Form a More Stable Carbocation Page: 248
6.8 The Addition of Borane to an Alkene: Hydroboration–Oxidation Page: 250
6.9 The Addition of a Halogen to an Alkene Page: 254
Problem 20 ♦ Page: 254
Problem 21 Page: 255
6.10 The Addition of a Peroxyacid to an Alkene Page: 257
Nomenclature of Epoxides Page: 258
Problem 27 ♦ Page: 258
Problem 28 ♦ Page: 259
Problem 29 Solved Page: 259
Solution to 29 a. Page: 259
Solution to 29 b. Page: 259
6.11 The Addition of Ozone to an Alkene: Ozonolysis Page: 259
Problem-Solving Strategy Page: 260
Solution to a. Page: 261
Solution to b. Page: 261
Solution to c. Page: 261
Problem 30 Page: 261
Problem 31 ♦ Page: 261
Problem 32 ♦ Page: 262
Problem 33 Solved Page: 262
Solution to 33 a. Page: 262
Solution to 33 b. Page: 262
Problem 34 Page: 262
6.12 Regioselective, Stereoselective, And Stereospecific Reactions Page: 263
Problem 35 ♦ Page: 263
6.13 The Stereochemistry of Electrophilic Addition Reactions Page: 264
The Stereochemistry of Addition Reactions That Form a Product with One Asymmetric Center Page: 264
Problem 36 ♦ Page: 265
Problem 37 Page: 265
Problem 38 Solved Page: 266
Solution Page: 266
The Stereochemistry of Addition Reactions That Form Products with Two Asymmetric Centers Page: 266
Addition Reactions That Form a Carbocation Intermediate Page: 266
Problem 39 Solved Page: 267
The Stereochemistry of Hydrogen Addition Page: 267
Problem 40 Solved Page: 269
Solution 40 a. Page: 269
Solution 40 b. Page: 269
The Stereochemistry of Peroxyacid Addition Page: 269
Problem 41 ♦ Page: 270
The Stereochemistry of Hydroboration–Oxidation Page: 271
Problem 42 ♦ Page: 271
The Stereochemistry of Addition Reactions That Form a Cyclic Bromonium or Chloronium Ion Intermediate Page: 272
Problem 43 Page: 273
Problem 44 Solved Page: 273
Solution Page: 274
A Mnemonic to the Rescue Page: 274
Problem-Solving Strategy Page: 274
Problem 45 Page: 275
Problem 46 Page: 275
Problem 47 Page: 275
Problem 48 Page: 275
Problem 49 Page: 275
Problem 50 ♦ Page: 275
6.14 The Stereochemistry of Enzyme-Catalyzed Reactions Page: 276
Problem 51 ♦ Page: 277
6.15 Enantiomers Can Be Distinguished by Biological Molecules Page: 277
Enzymes Page: 277
6.16 Reactions and Synthesis Page: 278
Problem 52 Solved Page: 279
Solution to 52 a. Page: 279
Solution to 52 b. Page: 279
Problem 53 Page: 279
Problem 54 ♦ Page: 280
Essential Concepts Page: 280
Summary of Reactions Page: 281
Problems Page: 282
7 The Reactions of Alkynes • An Introduction to Multistep Synthesis Page: 288
7.1 The Nomenclature of Alkynes Page: 290
Problem 1 ♦ Page: 291
Problem 2 ♦ Page: 291
Problem 3 ♦ Page: 291
Problem 4 ♦ Page: 291
Problem 5 Page: 291
7.2 How to Name a Compound That Has More than One Functional Group Page: 292
Problem 6 ♦ Page: 293
Problem 7 ♦ Page: 293
7.3 The Structure of Alkynes Page: 293
Problem 8 ♦ Page: 294
7.4 The Physical Properties of Unsaturated Hydrocarbons Page: 294
Problem 9 ♦ Page: 294
Problem 10 ♦ Page: 295
7.5 The Reactivity of Alkynes Page: 295
π-Complex Formation Page: 295
Alkynes Are Less Reactive Than Alkenes Page: 296
Problem 11 Solved Page: 296
Solution Page: 296
7.6 The Addition of Hydrogen Halides and the Addition of Halogens to an Alkyne Page: 296
Addition of a Hydrogen Halide to an Alkyne Page: 296
Addition to a Terminal Alkyne Page: 297
Addition to an Internal Alkyne Page: 298
Addition of a Halogen to an Alkyne Page: 298
Problem 12 ♦ Page: 298
Problem 13 Page: 299
7.7 The Addition of Water to an Alkyne Page: 299
7.8 The Addition of Borane to an Alkyne: Hydroboration–Oxidation Page: 301
Problem 17 Page: 302
Problem 18 ♦ Page: 302
7.9 The Addition of Hydrogen to an Alkyne Page: 302
7.10 A Hydrogen Bonded to an sp Carbon Is “Acidic” Page: 304
Problem 21 Page: 305
Problem 22 ♦ Page: 305
Problem 23 ♦ Page: 305
Problem-Solving Strategy Page: 305
Problem 24 ♦ Page: 306
Problem 25 Solved Page: 306
Solution Page: 306
Problem 26 ♦ Page: 306
7.11 Synthesis Using Acetylide Ions Page: 306
Problem 27 Solved Page: 307
Solution Page: 307
  7.12 An Introduction to Multistep Synthesis Page: 307
Factors That Affect the Design of a Synthesis Page: 307
Designing a Synthesis Page: 307
Problem 28 Page: 311
Essential Concepts Page: 312
Summary of Reactions Page: 313
Problems Page: 314
8 Delocalized Electrons Their Effect on Stability, pKa, and the Products of a ReactionAromaticity and Electronic EffectsAn Introduction to the Reactions of Benzene Page: 318
8.1 Delocalized Electrons Explain Benzene’s Structure Page: 319
The Puzzle of Benzene’s Structure Page: 319
Kekulé, Sabatier, and X-ray Diffraction Solve the Puzzle Page: 320
Problem 1 ♦ Page: 320
Problem 2 Page: 321
8.2 The Bonding in Benzene Page: 321
8.3 Resonance Contributors and the Resonance Hybrid Page: 322
The Difference Between a Resonance Contributor and a Resonance Hybrid Page: 323
8.4 How to Draw Resonance Contributors Page: 323
Rules for Drawing Resonance Contributors Page: 324
Example 1 Page: 324
Example 2 Page: 325
Example 3 Page: 325
Example 4 Page: 325
Problem 3 Page: 325
8.5 The Predicted Stabilities of Resonance Contributors Page: 326
Features That Decrease the Predicted Stability Page: 328
Problem-Solving Strategy Page: 328
Problem 4 ♦ Page: 328
Problem 5 SOLVED Page: 329
Solution  Page: 329
Problem 6 Page: 329
8.6 Delocalization Energy is the Additional Stability Delocalized Electrons Give to a Compound Page: 329
Problem 7 ♦ Page: 330
Problem 8 Page: 330
Problem 9 Page: 330
Problem 10 ♦ Page: 330
8.7 Delocalized Electrons Increase Stability Page: 330
Stability of Dienes Page: 330
Conjugated Dienes Page: 331
Allenes Page: 331
Problem 11 ♦ Page: 333
Problem 12 ♦ Page: 334
Stability of Allylic and Benzylic Cations Page: 334
Problem 13 ♦ Page: 335
 8.8 A Molecular Orbital Description of Stability Page: 335
Ethene Page: 335
1,3-Butadiene Page: 336
Problem 14 ♦ Page: 338
Problem 15 ♦ Page: 338
1,4-Pentadiene Page: 338
Problem 16 ♦ Page: 339
8.9 Delocalized Electrons Affect pKa Values Page: 339
Acetic Acid versus Ethanol Page: 339
Phenol versus Cyclohexanol Page: 340
Aniline versus Cyclohexylamine Page: 341
Problem-Solving Strategy Page: 341
Problem 17 ♦ Page: 342
Problem 18 ♦ Page: 342
Problem 19 ♦ Page: 342
8.10 Electronic Effects Page: 342
Inductive Electron Withdrawal Page: 343
Electron Donation by Hyperconjugation Page: 343
Electron Donation by Resonance Page: 343
Electron Withdrawal by Resonance Page: 343
Effect of Electron Donation and Electron Withdrawal on pKa Values Page: 344
Problem 20 ♦ Page: 344
Problem 21 ♦ Page: 345
Problem 22 SOLVED Page: 345
Problem 23 Page: 345
8.11      Delocalized Electrons Can Affect the Product of a Reaction Page: 346
Problem 24 ♦ Page: 346
Problem 25 SOLVED Page: 346
Solution  Page: 346
Problem 26 Page: 346
8.12 Reactions of Dienes Page: 347
Reactions of Isolated Dienes Page: 347
Problem 27 ♦ Page: 347
Reactions of Conjugated Dienes Page: 348
Problem 28 ♦ Page: 349
Problem 29 ♦ Page: 349
Problem 30 Page: 349
Problem 31 Page: 350
Problem 32 ♦ Page: 350
8.13     Thermodynamic Versus Kinetic Control Page: 350
Kinetic and Thermodynamic Products Page: 350
Mild Conditions Favor the Kinetic Product Page: 350
Vigorous Conditions Favor the Thermodynamic Product Page: 351
Reaction Coordinate Diagrams Explain the Temperature Dependence of the Products Page: 351
The Temperature at Which a Reaction Changes from Irreversible to Reversible Depends on the Reaction Page: 352
When 1,3-Butadiene Reacts with HBr, Why Is the 1,4-Addition Product the Thermodynamic Product? Page: 352
Why Is the 1,2-Addition Product Always the Kinetic Product? Page: 352
Problem 33 ♦ Page: 353
Problem 34 ♦ Page: 353
Identifying the Kinetic and Thermodynamic Products Page: 354
Problem 35 ♦ Page: 354
Problem 36 SOLVED Page: 354
Solution Page: 354
Problem 37 Page: 354
Problem 38 Page: 355
8.14 The Diels–Alder Reaction is a 1,4-Addition Reaction Page: 355
An Electron Withdrawing Group Increases the Reactivity of the Dienophile Page: 356
Examples of Diels–Alder Reactions Page: 356
Problem 39 ♦ Page: 356
A Molecular Orbital Description of the Diels–Alder Reaction Page: 357
Predicting the Product When Both Reagents Are Unsymmetrically Substituted Page: 357
Problem 40 ♦ Page: 358
Problem 41 Page: 358
Problem 42 ♦ Page: 358
Conformation of the Diene Page: 359
Exo and Endo Products Page: 359
Problem 43 ♦ Page: 360
Problem 44 Page: 360
Problem 45 SOLVED Page: 360
Solution Page: 360
The Stereochemistry of the Diels–Alder Reaction Page: 361
Problem 46 ♦ Page: 361
8.15 Retrosynthetic Analysis of the Diels–Alder Reaction Page: 361
Problem 47 ♦ Page: 362
8.16   Benzene is an Aromatic Compound Page: 362
8.17 The Two Criteria for Aromaticity Page: 363
Problem 48 ♦ Page: 364
Problem 49 ♦ Page: 364
8.18    Applying the Criteria for Aromaticity Page: 364
Problem 50 ♦ Page: 365
Problem 51 SOLVED Page: 365
Solution Page: 366
Problem 52 ♦ Page: 366
Problem 53 ♦ Page: 366
Problem-Solving Strategy Page: 366
Problem 54 Page: 366
8.19 A Molecular Orbital Description of Aromaticity Page: 367
Antiaromatic Compounds Page: 367
Problem 55 Page: 367
8.20    Aromatic Heterocyclic Compounds Page: 368
Pyridine Page: 368
Pyrrole, Furan, and Thiophene Page: 368
Problem 56 ♦ Page: 368
Problem 57 ♦ Page: 369
Problem 58 SOLVED Page: 369
Solution Page: 369
Problem 59 Page: 369
Problem 60 Page: 370
8.21 How Benzene Reacts Page: 370
8.22 Organizing What We Know about the Reactions of Organic Compounds Page: 372
Essential Concepts Page: 373
Section 8.0 Page: 373
Section 8.2 Page: 373
Section 8.3 Page: 373
Section 8.4 Page: 373
Section 8.5 Page: 373
Section 8.6 Page: 373
Section 8.7 Page: 373
Section 8.8 Page: 373
Section 8.9 Page: 374
Section 8.10 Page: 374
Section 8.12 Page: 374
Section 8.13 Page: 374
Section 8.14 Page: 374
Section 8.15 Page: 374
Section 8.19 Page: 374
Section 8.20 Page: 374
Section 8.21 Page: 374
Summary of Reactions Page: 374
Problems Page: 375
Rules for Drawing Resonance Contributors Page: 382
π Electrons Move Toward an sp2 Carbon That Is a Positively Charged Carbon Page: 382
Problem 1 Page: 382
Problem 2 Page: 383
π Electrons Move Toward an sp2 Carbon That Is a Doubly Bonded Carbon Page: 383
Problem 3 Page: 383
Problem 4 Page: 383
