Introduction 1
About This Book 2
Foolish Assumptions 3
Icons Used in This Book 3
Beyond the Book 4
Where to Go from Here 4
Part 1: Getting Started With Organic Chemistry 5
Chapter 1: The Wonderful World of Organic Chemistry 7
Shaking Hands with Organic Chemistry 7
What Are Organic Molecules, Exactly? 9
An Organic Chemist by Any Other Name 11
Synthetic organic chemists 11
Bioorganic chemists 11
Natural products chemists 12
Physical organic chemists 13
Organometallic chemists 13
Computational chemists 14
Materials chemists 14
Chapter 2: Dissecting Atoms: Atomic Structure and Bonding 15
Electron House Arrest: Shells and Orbitals 16
Electron apartments: Orbitals 17
Electron instruction manual: Electron configuration 19
Atom Marriage: Bonding 20
To Share or Not to Share: Ionic and Covalent Bonding 21
Mine! They're all mine! Ionic bonding 21
The name's Bond, Covalent Bond 22
Electron piggishness and electronegativity 23
Separating Charge: Dipole Moments 25
Problem solving: Predicting bond dipole moments 25
Problem solving: Predicting molecule dipole moments 26
Seeing Molecular Geometries 27
Mixing things up: Hybrid orbitals 28
Predicting hybridization for atoms 30
It's All Greek to Me: Sigma and Pi Bonding 31
Chapter 3: Speaking with Pictures: Drawing Structures 35
Picture-Talk: Lewis Structures 37
Taking charge: Assigning formal charges 37
Drawing structures 39
Atom packing: Condensed structures 39
Structural shorthand: Line-bond structures 40
Converting Lewis structures to line-bond structures 41
Determining the number of hydrogens on line-bond structures 43
So lonely: Determining lone pairs on atoms 44
Problem Solving: Arrow Pushing 44
Drawing Resonance Structures 46
Rules for resonance structures 47
Problem solving: Drawing resonance structures 48
Drawing more than two resonance structures 51
Assigning importance to resonance structures 52
Common mistakes in drawing resonance structures 54
Chapter 4: Covering the Bases (And the Acids) 57
A Defining Moment: Acid-Base Definitions 58
Arrhenius acids and bases: A little watery 58
Pulling for protons: Bronsted-Lowry acids and bases 59
Electron lovers and haters: Lewis acids and bases 59
Comparing Acidities of Organic Molecules 61
Comparing atoms 62
Seeing atom hybridization 62
Seeing electronegativity effects 63
Seeing resonance effects 64
Defining pKa: A Quantitative Scale of Acidity 64
Problem Solving: Predicting the Direction of Acid-Base Reactions at Equilibrium 65
Chapter 5: Reactivity Centers: Functional Groups 67
Hydrocarbons 68
Double the fun: The alkenes 68
Alkynes of fun 69
Smelly compounds: The aromatics 71
Singly Bonded Heteroatoms 72
Happy halides 72
For rubbing and drinking: Alcohols 73
What stinks? Thiols 74
How ethereal 75
Table of Contents ix
Carbonyl Compounds 75
Living on the edge: Aldehydes 75
Stuck in the middle: Ketones 76
Carboxylic acids 76
Sweet-smelling compounds: Esters 78
Nitrogen-containing functional groups 78
I am what I amide 79
Be nice, don't be amine person 79
Nitriles 80
Test Your Knowledge 80
Chapter 6: Seeing in 3-D: Stereochemistry 81
Drawing Molecules in 3-D 82
Comparing Stereoisomers and Constitutional Isomers 82
Mirror Image Molecules: Enantiomers 83
Seeing Chiral Centers 84
Assigning Configurations to Chiral Centers: The R/S Nomenclature 85
Problem Solving: Determining R/S Configuration 86
Step 1: Prioritizing the substituents 86
Step 2: Putting the number-four substituent in the back 86
Step 3: Drawing the curve 87
The Consequences of Symmetry: Meso Compounds 89
Rotating Plane-Polarized Light 90
