02_569023 ftoc.qxd 6/3/05 11:47 PM Page v Contents at a Glance Introduction .................................................................1 Part I: Going Organic: The Chemistry of Carbon ..............9 Chapter 1: The Wonderful World of Organic Chemistry .............................................11 Chapter 2: Dissecting Atoms: Atomic Structure and Bonding....................................19 Chapter 3: Speaking with Pictures: Drawing Structures..............................................41 Chapter 4: Covering the Bases (And the Acids)...........................................................65 Chapter 5: Reactivity Centers: Functional Groups.......................................................77 Chapter 6: Seeing in 3-D: Stereochemistry....................................................................93 Part II: Hydrocarbons ...............................................111 Chapter 7: The Bones of Organic Molecules: The Alkanes .......................................113 Chapter 8: Seeing Double: The Alkenes.......................................................................141 Chapter 9: It Takes Alkynes: The Carbon-Carbon Triple Bond.................................169 Part III: Functional Groups........................................177 Chapter 10: Replacing and Removing: Substitution and Elimination Reactions....179 Chapter 11: Getting Drunk on Organic Molecules: The Alcohols.............................195 Chapter 12: Side-By-Side: Conjugated Alkenes and the Diels-Alder Reaction ........205 Chapter 13: Lord of the Rings: Aromatic Compounds...............................................215 Part IV: Spectroscopy and Structure Determination .....247 Chapter 14: A Smashing Time: Mass Spectrometry...................................................249 Chapter 15: Seeing Good Vibrations: IR Spectroscopy..............................................267 Chapter 16: NMR Spectroscopy: Hold on to Your Hats, You’re Going Nuclear! .....279 Chapter 17: FollowingCOPYRIGHTED the Clues: Solving Problems MATERIAL in NMR.....................................301 Part V: The Part of Tens ............................................321 Chapter 18: Ten Keys for Surviving Orgo ....................................................................323 Chapter 19: Ten Cool Organic Discoveries..................................................................329 Chapter 20: Ten Great Organic Chemists ....................................................................337 02_569023 ftoc.qxd 6/3/05 11:47 PM Page vi Part VI: Appendixes ..................................................343 Appendix A: Working Multistep Synthesis Problems ................................................345 Appendix B: Working Reaction Mechanisms ..............................................................353 Appendix C: Glossary ....................................................................................................361 Index .......................................................................373 02_569023 ftoc.qxd 6/3/05 11:47 PM Page vii Table of Contents Introduction..................................................................1 About This Book...............................................................................................2 Conventions Used in This Book .....................................................................3 Foolish Assumptions .......................................................................................3 How This Book Is Organized...........................................................................4 Part I: Going Organic: The Chemistry of Carbon................................4 Part II: Hydrocarbons.............................................................................5 Part III: Functional Groups ....................................................................5 Part IV: Spectroscopy and Structure Determination .........................6 Part V: The Part of Tens.........................................................................6 Part VI: Appendixes................................................................................6 Icons Used in This Book..................................................................................6 Where to Go from Here....................................................................................7 Part I: Going Organic: The Chemistry of Carbon...............9 Chapter 1: The Wonderful World of Organic Chemistry . .11 Shaking Hands with Organic Chemistry......................................................11 What Are Organic Molecules, Exactly?........................................................13 An Organic Chemist by Any Other Name . ...............................................14 Synthetic organic chemist...................................................................15 Bioorganic chemist ..............................................................................15 Natural products chemist ...................................................................16 Physical organic chemist.....................................................................17 Organometallic chemist.......................................................................17 Computational chemist .......................................................................17 Materials chemist.................................................................................18 Chapter 2: Dissecting Atoms: Atomic Structure and Bonding . .19 Electron House-Arrest: Shells and Orbitals ................................................20 Electron apartments: Orbitals ............................................................21 Electron instruction manual: Electron configuration ......................23 Atom Marriage: Bonding ...............................................................................24 To Share or Not to Share: Ionic and Covalent Bonding.............................25 Mine! They’re all mine! Ionic bonding................................................25 The name’s Bond, Covalent Bond ......................................................27 Electron piggishness and electronegativity......................................27 02_569023 ftoc.qxd 6/3/05 11:47 PM Page viii viii Organic Chemistry I For Dummies Separating Charge: Dipole Moments ...........................................................29 Problem solving: Predicting bond dipole moments.........................30 Problem solving: Predicting molecule dipole moments..................31 Seeing Molecular Geometries.......................................................................32 Mixing things up: Hybrid orbitals ......................................................33 Predicting hybridization for atoms....................................................35 It’s All Greek to Me: Sigma and Pi Bonding .................................................36 Chapter 3: Speaking with Pictures: Drawing Structures . .41 Picture-Talk: Lewis Structures......................................................................43 Taking charge: Assigning formal charges ..........................................43 Drawing structures...............................................................................45 Atom packing: Condensed structures ...............................................46 Structural shorthand: Line-bond structures.....................................47 Converting Lewis structures to line-bond structures......................48 Determining the number of hydrogens on line-bond structures ..........................................................................................49 So lonely: Determining lone pairs on atoms .....................................51 Problem Solving: Arrow Pushing..................................................................51 Drawing Resonance Structures ....................................................................53 Rules for resonance structures ..........................................................54 Problem solving: Drawing resonance structures .............................56 Drawing more than two resonance structures .................................59 Assigning importance to resonance structures ...............................60 Common mistakes in drawing resonance structures ......................62 Chapter 4: Covering the Bases (And the Acids) . .65 A Defining Moment: Acid-Base Definitions .................................................66 Arrhenius acids and bases: A little watery .......................................66 Pulling for protons: Brønsted acids and bases.................................67 Electron lovers and haters: Lewis acids and bases .........................68 Comparing Acidities of Organic Molecules.................................................69 Comparing atoms .................................................................................70 Seeing atom hybridization ..................................................................71 Seeing electronegativity effects..........................................................72 Seeing resonance effects .....................................................................72 Defining pKa: A Quantitative Scale of Acidity.............................................73 Problem Solving: Predicting the Direction of Acid-Base Reactions at Equilibrium ...........................................................................74 Chapter 5: Reactivity Centers: Functional Groups . .77 Hydrocarbons.................................................................................................78