A Lone Pair Moves Toward an sp2 Carbon That Is a Doubly Bonded Carbon Page: 383
Problem 5 Page: 384
Problem 6 Page: 384
Problem 7 Page: 385
Problem 8 Page: 385
Problem 9 Page: 385
Problem 10 Page: 386
Problem 11 Page: 386
Problem 12 Page: 386
ANSWERS TO PROBLEMS ON DRAWING RESONANCE CONTRIBUTORS Page: 386
PARTTHREE Substitution and Elimination Reactions Page: 390
9 Substitution and Elimination Reactions of Alkyl Halides Page: 391
9.1 The SN2 Reaction Page: 393
Experimental Evidence for the Mechanism for an SN2 Reaction Page: 393
Problem 3 ♦ Page: 393
The Mechanism for an SN2 Reaction Page: 394
How the Mechanism Accounts for the Experimental Evidence Page: 395
Problem 4 ♦ Page: 397
Problem 5 ♦ Page: 398
Problem 6 ♦ SOLVED Page: 398
Solution to 6 a. Page: 398
Problem 7 SOLVED Page: 398
Solution Page: 398
Problem 8 Page: 398
9.2 Factors that Affect SN2 Reactions Page: 398
The Leaving Group in an SN2 Reaction Page: 398
Problem 9 ♦ Page: 399
The Nucleophile in an SN2 Reaction Page: 399
Effect of Basicity on Nucleophilicity Page: 400
Effect of Solvent on Nucleophilicity Page: 401
Problem 10 ♦ Page: 401
Why Is the Nucleophilicity Affected by the Solvent? Page: 402
Problem 11 ♦ Page: 402
Problem 12 ♦ Page: 402
Nucleophilicity Is Affected by Steric Effects Page: 403
Problem 13 SOLVED Page: 403
Solution Page: 403
Problem 14 ♦ Page: 403
A Wide Variety of Compounds Can Be Synthesized by SN2 Reactions Page: 403
Problem 15 ♦ Page: 404
Problem 16 SOLVED Page: 404
Solution Page: 404
Problem 17 Page: 405
9.3 The SN1 Reaction Page: 406
Experimental Evidence for the Mechanism for an SN1 Reaction Page: 406
The Mechanism for an SN1 Reaction Page: 406
How the Mechanism Accounts for the Experimental Evidence Page: 407
Most SN1 Reactions Lead to Partial Racemization Page: 408
Problem 18 ♦ Page: 409
9.4 Factors that Affect SN1 Reactions Page: 409
The Leaving Group in an SN1 Reaction Page: 409
The Nucleophile in an SN1 Reaction Page: 409
Problem 19 ♦ Page: 410
9.5 Competition Between SN2 and SN1 Reactions Page: 410
Problem-Solving Strategy Page: 411
Problem 20 Page: 411
Problem 21 ♦ Page: 411
9.6 Elimination Reactions of Alkyl Halides Page: 412
9.7 The E2 Reaction Page: 413
An E2 Reaction is Regioselective Page: 413
Alkyl Chlorides, Alkyl Bromides, and Alkyl Iodides Preferentially Form the More Stable Product Page: 414
Zaitsev’s Rule Page: 414
Problem 22 ♦ Page: 415
Limitations of Zaitsev’s Rule Page: 415
Alkyl Fluorides Preferentially Form the Less Stable Alkene Page: 416
Carbocation and Carbanion Stability Page: 417
Summary of the Regioselectivity of E2 Reactions Page: 418
Problem 23 ♦ Page: 418
Relative Reactivities in an E2 Reaction Page: 418
Problem 24 ♦ Page: 418
Problem 25 ♦ Page: 419
9.8 The E1 Reaction Page: 419
The E1 Reaction Is Regioselective Page: 420
The Leaving Group in E2 and E1 Reactions Page: 420
Problem 26 ♦ Page: 421
Problem 27 ♦ Page: 421
Problem 28 ♦ Page: 421
Problem-Solving Strategy Proposing a Mechanism Page: 421
Problem 29 Page: 421
9.9 Competition Between E2 and E1 Reactions Page: 422
Problem 30 Page: 422
Problem 31 SOLVED Page: 422
Solution Page: 422
Problem 32 Page: 422
9.10 E2 and E1 Reactions are Stereoselective Page: 423
The Stereoisomers Formed in an E2 Reaction Page: 423
Syn and Anti Elimination Page: 423
A Reactant with Two Hydrogens on the β-Carbon-Carbon Page: 423
A Reactant with One Hydrogen on the β-Carbon Page: 424
Problem-Solving Strategy Determining the Major Product of an E2 Reaction Page: 425
Problem 33 ♦ Page: 425
The Stereoisomers Formed in an E1 Reaction Page: 425
Problem 34 SOLVED Page: 426
Solution Page: 426
Problem 35 Page: 426
9.11 Elimination from Substituted Cyclohexanes Page: 427
E2 Reactions of Substituted Cyclohexanes Page: 427
Problem 36 ♦ Page: 428
Problem 37 ♦ Page: 428
E1 Reactions of Substituted Cyclohexanes Page: 428
Problem 38 Page: 428
9.12 Predicting the Products of the Reaction of an Alkyl Halide with a Nucleophile/Base Page: 429
SN2/E2 Reactions of Primary Alkyl Halides Page: 429
Steric Hindrance Favors the Elimination Product Page: 430
SN2/E2 Reactions of Secondary Alkyl Halides Page: 430
A Strong Base Favors the Elimination Product Page: 430
A Bulky Base Favors the Elimination Product Page: 430
A High Temperature Favors the Elimination Product Page: 431
E2 Reaction of a Tertiary Alkyl Halide Page: 431
SN1/E1 Reactions of Tertiary Alkyl Halides Page: 431
Problem 39 ♦ Page: 432
Problem 40 Page: 432
Problem 41 ♦ Page: 432
Problem 42 ♦ Page: 432
Problem 43 ♦ Page: 432
9.13 Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides Page: 433
Benzylic and Allylic Halides Page: 433
Substitution Reactions Page: 433
Problem-Solving Strategy Predicting Relative Reactivities Page: 434
Problem 44 Page: 434
Problem 45 ♦ Page: 435
Problem 46 ♦ Page: 435
Problem 47 Page: 435
Vinylic and Aryl Halides Page: 435
Substitution Reactions Page: 436
Problem 48 ♦ Page: 436
Problem 49 ♦ Page: 436
Problem 50 Page: 436
Problem 51 SOLVED Page: 436
Solution Page: 437
Problem 52 Page: 437
Problem-Solving Strategy Predicting Whether SN2/E2 or SN1/E1 Reactions Occur Page: 437
Solution to a. Page: 437
Solution to b. Page: 437
Problem 53 Page: 437
9.14 Solvent Effects Page: 438
How a Solvent Affects Reaction Rates in General Page: 438
How a Solvent Affects the Rate of an SN1 or E1 Reaction of an Alkyl Halide Page: 439
How a Solvent Affects the Rate of an SN2 or E2 Reaction of an Alkyl Halide Page: 440
Problem 54 ♦ Page: 441
Problem 55 ♦ Page: 441
Problem 56 ♦ Page: 441
Problem 57 SOLVED Page: 442
Solution Page: 442
Problem 58 ♦ Page: 442
Problem 59 ♦ Page: 442
9.15 Substitution and Elimination Reactions in Synthesis Page: 442
Using Substitution Reactions to Synthesize Compounds Page: 442
Problem 60 ♦ Page: 443
Problem 61 Page: 443
Using Elimination Reactions to Synthesize Alkenes Page: 443
Problem 62 ♦ Page: 444
Problem 63 Page: 444
9.16 Intermolecular Versus Intramolecular Reactions Page: 444
How to Determine Whether the Intermolecular or Intramolecular Reaction Predominates Page: 445
Problem 64 ♦ Page: 445
Problem-Solving Strategy Investigating How Stereochemistry Affects Reactivity Page: 446
Problem 65 Page: 446
Designing a Synthesis II 9.17 Approaching the Problem Page: 446
Problem 66 Page: 448
Essential Concepts Page: 449
Summary of Reactions Page: 450
Problems Page: 451
10 Reactions of Alcohols, Ethers, Epoxides, Amines, and Sulfur-Containing Compounds Page: 458
10.1 Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides Page: 459
Converting an OH Group into a Better Leaving Group Page: 459
Problem 1 ♦ Page: 459
The SN1 Reaction of Secondary and Tertiary Alcohols Page: 460
The SN2 Reaction of Primary Alcohols Page: 460
Problem 2 Solved Page: 461
Solution Page: 461
Problem 3 Page: 461
Problem 4 Solved Page: 462
Solution Page: 462
Problem 5 Page: 462
Problem 6 ♦ Page: 462
Problem 7 Solved Page: 462
Solution Page: 463
Problem 8 ♦ Page: 463
10.2 Other Methods Used to Convert Alcohols into Alkyl Halides Page: 463
10.3 Converting an Alcohol Into a Sulfonate Ester Page: 465
Forming a Sulfonate Ester Page: 465
Sulfonate Esters in Substitution Reactions Page: 466
Problem 10 Solved Page: 466
Solution Page: 467
Problem 11 Page: 467
Problem 12 Page: 468
10.4 Elimination Reactions of Alcohols: Dehydration Page: 468
The E1 Dehydration of Secondary and Tertiary Alcohols Page: 468
Problem 13 ♦ Page: 469
The E2 Dehydration of Primary Alcohols Page: 470
Problem 14 Page: 471
Problem 15 Page: 471
Problem-Solving Strategy Proposing a Mechanism Page: 471
Problem 16 Page: 472
Problem 17 Page: 472
Problem 18 Page: 472
The Stereochemistry of the Dehydration Reaction Page: 472
Problem 19 ♦ Page: 472
Problem 20 ♦ Page: 472
Changing an E1 Dehydration into an E2 Dehydration Page: 472
Problem 21 ♦ Page: 473
10.5   Oxidation of Alcohols Page: 474
Chromium-Based Oxidizing Agents Page: 474
Hypochlorous Acid as the Oxidizing Reagent Page: 474
The Swern Oxidation Page: 475
Problem 22 ♦ Page: 476
10.6 Nucleophilic Substitution Reactions of Ethers Page: 477
10.7 Nucleophilic Substitution Reactions of Epoxides Page: 480
Nucleophilic Substitution: Acidic Conditions Page: 480
Nucleophilic Substitution: Neutral or Basic Conditions Page: 482
Problem 27 ♦ Page: 482
Problem 28 ♦ Page: 483
Converting an Alkene to an Alcohol Without a Carbocation Rearrangement Page: 483
Problem 29 Page: 483
Trans and Cis Diols Page: 483
Problem 30 Page: 483
Problem 31 ♦ Page: 484
Problem 32 Page: 484
Problem 33 Page: 484
10.8 Arene Oxides Page: 485
Arene Oxides Can Be Carcinogens Page: 487
Carcinogenicity is Determined by Carbocation Stability Page: 488
Problem 38 Solved Page: 488
Solution Page: 489
Problem 39 Page: 489
Problem 40 ♦ Page: 489
Problem 41 Page: 489
10.9 Amines Do Not Undergo Substitution or Elimination Reactions Page: 490
Amines React as Bases and Nucleophiles Page: 490
Problem 42 Page: 491
10.10 Quaternary Ammonium Hydroxides Undergo Elimination Reactions Page: 492
The Reason for anti-Zaitsev Elimination Page: 493
Problem 47 ♦ Page: 493
Problem 48 Solved Page: 494
Solution Page: 494
Problem 49 Page: 494
10.11 Thiols, Sulfides, and Sulfonium Ions Page: 495
Thiols Page: 495
Sulfides Page: 495
Sulfonium Ions Page: 495
Problem 50 Page: 495
Problem 51 ♦ Page: 495
Problem 52 ♦ Page: 496
Problem 53 Page: 496
10.12 Methylating Agents Used by Chemists versus Those Used by Cells Page: 496
Methyl Halides Are the Methylating Agents Used by Chemists Page: 496
S-Adenosylmethionine Is a Methylating Agent Used by Cells Page: 497
Examples of Biological Methylation Reactions Page: 497
Problem 54 Page: 498
10.13 Organizing what we know about the Reactions of Organic Compounds Page: 499
Essential Concepts Page: 500
Summary of Reactions Page: 501
Problems Page: 503
11 Organometallic Compounds Page: 508
11.1 Organolithium and Organomagnesium Compounds Page: 509
Preparing Organolithium and Organomagnesium Compounds Page: 509
Organolithium and Organomagnesium Compounds Are Nucleophiles Page: 510
Problem 1 ♦ Page: 511
11.2 Transmetallation Page: 511
Problem 2 ♦ Page: 511
Problem 3 ♦ Page: 511
11.3 Organocuprates Page: 512
Forming Organocuprates Page: 512
An Organocuprate Replaces Cl, Br, or I with an Alkyl Group Page: 512