Multiple Chiral Centers: Diastereomers 91
Representing 3-D Structures on Paper: Fischer Projections 92
Rules for using Fischer projections 92
Determining R/S configuration from a Fischer projection 93
Seeing stereoisomerism with Fischer projections 94
Spotting meso compounds with Fischer projections 94
Keeping the Jargon Straight 95
Part 2: Hydrocarbons 97
Chapter 7: What's in a Name? Alkane Nomenclature 99
All in a Line: Straight-Chain Alkanes 100
Reaching Out: Branching Alkanes 100
Finding the longest chain 101
Numbering the chain 101
Seeing the substituents 102
Ordering the substituents 103
More than one of a kind 103
Naming complex substituents 104
Chapter 8: Drawing Alkanes 107
Converting a Name to a Structure 107
Conformation of Straight-Chain Alkanes 109
Newman! Conformational analysis and Newman projections 110
Conformations of butane 111
Full Circle: Cycloalkanes 113
The stereochemistry of cycloalkanes 113
Conformations of cyclohexane 114
Problem Solving: Drawing the Most Stable Chair Conformation 117
Reacting Alkanes: Free-Radical Halogenation 118
Getting things started: Initiation 119
Keeping the reaction going: Propagation 119
You're fired: Termination steps 119
Selectivity of chlorination and bromination 121
Chapter 9: Seeing Double: The Alkenes 123
Defining Alkenes 124
Taking Away Hydrogens: Degrees of Unsaturation 125
Determining degrees of unsaturation from a structure 126
Problem solving: Determining degrees of unsaturation from a molecular formula 127
The Nomenclature of Alkenes 128
Numbering the parent chain 128
Adding multiple double bonds 129
Common names of alkenes 129
The Stereochemistry of Alkenes 130
You on my side or their side? Cis and trans stereochemistry 130
Playing a game of high-low: E/Z stereochemistry 131
Stabilities of Alkenes 132
Alkene substitution 133
Stability of cis and trans isomers 133
Formation of Alkenes 134
Elimination of acid: Dehydrohalogenation 134
Losing water: Dehydration of alcohols 134
Alkenes from coupling: The Wittig reaction 135
Chapter 10: Reactions of Alkenes 137
Adding Hydrohalic Acids across Double Bonds 138
I'm Positive: Carbocations 139
Helping a neighbor: Hyperconjugation 139
Resonance stabilization of carbocations 140
Carbocation mischief: Rearrangements 141
Adding Water across Double Bonds 142
Markovnikov addition: Oxymercuration-demercuration 142
Anti-Markovnikov addition: Hydroboration 143
A double shot: Dihydroxylation 144
Double the fun: Bromination 145
Chopping Up Double Bonds: Ozonolysis 145
Double-Bond Cleavage: Permanganate Oxidation 146
Making Cyclopropanes with Carbenes 146
Making Cyclopropanes: The Simmons-Smith Reaction 147
Making Epoxides 148
Adding Hydrogen: Hydrogenation 148
Chapter 11: It Takes Alkynes: The Carbon-Carbon
Triple Bond 149
Naming Alkynes 150
Seeing Alkyne Orbitals 150
Alkynes in Rings 151
Making Alkynes 151
Losing two: Dehydrohalogenation 152
Coupling alkynes: Acetylide chemistry 152
Brominating alkynes: Double the fun 153
Saturating alkynes with hydrogen 154
Adding one hydrogen molecule to alkynes 154
Oxymercuration of alkynes 154
Hydroboration of alkynes 155
Part 3: functional groups 157
Chapter 12: Replacing and Removing: Substitution and Elimination Reactions 159
Group Swap: Substitution Reactions 160
Seeing Second-Order Substitution: The SN2 Mechanism 161
How fast? The rate equation for the SN2 reaction 161
Effect of the substrate on the SN2 reaction 162
Needs nucleus: The role of the nucleophile 163
Seeing the SN2 reaction in 3-D: Stereochemistry 165
Seeing solvent effects 165
I'm outta here: The leaving group 166
First-Order Substitution: The SN1 Reaction 167
How fast? The rate equation for the SN1 reaction 167
Seeing good SN1 substrates 168
Seeing solvent effects on the SN1 reaction 169
Stereochemistry of the SN1 reaction 170
Other fun facts about the SN1 reaction 170
Seeing Elimination Reactions 171
Seeing second-order eliminations: The E2 reaction 171
Seeing first-order elimination: The E1 reaction 172
Help! Distinguishing Substitution from Elimination 173
Chapter 13: Getting Drunk on Organic Molecules: The Alcohols 175
Classifying Alcohols 176
An Alcohol by Any Other Name: Naming Alcohols 176
Alcohol-Making Reactions 178
Adding water across double bonds 178
Reduction of carbonyl compounds 178
The Grignard reaction 179
Reactions of Alcohols 181
Losing water: Dehydration 181
Making ethers: Williamson ether synthesis 181
Oxidation of alcohols 181
CHAPTER 14: Side-by-Side: Conjugated Alkenes and the Diels-Alder Reaction 183
Seeing Conjugated Double Bonds 184
Addition of Hydrohalic Acids to Conjugated Alkenes 184
Seeing the reaction diagram of conjugate addition 185
Comparing kinetics and thermodynamics of conjugate addition 186
The Diels-Alder Reaction 187
Seeing the diene and the dienophile 187
The stereochemistry of addition 188
Seeing bicyclic products 189
Problem Solving: Determining Products of Diels-Alder Reactions 189
Chapter 15: Lord of the Rings: Aromatic Compounds 193
Defining Aromatic Compounds 194
The structure of benzene 194
Diversity of aromatic compounds 195
So, what exactly makes a molecule aromatic? 196
Huckel's 4n + 2 rule 196
Explaining Aromaticity: Molecular Orbital Theory 197
What the heck is molecular orbital theory? 197
Making molecular orbital diagrams 197
Two rings diverged in a wood: Frost circles 198
Making the molecular orbital diagram of benzene 199
Seeing the molecular orbitals of benzene 200
Making the molecular orbital diagram of cyclobutadiene 201
Problem Solving: Determining Aromaticity 202
Problem Solving: Predicting Acidities and Basicities 205
Comparing acidities 205
Comparing basicities 206
Naming Benzenes and Aromatics 207
Common names of substituted benzenes 207
Names of common aromatics 208
Chapter 16: Bringing Out the Howitzers: Reactions of Aromatic Compounds 209
Electrophilic Aromatic Substitution of Benzene 210
Adding alkyl substituents: Friedel-Crafts alkylation 210
Overcoming adversity: Friedel-Crafts acylation 212
Reducing nitro groups 213
Oxidation of alkylated benzenes 213
Adding Two: Synthesis of Disubstituted Benzenes 214
Electron donors: Ortho-para activators 215
Electron-withdrawing groups: Meta directors 215
Problem Solving: Synthesis of Substituted Benzenes 218
Nucleophiles Attack! Nucleophilic Aromatic Substitution 219
Part 4: Spectroscopy And Structure Determination 223
Chapter 17: A Smashing Time: Mass Spectrometry 225
Defining Mass Spectrometry 226
Taking Apart a Mass Spectrometer 226
The inlet 227
Electron ionization: The smasher 227
The sorter and weigher 228
Detector and spectrum 229
The Mass Spectrum 229
Kind and Caring: Sensitivity of Mass Spec 230
Resolving the Problem: Resolution 231
Changing the Weight: Isotopes 231
The Nitrogen Rule 233
Identifying Common Fragmentation Patterns 234
Smashing alkanes 234
Breaking next to a heteroatom: Alpha cleavage 235
Loss of water: Alcohols 236
Rearranging carbonyls: The McLafferty rearrangement 236
Breaking benzenes and double bonds 237
Self test: Working the problem 238
Key Ideas Checklist 239