Problem 4 Solved Page: 513
Solution Page: 513
Problem 5 Page: 513
Problem 6 Solved Page: 513
Solution Page: 513
Problem 7 Page: 514
An Organocuprate Is a Nucleophile Page: 514
Problem 8 ♦ Page: 514
Problem 9 Page: 514
Problem 10 Page: 514
Problem 11 Solved Page: 514
Solution Page: 514
11.4  Palladium-Catalyzed Coupling Reactions Page: 515
The Suzuki Reaction Page: 516
Examples of Suzuki Reactions Page: 516
Mechanism for the Suzuki Reaction Page: 516
Preparing the Organoboron Compound for a Suzuki Reaction Page: 517
Problem 12 Solved Page: 518
Solution to 12 a.  Page: 518
Problem 13 Page: 518
Problem 14 ♦ Page: 518
Problem 15 ♦ Page: 518
Problem 16 Page: 519
The Heck Reaction Page: 519
Examples of Heck Reactions Page: 519
Mechanism for the Heck Reaction Page: 519
Problem-Solving Strategy Page: 521
Problem 17 ♦ Page: 521
Problem 18 Solved Page: 521
Solution to 18 a.  Page: 522
Solution to 18 b.  Page: 522
Problem 19 Page: 522
Problem 20 Page: 522
Problem 21 ♦ Page: 522
11.5 Alkene Metathesis Page: 522
A Catalyst Used for Alkene Metathesis Page: 523
Examples of Alkene Metathesis Page: 523
Mechanism for Alkene Metathesis Page: 523
Problem 22 Page: 525
Problem 23 Page: 525
Problem 24 Solved Page: 525
Solution to 24 a.  Page: 525
Problem 25 Page: 525
Alkyne Metathesis Page: 525
Problem 26 ♦ Page: 525
Essential Concepts Page: 527
Section 11.0 Page: 527
Section 11.1 Page: 527
Section 11.2 Page: 527
Section 11.3 Page: 527
Section 11.4 Page: 527
Section 11.5 Page: 527
Summary of Reactions Page: 527
Problems Page: 528
12 Radicals Page: 532
12.1    Alkanes are Unreactive Compounds Page: 532
12.2 The Chlorination and Bromination of Alkanes Page: 534
Heterolysis and Homolysis Page: 534
Monochlorination of an Alkane Page: 534
Maximizing the Monohalogneated Product Page: 535
Monobromination of an Alkane Page: 535
Problem 1 Page: 535
Problem 2 Page: 536
12.3 Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron Page: 536
Problem 3 ♦ Page: 537
12.4    The Distribution of Products Depends on Probability and Reactivity Page: 537
Problem 4 ♦ Page: 538
Using Radical Halogenation in Synthesis Page: 538
Problem 5 Solved Page: 538
Solution Page: 539
Problem 6 Page: 539
12.5   The Reactivity–Selectivity Principle Page: 539
Problem 7 Solved Page: 539
Solution Page: 540
Problem 8 ♦ Page: 540
Explaining the Difference in Relative Rates Page: 540
The Reactivity-Selectivity Principle Page: 541
Problem-Solving Strategy Page: 541
Problem 9 ♦ Page: 541
Why Alkanes Undergo Only Chlorination and Bromination Page: 542
Problem 10 Solved Page: 542
Solution Page: 542
Problem 11 Page: 542
12.6 Formation of Explosive Peroxides Page: 542
Problem 12 ♦ Page: 542
12.7 The Addition of Radicals to an Alkene Page: 542
Problem 13 Page: 544
Peroxide Affects Only the Addition of HBr Page: 545
Problem 14 ♦ Page: 545
12.8  The Stereochemistry of Radical Substitution and Radical Addition Reactions Page: 546
Why Radical Substitution and Radical Addition Form a Racemic Mixture Page: 546
Problem 15 ♦ Page: 547
Problem 16 Page: 547
12.9   Radical Substitution of Allylic and Benzylic Hydrogens Page: 547
The Stability of Allylic and Benzylic Radicals Page: 547
NBS Is Used to Brominate Allylic Carbons Page: 548
Problem 17 Solved Page: 549
Solution Page: 549
Problem 18 Page: 549
Problem 19 ♦ Page: 549
Problem 20 Page: 549
Problem 21 Page: 549
Problem 22 Page: 549
A Bromine Radical Can Remove an Allylic Hydrogen and It Can Add to a Double Bond Page: 549
Designing a Synthesis III 12.10 More Practice with Multistep Synthesis Page: 550
Problem 23 Page: 552
12.11 Radical Reactions in Biological Systems Page: 552
Converting Nonpolar Compounds to Polar Compounds Page: 552
Oxidation of Fats and Oils Page: 553
Radical Inhibitors Page: 553
Problem 24 ♦ Page: 555
Problem 25 Page: 556
12.12 Radicals and Stratospheric Ozone Page: 556
Essential Concepts Page: 558
Section 12.1 Page: 558
Section 12.2 Page: 558
Section 12.3 Page: 558
Section 12.4 Page: 558
Section 12.5 Page: 558
Section 12.6 Page: 558
Section 12.7 Page: 558
Section 12.8 Page: 558
Section 12.9 Page: 558
Section 12.11 Page: 558
Section 12.12 Page: 558
Summary of Reactions Page: 559
Problems Page: 559
Drawing Curved Arrows in Radical Systems Page: 563
Drawing Curved Arrows in Radical Reactions Page: 563
Problem 1 Page: 563
Problem 2 Page: 563
Problem 3 Page: 564
Drawing Curved Arrows in Contributing Resonance Structures that are Radicals Page: 564
Problem 4 Page: 564
Answers to Problems on Drawing Curved Arrows in Radical Systems Page: 564
Problem 1 Page: 565
Problem 2 Page: 565
Problem 3 Page: 565
Problem 4 Page: 565
PART FOURIdentification of Organic Compounds Page: 566
13 Mass Spectrometry; Infrared Spectroscopy; UV/Vis Spectroscopy Page: 567
13.1 Mass Spectrometry Page: 569
Ionization of the Sample Page: 569
Detecting the Positively-Charged Fragments Page: 569
Output from a Mass Spectrometer Page: 570
Problem 1 ♦ Page: 570
13.2  The Mass Spectrum • Fragmentation Page: 570
Interpreting a Mass Spectrum Page: 570
Identifying Fragments Page: 571
Comparing the Mass Spectra of Pentane and Isopentane Page: 571
Problem 2 Page: 572
Problem 3 ♦ Page: 572
13.3 Using the m/z Value of the Molecular Ion to Calculate the Molecular Formula Page: 572
Problem 4 SOLVED Page: 572
Solution Page: 573
Problem 5 ♦ Page: 573
Problem 6 ♦ Page: 573
Problem 7 Page: 573
Problem-Solving Strategy Page: 573
Problem 8 ♦ Page: 573
13.4 Isotopes in Mass Spectrometry Page: 574
M+1 Peak Page: 574
M+2 Peak Page: 574
Problem 9 ♦ Page: 575
13.5   High-Resolution Mass Spectrometry Can Reveal Molecular Formulas Page: 575
Problem 10 ♦ Page: 575
Problem 11 ♦ Page: 575
13.6 The Fragmentation Patterns of Functional Groups Page: 575
Alkyl Halides Page: 575
Mass Spectrum of 1-Bromopropane Page: 576
Mass Spectrum of 2-Chloropropane Page: 576
Problem 12 Page: 577
Ethers Page: 577
Problem 13 ♦ Page: 578
Alcohols Page: 579
α-Cleavage Page: 579
Loss of Water Page: 580
Common Fragmentation Behavior of Alkyl Halides, Ethers, and Alcohols Page: 580
Problem 14 ♦ Page: 580
Ketones Page: 580
Problem 15 ♦ Page: 581
Problem 16 Page: 581
Problem 17 Page: 582
Problem 18 ♦ Page: 582
13.7 Other Ionization Methods Page: 583
13.8 Gas Chromatography–Mass Spectrometry Page: 583
13.9 Spectroscopy and the Electromagnetic Spectrum Page: 583
Characterizing Electromagnetic Radiation Page: 584
Problem 19 ♦ Page: 585
Problem 20 ♦ Page: 585
13.10 Infrared Spectroscopy Page: 585
Stretching and Bending Vibrations Page: 585
The Infrared Spectrum Page: 586
The Functional Group and Fingerprint Regions Page: 587
13.11 Characteristic Infrared Absorption Bands Page: 588
13.12 The Intensity of Absorption Bands Page: 589
13.13 The Position of Absorption Bands Page: 590
Hooke’s Law Page: 590
The Effect of Bond Order Page: 590
Problem 21 ♦ Page: 590
13.14 The Position and Shape of an Absorption Band is Affected by Electron Delocalization and Hydrogen Bonding Page: 591
Electron Delocalization Page: 591
Problem-Solving Strategy Page: 593
Problem 22 ♦ Page: 593
Problem 23 ♦ Page: 594
Problem 24 ♦ Page: 594
Problem 25 ♦ Page: 594
Hydrogen Bonding Page: 594
Problem 26 ♦ Page: 594
13.15C—H Absorption Bands Page: 595
Stretching Vibrations Page: 595
Bending Vibrations Page: 596
13.16 The Absence of Absorption Bands Page: 598
Problem 27 ♦ Page: 598
Problem 28 ♦ Page: 598
Problem 29 Page: 598
Problem 30 Page: 598
13.17 Some Vibrations are Infrared Inactive Page: 599
Problem 31 ♦ Page: 599
Problem 32 ♦ Page: 599
13.18 How to Interpret an Infrared Spectrum Page: 600
Problem 33 ♦ Page: 601
13.19 Ultraviolet and Visible Spectroscopy Page: 602
UV/Vis Light Causes an Electronic Transition Page: 602
13.20 The Beer–Lambert Law Page: 604
Problem 34 ♦ Page: 604
Problem 35 ♦ Page: 604
13.21 The Effect of Conjugation on λmax Page: 605
Problem 36 ♦ Page: 606
Problem 37 ♦ Page: 606
13.22 The Visible Spectrum and Color Page: 606
13.23 Some Uses of UV/Vis Spectroscopy Page: 607
Problem 38 ♦ Page: 609
Problem 39 ♦ Page: 609
Problem 40 ♦ Page: 609
Essential Concepts Page: 610
Problems Page: 611
14 NMR Spectroscopy Page: 620
14.1    An Introduction to NMR Spectroscopy Page: 620
α- and β-Spin States Page: 620
Flipping the Spin Page: 621
Energy Difference Between Spin States Depends on the Operating Frequency Page: 621
Problem 1 ♦ Page: 622
Problem 2 ♦ Page: 622
14.2    Fourier Transform NMR Page: 623
14.3 Shielding Causes Different Nuclei to Show Signals at Different Frequencies Page: 623
14.4    The Number of Signals in an H1 NMR Spectrum Page: 624
Problem-Solving Strategy Page: 625
Problem 3 Page: 625
Problem 4 ♦ Page: 626
Problem 5 Page: 626
Problem 6 Page: 626
14.5    The Chemical Shift Tells How Far the Signal Is from the Reference Signal Page: 626
The Reference Compound Page: 626
The Chemical Shift Page: 626
δ Is Independent of the Operating Frequency Page: 627
Problem 7 ♦ Page: 627
Problem 8 ♦ Page: 628
Problem 9 ♦ Page: 628
Problem 10 ♦ Page: 628
14.6  The Relative Positions of H1 NMR Signals Page: 628
Problem 11 ♦ Page: 628
14.7     The Characteristic Values of Chemical Shifts Page: 629
Methine, Methylene, and Methyl Protons Page: 629
Problem 12 ♦ Page: 630
Problem 13 ♦ Page: 630
Problem 14 Page: 630
14.8 Diamagnetic Anisotropy Page: 631
Benzene Ring Protons Page: 631
Alkene and Aldehyde Protons Page: 631
Alkyne Proton Page: 632
Problem 15 ♦ Page: 632
14.9  The Integration of NMR Signals Reveals the Relative Number of Protons Causing Each Signal Page: 632
Integration of the Signals Page: 633
Problem 16 ♦ Page: 633
Problem 17 Solved Page: 633
Solution Page: 634
Problem 18 ♦ Page: 634
14.10 The Splitting of Signals is Described by the N+1 Rule Page: 635
The N+1 Rule Page: 635
A Proton Is Not Split By Equivalent Protons Page: 636
Problem 19 ♦ Page: 636
Problem 20 Page: 636
Problem 21 ♦ Page: 637
14.11 What Causes Splitting? Page: 638
Forming a Doublet Page: 638
Forming a Quartet Page: 639
Long-Range Coupling Page: 640
Problem 22 Page: 640
14.12 More Examples of H1 Nmr Spectra Page: 641
Problem 23 Page: 641
A Quartet versus a Doublet of Doublets Page: 643
Example 4 Page: 643
Example 5 Page: 643
Problem 24 Page: 643
Problem 25 Page: 643
Problem 26 ♦ Page: 643