Chapter 18: Seeing Good Vibrations: IR Spectroscopy 241
Bond Calisthenics: Infrared Absorption 242
Applying Hooke's law to molecules 242
Seeing bond vibration and IR light absorption 244
Seeing absorption intensity 245
IR forbidden stretches 245
Dissecting an IR Spectrum 246
Identifying the Functional Groups 247
Sizing up the IR spectrum 248
Recognizing functional groups 248
Seeing to the Left of the C-H Absorptions 249
Big and fat: The alcohols 249
Milking the spectrum: Amines 250
Seeing to the Right of the C-H Absorptions 250
Big and tall: Carbonyl groups 250
Hydrocarbon stretches: Alkenes, alkynes, and aromatics 250
CHAPTER 19: NMR Spectroscopy: Hold onto Your Hats, You're Going Nuclear! 253
Why NMR? 254
How NMR Works 255
Giant magnets and molecules: NMR theory 255
Grab your jackets: Electron shielding 258
The NMR Spectrum 258
Standardizing chemical shifts 259
Seeing symmetry and chemical equivalency 259
The NMR Spectrum Manual: Dissecting the Pieces 261
Seeing the chemical shift 261
Incorporating the integration 263
Catching on to coupling 264
Considering Carbon NMR 270
Checklist: Putting the Pieces Together 271
Chapter 20: Following the Clues: Solving Problems in NMR 273
Follow the Clues 274
Clue 1: Determine the degrees of unsaturation from the molecular formula 275
Clue 2: Look at the IR spectrum to determine the major functional groups present in the unknown compound 276
Clue 3: Determine the peak ratios by measuring the heights of the integration curves 276
Clue 4: Break the NMR peaks into fragments using the integration from Clue 3 278
Clue 5: Combine the fragments in a way that fits with the NMR peak splitting, the chemical shift, and the degrees of unsaturation 279
Clue 6: Recheck your structure with the NMR and the IR spectrum to make sure it's an exact match 280
Working Problems 281
Example 1: Using the molecular formula and NMR to deduce the structure of a molecule 281
Example 2: Using the molecular formula, IR, and NMR to deduce the structure of a molecule 286
Three Common Mistakes in NMR Problem Solving 290
Mistake #1: Trying to determine a structure from the chemical shift 290
Mistake #2: Starting with coupling 291
Mistake #3: Confusing integration with coupling 291
Part 5: The Part Of Tens 293
Chapter 21: Ten (Or So) Great Organic Chemists 295
August Kekule 295
Friedrich Woehler 296
Archibald Scott Couper 296
Johan Josef Loschmidt 296
Louis Pasteur 296
Emil Fischer 297
Percy Julian 297
Robert Burns Woodward 298
Linus Pauling 298
Dorothy Hodgkin 299
John Pople 299
Chapter 22: Ten Cool Organic Discoveries 301
Explosives and Dynamite! 301
Fermentation 302
The Synthesis of Urea 302
The Handedness of Tartaric Acid 303
Diels-Alder Reaction 303
Buckyballs 304
Soap 305
Aspartame 305
Penicillin 306
Teflon 306
Chapter 23: Ten Cool Organic Molecules 307
Octanitrocubane 307
Fenestrane 308
Carbon Nanotubes 308
Bullvalene 309
The Norbornyl Cation 309
Capsaicin 310
Indigo 310
Maitotoxin 310
Molecular Cages 311
Fucitol 312
Part 6: Appendixes 313
Appendix A: Working Multistep Synthesis Problems 315
Why Multistep Synthesis? 315
The Five Commandments 317
Commandment 1: Thou shalt learn thy reactions 318
Commandment 2: Thou shalt compare carbon skeletons 318
Commandment 3: Thou shalt work backward 319
Commandment 4: Thou shalt check thyne answer 320
Commandment 5: Thou shalt work many problems 321
Appendix B: Working Reaction Mechanisms 323
The Two Unspoken Mechanism Types 324
Do's and Don'ts for Working Mechanisms 325
Types of Mechanisms 327
Appendix C: Glossary 329
Index 339