Problem 27 Page: 643
Problem 28 Page: 643
Problem 29 Page: 643
14.13  Coupling Constants Identify Coupled Protons Page: 644
Coupling Constants Distinguish Cis and Trans Isomers Page: 645
Summary Page: 645
Problem 30 ♦ Page: 645
Problem-Solving Strategy Page: 645
Problem 31 ♦ Page: 646
14.14 Splitting Diagrams Explain the Multiplicity of a Signal Page: 647
Splitting Diagram for a Doublet of Doublets Page: 647
Splitting Diagram for a Multiplet Page: 648
When Jab=Jac Page: 648
Summary Page: 649
Problem 32 Page: 649
14.15  Enantiotopic and Diastereotopic Hydrogens Page: 650
Enantiotopic Hydrogens Page: 650
Prochiral Carbons Page: 650
Diastereotopic Hydrogens Page: 650
Problem 33 ♦ Page: 651
Problem 34 Solved Page: 651
Solution Page: 651
Problem 35 Page: 651
Problem 36 Solved Page: 651
Solution Page: 651
14.16  The Time Dependence of NMR Spectroscopy Page: 652
14.17  Protons Bonded to Oxygen and Nitrogen Page: 652
Problem 37 Page: 652
Proton Exchange Page: 653
Problem 38 ♦ Page: 654
Problem 39 Page: 654
Problem 40 ♦ Page: 654
14.18  The Use of Deuterium in H1 NMR Spectroscopy Page: 654
14.19 The Resolution of H1 Nmr Spectra Page: 655
14.20  C13 Nmr Spectroscopy Page: 657
A C13 NMR Spectrum Page: 658
A Proton-Coupled C13 NMR Spectrum Page: 658
Problem 41 Page: 659
Problem 42 Page: 659
Problem 43 Page: 659
Problem-Solving Strategy Page: 660
Problem 44 ♦ Page: 660
14.21 DEPT C13 NMR Spectra Page: 662
14.22 Two-Dimensional NMR Spectroscopy Page: 663
COSY Spectra Page: 663
Analyzing COSY Spectra Page: 663
Problem 45 Page: 664
HETCOR Spectra Page: 664
Analyzing HETCOR Spectra Page: 664
Problem 46 ♦ Page: 665
14.23  NMR Used in Medicine is Called Magnetic Resonance Imaging Page: 665
14.24 X-Ray Crystallography Page: 666
Essential Concepts Page: 668
Problems Page: 669
Part Five Carbonyl Compounds Page: 685
15 Reactions of Carboxylic Acids and Carboxylic Acid Derivatives Page: 686
15.1 The Nomenclature of Carboxylic Acids and Carboxylic Acid Derivatives Page: 688
Naming Carboxylic Acids Page: 688
Naming Acyl Chlorides Page: 689
Naming Esters Page: 689
Problem 1 ♦ Page: 689
Naming Amides Page: 690
Problem 2 ♦ Page: 691
Problem 3 Page: 691
Derivatives of Carbonic Acid Page: 691
15.2 The Structures of Carboxylic Acids and Carboxylic Acid Derivatives Page: 692
Problem 4 ♦ Page: 692
Problem 5 ♦ Page: 692
Problem 6 ♦ Page: 693
15.3 The Physical Properties of Carbonyl Compounds Page: 693
Boiling Points Page: 693
Solubility Page: 693
15.4 How Carboxylic Acids and Carboxylic Acid Derivatives React Page: 694
Formation of a Tetrahedral Intermediate Page: 694
The Weaker Base Is Eliminated from the Tetrahedral Intermediate Page: 694
Comparing Nucleophilic Acyl Substitution with Nucleophilic Substitution Page: 695
Problem-Solving Strategy Page: 696
Problem 7 ♦ Page: 696
Problem 8 ♦ Page: 696
15.5 The Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives Page: 696
A Weak Base Makes the First Step Easier Page: 696
Problem 9 ♦ Page: 697
A Weak Base Makes the Second Step Easier Page: 697
Reaction Coordinate Diagrams for Nucleophilic Acyl Substitution Page: 697
Problem 10 ♦ Page: 698
Problem 11 ♦ Page: 698
15.6    Reactions of Acyl Chlorides Page: 698
Problem 12 Page: 700
Problem 13 Page: 700
Problem 14 SOLVED Page: 700
Solution to 14 a. Page: 700
Solution to 14 b. Page: 700
15.7 Reactions of Esters Page: 701
Problem 15 ♦ Page: 701
Problem 16 Page: 701
Problem 17 Page: 701
Problem 18 SOLVED Page: 702
Solution Page: 702
Problem 19 ♦ Page: 702
Problem 20 ♦ Page: 702
15.8 Acid-Catalyzed Ester Hydrolysis and Transesterification Page: 702
Hydrolysis of an Ester with a Primary or Secondary Alkyl Group Page: 702
Problem 21 ♦ Page: 704
Problem 22 Page: 704
How an Acid Increases the Rate of Ester Hydrolysis Page: 704
Problem 23 ♦ Page: 704
Problem 24 Page: 705
Hydrolysis of an Ester with a Tertiary Alkyl Group Page: 705
Transesterification Page: 705
Problem 25 ♦ Page: 705
Problem 26 Page: 705
Problem 27 Page: 706
15.9 Hydroxide-Ion-Promoted Ester Hydrolysis Page: 706
How Hydroxide Ion Increases the Rate of Ester Hydrolysis Page: 706
Hydroxide Ion Promotes Only Hydrolysis Reactions Page: 707
Problem 28 ♦ Page: 708
Problem 29 ♦ Page: 708
Problem 30 SOLVED Page: 708
Solution Page: 709
15.10 Reactions of Carboxylic Acids Page: 709
A Carboxylic Acid and an Alcohol Undergo a Nucleophilic Acyl Substitution Reaction Page: 709
A Carboxylic Acid and an Amine Undergo an Acid–Base Reaction Page: 710
Problem 31 ♦ Page: 710
Problem-Solving Strategy Page: 710
Problem 32 Page: 710
15.11 Reactions of Amides Page: 711
Problem 33 ♦ Page: 711
Problem 34 ♦ Page: 712
15.12 Acid-Catalyzed Amide Hydrolysis and Alcoholysis Page: 712
Why a Catalyst Is Required for Hydrolysis and Alcoholysis of an Amide Page: 713
Problem 35 Page: 714
Problem 36 ♦ Page: 715
15.13 Hydroxide-Ion-Promoted Hydrolysis of Amides Page: 715
Problem 37 ♦ Page: 716
15.14  Hydrolysis of an Imide: A Way to Synthesize a Primary Amine Page: 716
Problem 38 ♦ Page: 717
Problem 39 Page: 717
15.15 Nitriles Page: 717
Naming Nitriles Page: 717
Problem 40 ♦ Page: 717
Reactions of Nitriles Page: 718
Using Nitriles in Synthesis Page: 718
Problem 41 ♦ Page: 718
Problem 42 SOLVED Page: 719
Solution Page: 719
15.16 Acid Anhydrides Page: 719
Naming Anhydrides Page: 719
Reactions of Anhydrides Page: 719
Problem 43 Page: 720
Problem 44 Page: 721
Problem 45 ♦ Page: 721
15.17 Dicarboxylic Acids Page: 721
pKa Values Page: 721
Dehydration Page: 722
Problem 46 Page: 723
15.18  How Chemists Activate Carboxylic Acids Page: 723
Activating Carboxylic Acids in the Lab Page: 723
Problem 47 ♦ Page: 724
15.19 How Cells Activate Carboxylic Acids Page: 724
Cells Use ATP to Activate Carboxylic Acids Page: 724
Forming an Acyl Phosphate Page: 725
Forming an Acyl Adenylate Page: 725
Reaction with ATP Occurs at the Active Site of an Enzyme Page: 725
Activating a Carboxylic Acid by Converting It to a Thioester Page: 726
Why Thioesters Are More Reactive Than Esters Page: 726
Coenzyme A Is the Thiol Used by Cells Page: 726
Essential Concepts Page: 728
Summary of Reactions Page: 729
Problems Page: 731
16 Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid Derivatives Page: 739
16.1 The Nomenclature of Aldehydes and Ketones Page: 740
Naming Aldehydes Page: 740
Naming Ketones Page: 741
Problem 1 ♦ Page: 742
Problem 2 ♦ Page: 742
Naming Compounds with Two Functional Groups Page: 742
Problem 3 Page: 743
16.2 The Relative Reactivities of Carbonyl Compounds Page: 743
Problem 4 ♦ Page: 744
16.3 How Aldehydes and Ketones React Page: 744
Nucleophilic Acyl Substitution Page: 744
Nucleophilic Addition Page: 744
Nucleophilic Addition-Elimination Page: 745
16.4 Reactions of Carbonyl Compounds with Carbon Nucleophiles Page: 745
Reactions with Grignard Reagents Page: 745
Reactions of Aldehydes and Ketones with Grignard Reagents Page: 745
Problem 5 ♦ Page: 747
Problem 6 ♦ Page: 747
Problem 7 ♦ Page: 747
Reactions of Esters and Acyl Chlorides with Grignard Reagents Page: 747
Problem 8 SOLVED Page: 748
Solution to 8 a. Page: 749
Solution to 8 b. (A) Page: 749
Problem 9 ♦ Page: 749
Problem 10 Page: 749
Problem-Solving Strategy Predicting the Products of a Reaction with a Grignard Reagent Page: 749
Problem 11 ♦ Page: 749
Retrosynthetic Analysis Page: 749
Problem 12 Page: 750
Reaction with Acetylide Ions Page: 750
Problem 13 Page: 750
Problem 14 ♦ Page: 750
Reaction with Cyanide Ion Page: 750
Problem 15 ♦ Page: 751
Problem 16 ♦ Page: 751
Problem 17 ♦ Page: 751
Using Cyanohydrins in Synthesis Page: 751
Problem 18 SOLVED Page: 752
Solution to 18 a. Page: 752
Solution to 18 b. Page: 752
Problem 19 Page: 752
16.5 Reactions of Carbonyl Compounds with Hydride Ion Page: 752
Reactions of Aldehydes and Ketones with Hydride Ion Page: 752
Problem 20 ♦ Page: 753
Reaction of an Acyl Chloride with Hydride Ion Page: 753
Reaction of an Ester with Hydride Ion Page: 754
Reaction of a Carboxylic Acid with Hydride Ion Page: 755
Problem 21 ♦ Page: 755
Reaction of an Amide with Hydride Ion Page: 755
Problem 22 ♦ Page: 756
Problem 23 Page: 757
16.6 More About Reduction Reactions Page: 757
Reduction by Addition of a Hydride Ion and a Proton Page: 757
Reduction by Addition of Two Hydrogen Atoms Page: 757
Problem 24 ♦ Page: 758
Reduction by Addition of an Electron, a Proton, an Electron, a Proton Page: 758
16.7 Chemoselective Reactions Page: 759
Problem 25 Page: 759
Problem 26 Page: 759
16.8 Reactions of Aldehydes and Ketones with Nitrogen Nucleophiles Page: 760
Reactions with Primary Amines Page: 760
Forming Imine Derivatives Page: 760
The Mechanism Page: 760
Controlling the pH Page: 761
Imine Hydrolysis Page: 762
Problem 27 Page: 762
Problem 28 ♦ Page: 762
Problem 29 ♦ Page: 762
Problem 30 ♦ Page: 762
Problem 31 Page: 762
Reactions with Secondary Amines Page: 763
The Mechanism Page: 763
Enamine Hydrolysis Page: 764
Problem 32 Page: 764
Problem 33 Page: 764
Reductive Amination Page: 764
Problem 34 ♦ Page: 765
Problem 35 Page: 765
16.9 Reactions of Aldehydes and Ketones with Oxygen Nucleophiles Page: 766
Reaction with Water Page: 766
Problem 36 Page: 767
How Much Aldehyde or Ketone Is Hydrated? Page: 767
Problem 37 ♦ Page: 768
Problem 38 Page: 768
Proving that the Hydrate Is Formed Page: 768
Reaction with Alcohols Page: 769
Problem 39 ♦ Page: 770
Problem-Solving Strategy Page: 770
Problem 40 Page: 771
Problem 41 Page: 771
Summary of the Reactions of Aldehydes and Ketones with Nitrogen and Oxygen Nucleophiles Page: 771
16.10 Protecting Groups Page: 772
Protecting a Ketone or an Aldehyde Page: 772
Problem 42 ♦ Page: 772
Problem 43 Page: 772
Protecting an OH Group Page: 773
Problem 44 Page: 773
Problem 45 ♦ Page: 773
Problem 46 Page: 773
16.11 Reactions Of Aldehydes And Ketones With Sulfur Nucleophiles Page: 774
16.12 Reactions of Aldehydes and Ketones with a Peroxyacid Page: 774
Problem 47 ♦ Page: 775
16.13 The Wittig Reaction Forms an Alkene Page: 776
Preparing the Phosphonium Ylide Page: 776
Importance of the Wittig Reaction Page: 776
Retrosynthetic Analysis Page: 777
Problem 48 SOLVED Page: 778
Solution to 48 a. Page: 778
Solution to 48 b. Page: 778
Solution to 48 c. Page: 778
Problem 49 Page: 778
Designing a Synthesis IV 16.14    Disconnections, Synthons, and Synthetic Equivalents Page: 779
Problem 50 Page: 780
16.15 Nucleophilic Addition to α,β-Unsaturated Aldehydes and Ketones Page: 781
Direct Addition and Conjugate Addition Page: 781
When the Nucleophile Is a Weak Base Page: 782
When the Nucleophile Is a Strong Base Page: 783
Grignard Reagents and Organocuprates Page: 784
Problem 51 Page: 784
Hard and Soft Electrophiles and Nucleophiles Page: 784
16.16 Nucleophilic Addition to α,β-UNSATURATED CARBOXYLIC ACID Derivatives Page: 785
Problem 52 Page: 785
16.17 Conjugate Addition Reactions in Biological Systems Page: 786
Essential Concepts Page: 787
Summary of Reactions Page: 788
Problems Page: 791
17 Reactions at the α-Carbon Page: 801
17.1 The Acidity of an α-Hydrogen Page: 802
Hydrogens Bonded to s p 3 Carbons Adjacent to Carbonyl Carbons Are Relatively Acidic Page: 802
Electron Delocalization Stabilizes the Conjugate Base Page: 803
Problem 1 ♦ Page: 803
Problem 2 ♦ Page: 804
Problem-Solving Strategy Page: 804
Problem 3 ♦ Page: 804
Problem 4 ♦ Page: 804
Problem 5 ♦ Page: 805
17.2 Keto–Enol Tautomers Page: 805
Problem 6 Page: 806
17.3  Keto–Enol Interconversion Page: 806
Base-Catalyzed Keto–Enol Interconversion Page: 806
Acid-Catalyzed Keto–Enol Interconversion Page: 806
Problem 7 ♦ Page: 807
Problem 8 Page: 807
17.4  Halogenation of the α-Carbon of Aldehydes and Ketones Page: 807
Acid-Catalyzed Halogenation Page: 807
Base-Promoted Halogenation Page: 808
Comparing Keto–Enol Interconversion and α-Substitution Page: 808
Problem 9 Page: 808
Problem 10 ♦ Page: 808
17.5 Halogenation of the α-Carbon of Carboxylic Acids Page: 809
Replacing the α-Halogen of Carbonyl Compounds Page: 809
Problem 11 Page: 809
17.6   Forming an Enolate Ion Page: 810
Problem 12 ♦ Page: 810
17.7 Alkylating the α-Carbon Page: 811
Problem 13 Page: 811
Alkylating Unsymmetrical Ketones Page: 812
Kinetic Enolate Ion Page: 812
Thermodynamic Enolate Ion Page: 812
Problem-Solving Strategy Page: 813
Problem 14 Page: 813
Problem 15 ♦ Page: 814
Problem 16 Page: 814
17.8 Alkylating and Acylating the α-Carbon Via an Enamine Intermediate Page: 814
Problem 17 Page: 815
17.9   Alkylating the β-Carbon Page: 815
Alkylating the β-Carbon via an Enamine Page: 815
Alkylating the β-Carbon via a Michael Reaction Page: 816
Problem 18 Page: 816
Problem 19 ♦ Page: 817
17.10 An Aldol Addition Forms A β-Hydroxyaldehyde or A β-Hydroxyketone Page: 817
An Aldol Addition Page: 817
Problem 20 Page: 818
A Retro-Aldol Addition Page: 818
Problem 21 ♦ Page: 819
17.11  The Dehydration of Aldol Addition Products Forms α,β-Unsaturated Aldehydes and Ketones Page: 819
Dehydration Under Acidic Conditions Page: 819
Dehydration Under Basic Conditions Page: 819
Problem 22 ♦ Page: 820
Problem 23 SOLVED Page: 820
Solution Page: 820
Problem 24 Page: 820
17.12 A Crossed Aldol Addition Page: 821
Obtaining Primarily One Product When One Carbonyl Compound Does Not Have α-Hydrogens Page: 821
Obtaining Primarily One Product When Both Carbonyl Compounds Have α-Hydrogens Page: 821
Retrosynthetic Analysis Page: 822
retrosynthetic analysis Page: 822
synthesis Page: 822
retrosynthetic analysis Page: 822
synthesis Page: 822
Problem 25 Page: 823
Problem 26 Page: 823
Problem 27 Page: 823
17.13 A Claisen Condensation Forms a β-Keto Ester Page: 824
Comparing a Claisen Condensation with an Aldol Addition Page: 824
A Claisen Condensation Requires an Ester with Two α-Hydrogens Page: 825
Problem 28 ♦ Page: 825
Problem 29 ♦ Page: 825
A Crossed Claisen Condensation Page: 826
Problem 30 Page: 826
17.14 Other Crossed Condensations Page: 827
Problem 31 Page: 827
17.15 Intramolecular Condensations and Intramolecular Aldol Additions Page: 827
Intramolecular Claisen Condensations Page: 827
Problem 32 Page: 828
Intramolecular Aldol Additions Page: 828
Problem 33 ♦ Page: 829
Problem 34 Page: 829
Problem 35 ♦ Page: 829
17.16 The Robinson Annulation Page: 830
Problem-Solving Strategy Page: 830
Problem 36 Page: 830
Retrosynthetic Analysis Page: 831
Problem 37 Page: 831
17.17 CO 2 can be Removed from a Carboxylic Acid that has a Carbonyl Group at the 3-Position Page: 831
Problem 38 ♦ Page: 832
17.18 The Malonic Ester Synthesis: A Way to Synthesize a Carboxylic Acid Page: 833
Retrosynthetic Analysis Page: 834
Problem 39 ♦ Page: 834
Problem 40 Page: 834
17.19 The Acetoacetic Ester Synthesis: A Way to Synthesize a Methyl Ketone Page: 834
Retrosynthetic Analysis Page: 835
Problem 41 ♦ Page: 835
Problem 42 SOLVED Page: 835
Designing a Synthesis V 17.20 Making New Carbon–Carbon Bonds Page: 836
Problem 43 Page: 837
17.21  Reactions at the α-Carbon in Living Systems Page: 838
A Biological Aldol Addition Page: 838
Problem 44 Page: 838
A Biological Aldol Condensation Page: 838
A Biological Claisen Condensation Page: 839
Problem 45 ♦ Page: 840
Problem 46 ♦ Page: 840
A Biological Decarboxylation Page: 841
Problem 47 Page: 841
17.22 Organizing What We Know about the Reactions of Organic Compounds Page: 841
Essential Concepts Page: 843
Summary of Reactions Page: 844
Problems Page: 846
Essential Skill Tutorial Enhanced by Mastering Chemistry® Page: 853
Synthesis and Retrosynthetic Analysis Page: 853
Changing the Functional Group Page: 854
Functionalizing a Carbon Page: 854
Changing the Position of the Functional Group Page: 854
Changing the Carbon Skeleton Page: 854
Problem 1 Page: 855
Adding One Carbon to the Carbon Skeleton Page: 855
Adding More Than One Carbon to the Carbon Skeleton Page: 855
Problem 2 Page: 856
Problem 3 Page: 856
Using Retrosynthetic Analysis to Create a Functional Group Page: 856
Problem 4 Page: 856
Problem 5 Page: 856
Using Disconnections in Retrosynthetic Analysis Page: 857
Problem 6 Page: 857
Using the Relative Positions of two Functional Groups to Design a Synthesis Page: 858
Problem 7 Page: 859
Problem 8 Page: 859
Problem 9 Page: 859
Problem 10 Page: 859
Problem 11 Page: 860
Examples of Multistep Organic Synthesis Page: 860
Answers to Problems Page: 862
Problem 1 Page: 862
Problem 2 Page: 862
Problem 3 Page: 862
Problem 4 Page: 863
Problem 5 Page: 863
Problem 6 Page: 863
Problem 7 Page: 864
Problem 8 Page: 864
Problem 9 Page: 864
Problem 10 Page: 865
Problem 11 Page: 866
Part Six Aromatic Compounds Page: 867
18 Reactions of Benzene and Substituted Benzenes Page: 868
18.1 The Nomenclature of Monosubstituted Benzenes Page: 869
Problem 1 ♦ Page: 870
18.2 The General Mechanism for Electrophilic Aromatic Substitution Reactions Page: 871
18.3 Halogenation of Benzene Page: 872
Bromination and Chlorination of Benzene Page: 872
Problem 2 ♦ Page: 873
Iodination of Benzene Page: 873
18.4 Nitration of Benzene Page: 874
Problem 3 SOLVED Page: 874
Solution Page: 875
18.5 Sulfonation of Benzene Page: 875
18.6 Friedel–Crafts Acylation of Benzene Page: 876
Problem 4 Page: 877
18.7 Friedel–Crafts Alkylation of Benzene Page: 877
Carbocation Rearrangement Page: 878
Problem 5 ♦ Page: 879
18.8 Alkylation of Benzene by Acylation–Reduction Page: 880
18.9 Using Coupling Reactions to Alkylate Benzene Page: 881
Problem 6 Page: 881
18.10 How Some Substituents on a Benzene Ring Can Be Chemically Changed Page: 882
Substitution and Elimination Reactions Page: 882
Oxidation and Reduction Reactions Page: 882
Problem 7 ♦ Page: 883
Problem 8 SOLVED Page: 883
Solution to 8 a. Page: 884
18.11 The Nomenclature of Disubstituted and Polysubstituted Benzenes Page: 884
Naming Disubstituted Benzenes Page: 884
Problem 9 ♦ Page: 884
Problem 10 Page: 885
Naming Polysubstituted Benzenes Page: 885
Problem 11 Page: 885
Problem 12 ♦ Page: 885
18.12 The Effect of Substituents on Reactivity Page: 886
Electron Donation Increases Reactivity Electron Withdrawal Decreases Reactivity Page: 886
Relative Reactivity of Substituted Benzenes Page: 886
Strongly Activating Substituents Page: 886
Moderately Activating Substituents Page: 887
Weakly Activating Substituents Page: 888
Weakly Deactivating Substituents Page: 888
Moderately Deactivating Substituents Page: 889
Strongly Deactivating Substituents Page: 889
Problem 13 SOLVED Page: 889
Solution Page: 890
Problem 14 Page: 890
Problem 15 ♦ Page: 890
18.13 The Effect of Substituents on Orientation Page: 890
Substituents That Donate Electrons by Resonance are Ortho–Para Directors Page: 891
Substituents That Donate Electrons by Hyperconjugation are Ortho–Para Directors Page: 891
Substituents That Cannot Donate Electrons by Resonance or by Hyperconjugation are Meta Directors Page: 891
Problem 16 Page: 893
Problem 17 ♦ Page: 893
Problem 18 ♦ Page: 893
18.14 The Ortho–Para Ratio Page: 894
18.15 Additional Considerations Regarding Substituent Effects Page: 894
Halogenation Page: 894
Friedel–Crafts Acylation and Alkylation Page: 895
Problem 19 SOLVED Page: 895
Solution Page: 895
Problem 20 Page: 895
Problem 21 ♦ Page: 895
Designing a Synthesis VI 18.16 The Synthesis of Monosubstituted and Disubstituted Benzenes Page: 896
Problem 22 ♦ Page: 897
Problem 23 Page: 897
Problem 24 Page: 898
18.17 The Synthesis of Trisubstituted Benzenes Page: 898
Problem 25 ♦ Page: 899
Problem 26 ♦ Page: 899
Problem 27 SOLVED Page: 899
Solution Page: 899
18.18 Synthesizing Substituted Benzenes Using Arenediazonium Salts Page: 900
Sandmeyer Reactions Page: 900
Replacing a Diazonium Group with an Iodo Substituent Page: 901
The Schiemann Reaction Page: 901
Synthesizing a Phenol Page: 901
Replacing a Diazonium Group with a Hydrogen Page: 901
Retrosynthetic Analysis Page: 902
Problem 28 ♦ Page: 902
Problem 29 Page: 902
Problem 30 Page: 902
Problem 31 Page: 902
18.19 Azobenzenes Page: 903
Problem 32 Page: 903
Problem 33 Page: 904
Problem 34 Page: 904
18.20 The Mechanism for the Formation of a Diazonium Ion Page: 905
Problem 35 ♦ Page: 905
Problem 36 Page: 906
Problem 37 Page: 906
18.21 Nucleophilic Aromatic Substitution Page: 907
The Mechanism for Nucleophilic Aromatic Substitution Page: 907
Examples of Nucleophilic Aromatic Substitution Page: 908
Problem 38 Page: 908
Problem 39 ♦ Page: 908
Problem 40 Page: 908
Designing a Synthesis VII  18.22 The Synthesis of Cyclic Compounds Page: 909
Problem 41 Page: 910
Essential Concepts Page: 910
Summary of Reactions Page: 911
Problems Page: 913
19 More About Amines • Reactions of Heterocyclic Compounds Page: 924
19.1 More About Nomenclature Page: 925
Naming Nitrogen-Containing Saturated Heterocycles Page: 925
Naming Oxygen- and Sulfur-Containing Saturated Heterocycles Page: 925
Problem 1 ♦ Page: 926
19.2    More About the Acid–Base Properties of Amines Page: 926
Problem 2 SOLVED Page: 926
Solution Page: 927
Problem 3 ♦ Page: 927
Problem 4 ♦ Page: 927
19.3 Amines React as Bases and as Nucleophiles Page: 927
Amines Are Bases Page: 927
Amines are Nucleophiles Page: 928
Problem 5 Page: 928
19.4    Synthesis of Amines Page: 929
19.5    Aromatic Five-Membered-Ring Heterocycles Page: 929
Aromaticity of Pyrrole, Furan, and Thiophene Page: 929
Problem 6 Page: 930
Acid-Base Properties of Pyrrole Page: 930
Problem-Solving Strategy Page: 931
Problem 7 ♦ Page: 932
Electrophilic Aromatic Substitution Reactions Page: 932
Relative Reactivity Page: 933
Problem 8 Page: 933
19.6    Aromatic Six-Membered-Ring Heterocycles Page: 934
Aromaticity of Pyridine Page: 934
Acid-Base Properties of Pyridine Page: 934
Pyridine Reacts as a Nucleophile Page: 934
Problem 9 SOLVED Page: 934
Solution Page: 935
Problem 10 ♦ Page: 935
Electrophilic Aromatic Substitution Reactions Page: 935
Nucleophilic Aromatic Substitution Reactions Page: 936
Problem 11 Page: 937
Problem 12 Page: 937
Reactions of Substituted Pyridines Page: 937
Problem 13 ♦ Page: 938
19.7    Some Heterocyclic Amines Have Important Roles in Nature Page: 939
Imidazole Page: 939
Problem 14 ♦ Page: 940
Problem 15 ♦ Page: 941
Problem 16 ♦ Page: 941
Problem 17 ♦ Page: 941
Problem 18 ♦ Page: 941
Purine and Pyrimidine Page: 941
Problem 19 ♦ Page: 941
Problem 20 ♦ Page: 942
Porphyrin Page: 942
19.8    Organizing What We Know about the Reactions of Organic Compounds Page: 943
Essential Concepts Page: 944
Summary of Reactions Page: 945
Problems Page: 946
Part Seven Bioorganic Compounds Page: 949
20 The Organic Chemistry of Carbohydrates Page: 950
20.1    Classifying Carbohydrates Page: 951
Monosaccharides Are Either Aldoses or Ketoses Page: 951
Problem 1 ♦ Page: 952
20.2    The d and l Notation Page: 952
Problem 2 Page: 953
Problem 3 ♦ Page: 953
20.3    The Configurations of Aldoses Page: 953
Problem 4 ♦ Page: 954
Problem 5 ♦ Page: 954
Problem 6 ♦ Page: 954
20.4    The Configurations of Ketoses Page: 955
Problem 7 ♦ Page: 955
Problem 8 ♦ Page: 955
20.5    The Reactions of Monosaccharides in Basic Solutions Page: 956
Epimerization Page: 956
The Enediol Rearrangement Page: 956
Problem 9 Page: 957
Problem 10 Page: 957
Problem 11 ♦ Page: 957
20.6    Oxidation–Reduction Reactions of Monosaccharides Page: 957
Reduction Page: 957
Problem 12 ♦ Page: 957
Problem 13 ♦ Page: 957
Oxidation Page: 957
Problem 14 ♦ Page: 958
20.7    Lengthening the Chain: The Kiliani–Fischer Synthesis Page: 958
Problem 15 ♦ Page: 959
20.8    Shortening The Chain: The Wohl Degradation Page: 959
Problem 16 ♦ Page: 960
20.9    The Stereochemistry of Glucose: The Fischer Proof Page: 960
Problem 17 SOLVED Page: 962
Solution Page: 962
Problem 18 ♦ Page: 962
20.10    Monosaccharides Form Cyclic Hemiacetals Page: 962
Structures of α-D-Glucose and β-D-Glucose Page: 962
Anomers Page: 963
Cyclic Compounds Are in Equilibrium with the Open-Chain Compound Page: 963
Aldoses Exist Predominately as Cyclic Compounds Page: 963
Pyranoses and Furanoses Page: 964
Ketoses Exist Predominately as Cyclic Compounds Page: 964
Mutarotation Page: 964
Problem 19 SOLVED Page: 965
Solution to 19 a. Page: 965
Problem 20 Page: 965
Problem 21 Page: 965
Problem 22 ♦ Page: 965
20.11   Glucose Is the Most Stable Aldohexose Page: 965
Drawing a Chair Conformer of d-Glucose Page: 965
Drawing Chair Conformers of Other Pyranoses Page: 966
Drawing a Chair Conformer of an l-Pyranose Page: 966
Problem 23 ♦ Page: 966
Problem 24 ♦ Page: 966
20.12 Formation of Glycosides Page: 967
Mechanism for Glycoside Formation Page: 967
Problem 25 ♦ Page: 968
N-Glycosides Page: 968
Problem 26 ♦ Page: 968
20.13 The Anomeric Effect Page: 968
20.14 Reducing and Nonreducing Sugars Page: 969
Problem 27 SOLVED Page: 969
Solution Page: 969
Problem 28 ♦ Page: 969
20.15 Disaccharides Page: 969
Maltose Page: 969
Cellobiose Page: 970
Lactose Page: 970
Determining the Sugar in Lactose That Has the Hemiacetal Group Page: 970
Sucrose Page: 971
Problem 29 ♦ Page: 972
Problem 30 ♦ Page: 972
20.16 Polysaccharides Page: 973
Starch Page: 973
Cellulose Page: 973
Physical Properties of Starch and Cellulose Page: 974
Chitin Page: 974
Problem 31 ♦ Page: 975
20.17 Some Naturally Occurring Compounds Derived from Carbohydrates Page: 976
Deoxy Sugars Page: 976
Amino Sugars Page: 976
Vitamin C Page: 976
Problem 32 ♦ Page: 977
20.18 Carbohydrates on Cell Surfaces Page: 978
Blood Types Page: 978
Problem 33 ♦ Page: 979
20.19 Artificial Sweeteners Page: 979
Saccharin Page: 979
Dulcin and Sodium Cyclamate Page: 980
Aspartame Page: 980
Acesulfame Potassium and Sucralose Page: 980
Advantame Page: 980
Essential Concepts Page: 981
Summary of Reactions Page: 982
Problems Page: 983
21 Amino Acids, Peptides, and  Proteins Page: 986
21.1   The Nomenclature of Amino Acids Page: 987
The Most Common Naturally Occurring Amino Acids Page: 987
Aliphatic Side-Chain Amino Acids Page: 989
Amino Acids with Alcohol- and Sulfur-Containing Side Chains Page: 990
Acidic Amino Acids and Amides of Acidic Amino Acids Page: 990
Basic Amino Acids Page: 990
Amino Acids with Benzene Rings Page: 990
Heterocyclic Amino Acids Page: 990
Essential Amino Acids Page: 991
Problem 1 Page: 991
21.2   The Configuration of Amino Acids Page: 991
Problem 2 ♦ Page: 992
Problem 3 SOLVED Page: 992
Solution Page: 993
Problem 4 ♦ Page: 993
21.3    Acid–Base Properties of Amino Acids Page: 993
Problem 5 ♦ Page: 994
Problem 6 ♦ Page: 994
Problem 7 SOLVED Page: 994
Solution to 7 a. Page: 994
Problem 8 ♦ Page: 994
Problem 9 Page: 995
21.4   The Isoelectric Point Page: 995
Determining the pI of an Amino Acid without an Ionizable Side Chain Page: 995
Determining the pI of an Amino Acid with an Ionizable Side Chain Page: 995
Problem 10 ♦ Page: 995
Problem 11 ♦ Page: 996
Problem 12 Page: 996
Problem 13♦ Page: 996
Problem 14 Page: 996
21.5 Separating Amino Acids Page: 996
Electrophoresis Page: 996
Forming the Colored Product Page: 996
Problem 15 ♦ Page: 997
Paper/Thin-Layer Chromatography Page: 997
Problem 16 ♦ Page: 998
Ion-Exchange Chromatography Page: 998
An Amino Acid Analyzer Page: 999
Problem 17 Page: 999
Problem 18 Page: 1000
Problem 19 ♦ Page: 1000
21.6 Synthesis of Amino Acids Page: 1000
HVZ Reaction Followed by Reaction with Ammonia Page: 1000
Problem 20 ♦ Page: 1000
Reductive Amination Page: 1000
Problem 21 ♦ Page: 1001
N-Phthalimidomalonic Ester Synthesis Page: 1001
Strecker Synthesis Page: 1002
Problem 22 ♦ Page: 1002
Problem 23 ♦ Page: 1002
Problem 24 ♦ Page: 1002
21.7 Resolution of Racemic Mixtures of Amino Acids Page: 1002
Problem 25 Page: 1003
21.8 Peptide Bonds and Disulfide Bonds Page: 1003
Peptide Bonds Page: 1003
Problem 26 Page: 1004
Problem 27 Page: 1004
Problem 28 ♦ Page: 1004
Disulfide Bonds Page: 1004
21.9 Some Interesting Peptides Page: 1006
Problem 29 Page: 1007
Problem 30 ♦ Page: 1007
Problem 31 Page: 1007
21.10 The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation Page: 1007
Protecting the Amino Group Page: 1007
Activating the Carboxyl Group Page: 1008
Adding the Second Amino Acid Page: 1008
Adding More Amino Acids Page: 1008
Removing the Protecting Group on the N-Terminal End Page: 1009
Yield Limitations Page: 1009
Problem 32 ♦ Page: 1010
Problem 33 Page: 1010
Problem 34 Page: 1010
Problem 35 ♦ Page: 1010
21.11 Automated Peptide Synthesis Page: 1010
Adding the C-Terminal Amino Acid to the Solid Support Page: 1010
Adding Subsequent Amino Acids Page: 1010
Advantage of the Merrifield Method Page: 1011
Genetic Engineering Page: 1012
Problem 36 Page: 1012
21.12   An Introduction to Protein Structure Page: 1013
21.13 How to Determine the Primary Structure of a Polypeptide or a Protein Page: 1013
Breaking the Disulfide Bridges Page: 1013
Problem 37 Page: 1013
Determining the Number and Kinds of Amino Acids Page: 1014
Determining the N-Terminal Amino Acid Page: 1014
Problem 38 ♦ Page: 1015
Determining the C-Terminal Amino Acid Page: 1015
Partial Hydrolysis Page: 1015
Problem-Solving Strategy Sequencing an Oligopeptide Page: 1015
Problem 39 ♦ Page: 1016
Hydrolysis Using Endopeptidases Page: 1016
Hydrolysis Using Cyanogen Bromide Page: 1017
Problem 40 Page: 1017
Problem 41 ♦ Page: 1017
Problem 42 SOLVED Page: 1017
Solution Page: 1018
Problem 43 ♦ Page: 1019
Problem 44 Page: 1019
21.14 Secondary Structure Page: 1019
α-Helix Page: 1019
β-Pleated sheet Page: 1020
Coil Conformation Page: 1021
Problem 45 ♦ Page: 1021
21.15 Tertiary Structure Page: 1022
Stabilizing Interactions Page: 1022
Hydrophobic Interactions Page: 1023
Problem 46 ♦ Page: 1023
21.16      Quaternary Structure Page: 1024
Problem 47 ♦ Page: 1024
21.17 Protein Denaturation Page: 1025
Problem 48 Page: 1025
Essential Concepts Page: 1025
Problems Page: 1026
22 Catalysis in Organic Reactions and in Enzymatic Reactions Page: 1030
22.1   Catalysis In Organic Reactions Page: 1032
22.2    Acid Catalysis Page: 1032
Reviewing Acid-Catalyzed Hydrolysis of an Ester Page: 1032
Problem 2 Page: 1033
How an Acid Increases the Rate of Hydrolysis Page: 1033
Specific-Acid and General-Acid Catalysis Page: 1033
Problem 3 ♦ Page: 1035
Problem 4 Page: 1035
Problem 5 SOLVED Page: 1035
Solution Page: 1035
22.3 Base Catalysis Page: 1035
Specific-Base and General-Base Catalysis Page: 1035
Problem 6 Page: 1036
22.4 Nucleophilic Catalysis Page: 1037
Reactions Employing a Nucleophilic Catalyst Page: 1037
Example 1 Page: 1037
Example 2 Page: 1037
22.5 Metal-Ion Catalysis Page: 1038
Reactions Employing a Metal-Ion Catalyst Page: 1038
Example 1 Page: 1039
Example 2 Page: 1039
Problem 7 ♦ Page: 1039
Problem 8 Page: 1040
22.6   Intramolecular Reactions Page: 1040
Relative Rates Page: 1040
Problem 9 ♦ Page: 1042
22.7 Intramolecular Catalysis Page: 1042
Intramolecular Nucleophilic Catalysis Page: 1042
Problem 10 ♦ Page: 1043
Intramolecular General-Base Catalysis Page: 1043
Problem 11 SOLVED Page: 1043
Solution Page: 1044
Problem 12 ♦ Page: 1044
Problem 13 Page: 1044
22.8 Catalysis in Biological Reactions Page: 1044
Binding the Substrate Page: 1044
Catalyzing the Reaction Page: 1045
22.9 An Enzyme-Catalyzed Reaction That Is Reminiscent of Acid-Catalyzed Amide Hydrolysis Page: 1046
Binding the Substrate Page: 1046
Catalyzing the Reaction Page: 1048
Problem 14 SOLVED Page: 1048
Solution Page: 1048
Problem 15 ♦ Page: 1048
Problem 16 ♦ Page: 1048
Problem 17 Page: 1048
22.10  Another Enzyme-Catalyzed Reaction That Is Reminiscent of Acid-Catalyzed Amide Hydrolysis Page: 1049
The Specificity of the Serine Proteases Page: 1049
The Mechanism Page: 1049
Problem 18 ♦ Page: 1051
Problem 19 Page: 1051
Site-Specific Mutagenesis Page: 1051
22.11 An Enzyme-Catalyzed Reaction That Involves Two Sequential S N 2 Reactions Page: 1052
Binding the Substrate Page: 1052
Catalyzing the Reaction Page: 1052
Problem 20 ♦ Page: 1053
pH–Activity Profile Page: 1054
Problem 21 Page: 1055
22.12 An Enzyme-Catalyzed Reaction That Is Reminiscent of the Base-Catalyzed Enediol Rearrangement Page: 1056
Problem 22 Page: 1056
Problem 23 ♦ Page: 1057
22.13 An Enzyme Catalyzed-Reaction That Is Reminiscent of a Retro-Aldol Addition Page: 1057
Problem 24 Page: 1058
Problem 25 Page: 1059
Problem 26 ♦ Page: 1059
Problem 27 Page: 1059
Problem 28 ♦ Page: 1059
Essential Concepts Page: 1059
Problems Page: 1060
23 The Organic Chemistry of the Coenzymes, Compounds Derived from Vitamins Page: 1063
23.1   Niacin: The Vitamin Needed for Many Redox Reactions Page: 1066
The Pyridine Nucleotide Coenzymes Page: 1066
Many Catabolic Reactions are Oxidations Many Anabolic Reactions are Reductions Page: 1066
The Structure of a Pyridine Nucleotide Coenzyme Page: 1067
Examples of Enzyme-Catalyzed Reactions that Require a Pyridine Nucleotide Coenzyme Page: 1067
How Does NAD+ Oxidize a Substrate? Page: 1068
Problem 2 ♦ Page: 1069
How Does NADPH Reduce a Substrate? Page: 1069
Molecular Recognition and Selectivity Page: 1070
Problem 3 ♦ Page: 1071
23.2 Riboflavin: Another Vitamin Used in Redox Reactions Page: 1071
Examples of Enzyme-Catalyzed Reactions that Require FAD Page: 1072
Problem 4 ♦ Page: 1072
Mechanisms for Oxidation by FAD Page: 1072
Problem 5 ♦ Page: 1073
Comparing FAD and NAD+ Page: 1074
Problem 6 SOLVED Page: 1074
Solution Page: 1074
Problem 7 Page: 1075
23.3  Vitamin B1: The Vitamin Needed for Acyl Group Transfer Page: 1075
Pyruvate Decarboxylase Transfers an Acyl Group to H+ Page: 1075
Problem 8 Page: 1076
Problem 9 Page: 1076
Problem 10 Page: 1076
The Pyruvate Dehydrogenase Complex Transfers an Acyl Group to CoASH Page: 1076
Coenzyme A Page: 1077
Problem 11 SOLVED Page: 1078
Solution Page: 1078
Problem 12 Page: 1079
Mechanistic Similarities Page: 1079
23.4 Biotin: The Vitamin Needed for Carboxylation of An α-Carbon Page: 1079
Examples of Enzyme-Catalyzed Reactions that Require Biotin Page: 1080
Forming Activated Bicarbonate Page: 1080
The Mechanism for Carboxylation Page: 1080
23.5  Vitamin B6: The Vitamin Needed for Amino Acid Transformations Page: 1081
Examples of Enzyme-Catalyzed Reactions that Require PLP Page: 1081
Transimination Page: 1082
Decarboxylation Page: 1083
Racemization Page: 1083
Transamination Page: 1083
Problem 13 ♦ Page: 1085
Problem 14 ♦ Page: 1085
Problem 15 ♦ Page: 1085
Problem 16 ♦ Page: 1085
Problem 17 Page: 1085
Problem 18 Page: 1086
23.6 Vitamin B12: The Vitamin Needed for Certain Isomerizations Page: 1086
Examples of Enzyme-Catalyzed Reactions that Require Coenzyme B12 Page: 1086
The Mechanism for a B12 -Requiring Enzyme Page: 1087
Problem 19 Page: 1088
Problem 20 ♦ Page: 1088
23.7 Folic Acid: The Vitamin Needed for ­ One-Carbon Transfer Page: 1088
Examples of Enzyme-Catalyzed Reactions that Require a ­ THF-Coenzyme Page: 1088
Thymidylate Synthase: The Enzyme that Converts U to T Page: 1089
Cancer Chemotherapy Page: 1090
Inhibitors Page: 1092
Problem 21 ♦ Page: 1092
Problem 22 Page: 1092
23.8      Vitamin K: The Vitamin Needed for Carboxylation of Glutamate Page: 1093
The Mechanism Page: 1093
Problem 23 ♦ Page: 1094
Essential Concepts Page: 1095
Problems Page: 1096
24 The Organic Chemistry of the Metabolic Pathways Page: 1099
24.1 ATP is Used for Phosphoryl Transfer Reactions Page: 1100
ATP Reacts with Nucleophiles Page: 1100
The Enzyme Determines which Phosphorus is Attacked Page: 1101
Another Way to Activate a Carboxylate Ion Page: 1101
24.2    Why Atp is Kinetically Stable in A Cell Page: 1102
24.3  The “High-Energy” Character of Phosphoanhydride Bonds Page: 1102
Problem 1 SOLVED Page: 1102
Solution Page: 1103
Problem 2 Page: 1104
24.4 The Four Stages of Catabolism Page: 1104
The First Stage of Catabolism Page: 1104
The Second Stage of Catabolism Page: 1104
The Third Stage of Catabolism Page: 1105
The Fourth Stage of Catabolism Page: 1105
24.5    The Catabolism of Fats: Stages 1 and 2 Page: 1105
Fats are Hydrolyzed to Glycerol and Fatty Acids Page: 1105
Glycerol is Converted to Dihydroxyacetone Phosphate Page: 1105
Problem 3 Page: 1106
Problem 4 Page: 1106
A Fatty Acid is Activated to a Fatty Acyl-CoA Page: 1106
A Fatty Acyl-CoA is Converted to Acetyl-CoA Molecules Page: 1106
Problem 5 ♦ Page: 1108
Problem 6 ♦ Page: 1108
Problem 7 ♦ Page: 1108
24.6   The Catabolism of Carbohydrates: Stages 1 and 2 Page: 1108
Carbohydrates are Hydrolyzed to Glucose Molecules Page: 1108
Glucose is Converted to Pyruvate Page: 1108
ATP is Used for Molecular Recognition Page: 1111
Coupled Reactions Page: 1111
Problem 8 Page: 1111
Problem 9 Page: 1111
Problem-Solving Strategy Page: 1111
Problem 10 ♦ Page: 1111
24.7    The Fate Of Pyruvate Page: 1112
Under Aerobic Conditions Page: 1112
Under Anaerobic Conditions Page: 1112
The Fate of Pyruvate in Yeast Page: 1112
Problem 11 ♦ Page: 1113
Problem 12 ♦ Page: 1113
Problem 13 ♦ Page: 1113
Problem 14 Page: 1113
24.8       The Catabolism of Proteins: Stages 1 and 2 Page: 1113
Proteins are Hydrolyzed to Amino Acids Page: 1113
Amino Acids are Converted to Compounds that Can Enter the Citric Acid Cycle Page: 1113
Problem 15 ♦ Page: 1114
24.9 The Citric Acid Cycle: Stage 3 Page: 1114
Problem 16 Page: 1118
Problem 17 ♦ Page: 1118
Problem 18 ♦ Page: 1118
Problem 19 ♦ Page: 1118
Problem 20 Page: 1118
Problem 21 ♦ Page: 1118
24.10 Oxidative Phosphorylation: Stage 4 Page: 1118
Problem 22 ♦ Page: 1119
24.11 Anabolism Page: 1119
24.12    Gluconeogenesis Page: 1120
Problem 23 ♦ Page: 1121
24.13 Regulating Metabolic Pathways Page: 1122
Regulatory Enzymes Page: 1122
Feedback Inhibitors Page: 1122
Hexokinase Page: 1122
Allosteric Inhibitors and Activators Page: 1122
Phosphofructokinase Page: 1122
Pyruvate carboxylase Page: 1122
24.14 Amino Acid Biosynthesis Page: 1123
Problem 24 Page: 1123
Essential Concepts Page: 1124
Problems Page: 1125
25 The Organic Chemistry of Lipids Page: 1127
25.1 Fatty Acids Are Long-Chain Carboxylic Acids Page: 1128
Problem 1 Page: 1129
25.2 Waxes Are High-Molecular-Weight Esters Page: 1130
25.3 Fats and Oils Are Triglycerides Page: 1130
Fats and Oils Page: 1130
Converting Oils to Fats Page: 1131
Problem 2 ♦ Page: 1131
Problem 3 Page: 1131
Problem 4 Page: 1131
25.4 Soaps and Micelles Page: 1132
Soap Page: 1132
Micelles Page: 1133
Detergents Page: 1133
Problem 5 SOLVED Page: 1134
25.5 Phospholipids Are Components of Cell Membranes Page: 1134
Phosphoglycerides Page: 1134
Problem 6 ♦ Page: 1135
Membranes Page: 1135
Sphingolipids Page: 1136
Problem 7 ♦ Page: 1137
Problem 8 ♦ Page: 1137
Problem 9 Page: 1137
25.6  Prostaglandins Regulate Physiological Responses Page: 1137
Problem 10 Page: 1138
Biosynthesis of Prostaglandins Page: 1138
Thromboxanes and Prostacyclins Page: 1139
Leukotrienes Page: 1139
25.7    Terpenes Contain Carbon Atoms in Multiples of Five Page: 1139
Classes of Terpenes Page: 1140
Problem 11 SOLVED Page: 1141
Solution Page: 1141
Problem 12 Page: 1141
Problem 13 ♦ Page: 1141
Problem 14 Page: 1141
25.8 How Terpenes are Biosynthesized Page: 1141
Biosynthesis of Isopentenyl Pyrophosphate Page: 1141
Problem 15 Page: 1142
Problem 16 ♦ Page: 1142
Problem 17 Page: 1142
Problem 18 SOLVED Page: 1142
Solution Page: 1142
Biosynthesis of Dimethylallyl Pyrophosphate Page: 1142
Reaction of Dimethylallyl Pyrophosphate with Isopentenyl Pyrophosphate Page: 1143
Synthesizing Monoterpenes Page: 1143
Problem-Solving Strategy Page: 1144
Problem 19 Page: 1144
Problem 20 Page: 1144
Reaction of Geranyl Pyrophosphate with Isopentenyl Pyrophosphate Page: 1144
Problem 21 ♦ Page: 1145
Joining Two Molecules of Farnesyl Pyrophosphate Page: 1145
Reaction of Farnesyl Pyrophosphate with Isopentenyl Pyrophosphate Page: 1145
Problem 22 Page: 1146
Problem 23 SOLVED Page: 1146
Solution Page: 1146
Problem 24 Page: 1146
25.9    How Nature Synthesizes Cholesterol Page: 1147
Problem 25 ♦ Page: 1147
25.10    Steroids Page: 1148
Problem 26 ♦ Page: 1148
Cholesterol Page: 1148
Problem 27 ♦ Page: 1148
Problem 28 Page: 1148
Steroid Hormones Page: 1148
Glucocorticoids and Mineralcorticoids Page: 1148
Problem 29 Page: 1149
Androgens Page: 1149
Estrogens Page: 1149
Bile Acids Page: 1150
Problem 30 ♦ Page: 1150
25.11 Synthetic Steroids Page: 1150
Essential Concepts Page: 1151
Problems Page: 1152
26 The Chemistry of the Nucleic Acids Page: 1155
26.1    Nucleosides and Nucleotides Page: 1155
The Bases in DNA and RNA Page: 1155
Nucleosides Page: 1156
Nucleotides Page: 1157
Problem 1 Page: 1158
Problem 2 Page: 1159
26.2      Nucleic Acids Are Composed of Nucleotide Subunits Page: 1159
Biosynthesis of Nucleic Acids Page: 1159
The Primary Structure of a Nucleic Acid Page: 1160
26.3    The Secondary Structure of DNA Page: 1161
The DNA Strands are Complementary Page: 1161
Hydrogen Bonding Dictates Base Pairing Page: 1161
Problem 3 Page: 1161
Problem 4 Page: 1161
Problem 5 ♦ Page: 1161
The Double Helix Page: 1161
26.4    Why Dna Does Not Have A 2′-Oh Group Page: 1163
Problem 6 Page: 1163
26.5    The Biosynthesis of DNA Is Called Replication Page: 1163
Problem 7 Page: 1164
26.6    DNA and Heredity Page: 1164
26.7    The Biosynthesis of RNA Is Called Transcription Page: 1165
Problem 8 ♦ Page: 1166
26.8    The RNAs Used for Protein Biosynthesis Page: 1167
An Amino Acid Is Attached to a tRNA at Its 3 ′ -End Page: 1167
The Synthetases Correct Their Mistakes Page: 1168
26.9    The Biosynthesis of Proteins Is Called Translation Page: 1169
Codons Page: 1169
How Translation Occurs Page: 1170
Problem 9 ♦ Page: 1172
Problem 10 ♦ Page: 1172
Problem 11 Page: 1172
Where Transcription and Translation Take Place Page: 1172
Problem 12 ♦ Page: 1172
Problem 13 ♦ Page: 1173
Problem 14 Page: 1173
26.10  Why DNA Contains Thymine Instead of Uracil Page: 1173
Problem 15 ♦ Page: 1174
Problem 16 Page: 1174
26.11  Antiviral Drugs Page: 1174
Acyclovir Page: 1174
Cytarabine Page: 1174
Idoxuridine Page: 1175
26.12 How the Base Sequence of DNA Is Determined Page: 1175
Restriction Endonucleases Page: 1175
Problem 17 ♦ Page: 1176
Pyrosequencing Page: 1176
26.13 Genetic Engineering Page: 1177
Essential Concepts Page: 1178
Problems Page: 1178
PartEightSpecial Topics in Organic Chemistry Page: 1181
27 Synthetic Polymers Page: 1182
27.1     There Are Two Major Classes of Synthetic Polymers Page: 1183
Chain-Growth Polymers Page: 1183
Step-Growth Polymers Page: 1183
27.2  An Introduction to Chain-Growth Polymers Page: 1184
27.3    Radical Polymerization Page: 1184
Head-to-Tail Addition Page: 1186
Monomers that Undergo Radical Polymerization Page: 1186
Radical Initiators Page: 1187
Problem 1 ♦ Page: 1187
Problem 2 ♦ Page: 1188
Problem 3 Page: 1188
Problem 4 Page: 1188
Branching of the Polymer Chain Page: 1188
Problem 5 ♦ Page: 1189
Problem 6 Page: 1189
Plasticizers Page: 1189
27.4 Cationic Polymerization Page: 1189
Rearrangement of the Carbocation Page: 1190
Problem 7 ♦ Page: 1191
27.5  Anionic Polymerization Page: 1192
Problem 8 ♦ Page: 1193
What Determines the Mechanism? Page: 1193
Problem 9 ♦ Page: 1193
27.6  Ring-Opening Polymerizations Page: 1193
Problem 10 Page: 1194
Problem 11 Page: 1194
Problem 12 ♦ Page: 1194
Problem 13 ♦ Page: 1194
27.7    Stereochemistry of Polymerization • Ziegler–Natta Catalysts Page: 1195
Controlling the Configuration Page: 1195
The Mechanism Page: 1195
27.8   Polymerization of Dienes Page: 1196
Natural Rubber Page: 1196
Problem 14 Page: 1197
Synthetic Rubber Page: 1197
Vulcanization Page: 1197
Problem 15 Page: 1198
27.9    Copolymers Page: 1198
27.10  An Introduction to Step-Growth Polymers Page: 1199
27.11 Classes of Step-Growth Polymers Page: 1200
Polyamides Page: 1200
Problem 16 ♦ Page: 1200
Problem 17 Page: 1200
Aramides Page: 1200
Polyesters Page: 1201
Problem 18 Page: 1202
Polycarbonates Page: 1202
Epoxy Resins Page: 1202
Problem 19 Page: 1202
Polyurethanes Page: 1203
Problem 20 Page: 1204
27.12    Physical Properties of Polymers Page: 1204
Thermoplastic Polymers Page: 1204
Thermosetting Polymers Page: 1205
Problem 21 Page: 1205
Problem 22 Page: 1205
Elastomers Page: 1205
Oriented Polymers Page: 1206
27.13 Recycling Polymers Page: 1206
27.14 Biodegradable Polymers Page: 1207
Problem 23 Page: 1207
Essential Concepts Page: 1208
Problems Page: 1208
28 Pericyclic Reactions Page: 1212
28.1    There are Three Kinds of Pericyclic Reactions Page: 1213
Electrocyclic Reactions Page: 1213
Cycloaddition Reactions Page: 1213
Sigmatropic Rearrangements Page: 1213
Common Features of Pericyclic Reactions Page: 1213
Conservation of Orbital Symmetry Page: 1214
Problem 1 ♦ Page: 1215
28.2    Molecular Orbitals and Orbital Symmetry Page: 1215
Molecular Orbital Description of Ethene Page: 1215
Molecular Orbital Description of 1,3-Butadiene Page: 1216
Analyzing Molecular Orbitals Page: 1216
Molecular Orbital Description of 1,3,5-Hexatriene Page: 1217
Problem 2 ♦ Page: 1218
Problem 3 ♦ Page: 1218
Problem 4 Page: 1218
28.3    Electrocyclic Reactions Page: 1218
Conrotatory and Disrotatory Ring Closure Page: 1220
Symmetry-Allowed and Symmetry-Forbidden Pathways Page: 1220
Explaining the Configuration of the Product(s) of an Electrocyclic Reaction Page: 1221
Example 1 Page: 1221
Example 2 Page: 1221
Example 3 Page: 1221
Example 4 Page: 1222
Woodward–Hoffmann Rules for Electrocyclic Reactions Page: 1222
Problem 5 Page: 1223
Problem 6 ♦ Page: 1223
Using the Woodward–Hoffmann Rules for Electrocyclic Reactions Page: 1223
Problem 7 ♦ Page: 1224
Problem 8 ♦ Page: 1224
28.4    Cycloaddition Reactions Page: 1224
Classifying Cycloaddition Reactions Page: 1224
Suprafacial and Antarafacial Bond Formation Page: 1224
[ 4+2 ] Cycloaddition Reactions Page: 1225
[ 2+2 ] Cycloaddition Reactions Page: 1226
Woodward–Hoffmann Rules for Cycloaddition Reactions Page: 1226
Problem 9 Solved Page: 1227
Solution Page: 1227
Problem 10 Page: 1227
Problem 11 ♦ Page: 1227
28.5    Sigmatropic Rearrangements Page: 1227
Describing Sigmatropic Rearrangements Page: 1227
Problem 12 Page: 1228
Suprafacial and Antarafacial Rearrangement Page: 1228
Woodward–Hoffmann Rules for Sigmatropic Rearrangements Page: 1229
Cope and Claisen Rearrangements Page: 1229
Problem 13 ♦ Page: 1229
Migration of Hydrogen Page: 1230
Problem 14 ♦ Page: 1231
Problem 15 Page: 1231
Problem 16 Solved Page: 1231
Solution Page: 1231
Migration of Carbon Page: 1231
Problem 17 Page: 1232
Problem 18 ♦ Page: 1232
28.6    Pericyclic Reactions In Biological Systems Page: 1232
A Biological Cycloaddition Reaction Page: 1232
A Biological Electrocyclic Reaction and Sigmatropic Rearrangement Page: 1233
Problem 19 ♦ Page: 1234
Problem 20 Page: 1235
Problem 21 ♦ Page: 1235
28.7    Summary of the Selection Rules for Pericyclic Reactions Page: 1235
Problem 22 Page: 1235
Essential Concepts Page: 1236
Problems Page: 1236
Appendix I Page: A-1
AppendixIIKinetics Page: A-3
How to Determine Rate Constants Page: A-3
First-Order Reaction Page: A-3
Half-Life of a First-Order Reaction Page: A-3
Second-Order Reaction Page: A-3
Half-Life of a Second-Order Reaction Page: A-4
Pseudo-First-Order Reaction Page: A-4
Problems Page: A-4
Solutions to Problems Page: A-5
Appendix IIISummary of Methods Usedto Synthesize a ParticularFunctional Group Page: A-8
SYNTHESIS OF ACETALS Page: A-8
SYNTHESIS OF ACID ANHYDRIDES Page: A-8
SYNTHESIS OF ACYL CHLORIDES OR ACYL BROMIDES Page: A-8
SYNTHESIS OF ALCOHOLS Page: A-8
SYNTHESIS OF ALDEHYDES Page: A-8
SYNTHESIS OF ALKANES Page: A-8
SYNTHESIS OF ALKENES Page: A-8
SYNTHESIS OF ALKYL HALIDES Page: A-9
SYNTHESIS OF ALKYNES Page: A-9
SYNTHESIS OF AMIDES Page: A-9
SYNTHESIS OF AMINES Page: A-9
SYNTHESIS OF AMINO ACIDS Page: A-9
SYNTHESIS OF CARBOXYLIC ACIDS Page: A-9
SYNTHESIS OF CYANOHYDRINS Page: A-9
SYNTHESIS OF DIHALIDES Page: A-9
SYNTHESIS OF 1,2-DIOLS Page: A-9
SYNTHESIS OF DISULFIDES Page: A-9
SYNTHESIS OF ENAMINES Page: A-9
SYNTHESIS OF EPOXIDES Page: A-9
SYNTHESIS OF ESTERS Page: A-10
SYNTHESIS OF ETHERS Page: A-10
SYNTHESIS OF HALOHYDRINS Page: A-10
SYNTHESIS OF IMINES Page: A-10
SYNTHESIS OF KETONES Page: A-10
SYNTHESIS OF α , β -UNSATURATED KETONES Page: A-10
SYNTHESIS OF NITRILES Page: A-10
SYNTHESIS OF SUBSTITUTED BENZENES Page: A-10
SYNTHESIS OF SULFIDES Page: A-10
SYNTHESIS OF THIOLS Page: A-10
Appendix IV Summary of Methods Employed to Form Carbon–Carbon Bonds Page: A-11
Appendix V Spectroscopy Tables Page: A-12
AppendixVI Physical Properties of Organic Compounds Page: A-18
Answers to Selected Problems Page: A-20
Chapter 1 Remembering General Chemistry: Electronic Structure and Bonding Page: ANS-1
Chapter 2 Acids And Bases: Central to Understanding Organic Chemistry Page: ANS-1
Chapter 3 An Introduction to Organic Compounds Page: ANS-1
Chapter 4 Isomers: The Arrangement of Atoms in Space Page: ANS-2
Chapter 5 Alkenes • Thermodynamics and Kinetics Page: ANS-3
Chapter 6 The Reactions of Alkenes • The Stereochemistry of Addition Reactions Page: ANS-3
Chapter 7 The Reactions of Alkynes: An Introduction to Multistep Synthesis Page: ANS-3
Chapter 8 Delocalized Electrons • Aromaticity and Electronic Effects Page: ANS-4
Chapter 9 Substitution and Elimination Reactions of Alkyl Halides Page: ANS-5
Chapter 10 Reactions of Alcohols, Ethers, Epoxides, Amines, and Sulfur-Containing Compounds Page: ANS-5
Chapter 11 Organometallic Compounds Page: ANS-6
Chapter 12 Radicals Page: ANS-6
Chapter 13 Mass Spectrometry • Infrared Spectroscopy • Ultraviolet/Visible Spectroscopy Page: ANS-6
Chapter 14 NMR Spectroscopy Page: ANS-6
Chapter 15 Reactions of Carboxylic Acids and Carboxylic Acid Derivatives Page: ANS-7
Chapter 16 Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid Derivatives Page: ANS-7
Chapter 17 Reactions at the α-Carbon Page: ANS-7
Chapter 18 Reactions of Benzene and Substituted Benzenes Page: ANS-8
Chapter 19 More About Amines • Reactions of Heterocyclic Compounds Page: ANS-8
Chapter 20 The Organic Chemistry of Carbohydrates Page: ANS-9
Chapter 21 Amino Acids, Peptides, and Proteins Page: ANS-9
Chapter 22 Catalysis in Organic Reactions and in Enzymatic Reactions Page: ANS-9
Chapter 23 The Organic Chemistry of the Coenzymes, Compounds Derived from Vitamins Page: ANS-9
Chapter 24 The Organic Chemistry of the Metabolic Pathways Page: ANS-10
Chapter 25 The Organic Chemistry of Lipids Page: ANS-10
Chapter 26 The Chemistry of the Nucleic Acids Page: ANS-10
Chapter 27 Synthetic Polymers Page: ANS-10
Chapter 28 Pericyclic Reactions Page: ANS-10
Glossary Page: G-1
Credits Page: C-1
CHAPTER 1 Page: C-1
CHAPTER 2 Page: C-1
CHAPTER 3 Page: C-1
CHAPTER 4 Page: C-1
CHAPTER 5 Page: C-1
CHAPTER 6 Page: C-1
CHAPTER 7 Page: C-1
CHAPTER 8 Page: C-1
CHAPTER 9 Page: C-1
CHAPTER 10 Page: C-1
CHAPTER 11 Page: C-1
CHAPTER 12 Page: C-1
CHAPTER 13 Page: C-1
CHAPTER 14 Page: C-1
CHAPTER 15 Page: C-1
CHAPTER 16 Page: C-1
CHAPTER 17 Page: C-1
CHAPTER 18 Page: C-1
CHAPTER 19 Page: C-1
CHAPTER 20 Page: C-1
CHAPTER 21 Page: C-1
CHAPTER 22 Page: C-1
CHAPTER 23 Page: C-1
CHAPTER 24 Page: C-1
CHAPTER 25 Page: C-2
CHAPTER 26 Page: C-2
CHAPTER 27 Page: C-2
CHAPTER 28 Page: C-2
Index Page: I-1
A Page: I-1
B Page: I-2
C Page: I-4
D Page: I-5
E Page: I-6
F Page: I-7
G Page: I-7
H Page: I-8
I Page: I-9
J Page: I-9
K Page: I-9
L Page: I-9
M Page: I-9
N Page: I-11
O Page: I-11
P Page: I-12
Q Page: I-13
R Page: I-13
S Page: I-14
T Page: I-15
U Page: I-16
V Page: I-16
W Page: I-16
X Page: I-16
Y Page: I-16
Z Page: I-16
Introduction Page: FEP-1
To the Student Page: FEP-1
Organizing What We Know About The Reactions of Organic Chemistry Page: FEP-1
Useful References Page: BEP-1