《有机化学》课程教学资源（参考书籍）Organic Chemistry, 3rd Ed, Janice Gorzynski Smith 2011, University of Hawai’i at Ma-noa

Third Edition Organic Chemistry Janice Gorzynski Smith

Periodic Table of the Elements Group number→1A 8 Key H 67 1.0079 He 2 Atomic numbe Ho Symbol 3A 4A 7A 164.92 Atomic weight An element B c 型 ● 三 N 3B 48 5B 6B 7B 8B 8B 8B 1B 29 T Y Co N 兰 7 S 三 型 Rh Ca 2 n·T 5日 7 2 2 27 28 2B4 Lanthanides 6 Ce Nd Pm Sm Gd Tb Ho Er Tm b Lu 器 50 97 94 95 97 8 00 101 102 Actinide Th Pa Am Bk Es Fm Md 310359 24 25j

Period number Group number Lanthanides Actinides Key 1 1 1 H Hydrogen 1.0079 67 Ho Holmium 164.9303 86 Rn Radon (222) 54 Xe Xenon 131.29 36 Kr Krypton 83.80 18 Ar Argon 39.948 10 Ne Neon 20.1797 53 I Iodine 126.9045 35 Br Bromine 79.904 17 Cl Chlorine 35.4527 9 F Fluorine 18.9984 34 Se Selenium 78.96 16 S Sulfur 32.066 8 O Oxygen 15.9994 15 P Phosphorus 30.9738 7 N Nitrogen 14.0067 6 C Carbon 12.011 2 He Helium 4.0026 2 3 Li Lithium 6.941 3 11 Na Sodium 22.9898 4 19 K Potassium 39.0983 5 2 3 4 5 37 Rb Rubidium 85.4678 6 55 Cs Cesium 132.9054 7 87 Fr Francium (223) 4 Be Beryllium 9.0122 12 Mg Magnesium 24.3050 20 Ca Calcium 40.078 38 Sr Strontium 87.62 56 Ba Barium 137.327 88 Ra Radium (226) 21 Sc Scandium 44.9559 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B 39 Y Yttrium 88.9059 22 Ti Titanium 47.88 40 Zr Zirconium 91.224 72 Hf Hafnium 178.49 104 Rf Rutherfordium (267) 23 V Vanadium 50.9415 41 Nb Niobium 92.9064 73 Ta Tantalum 180.9479 105 Db Dubnium (268) 24 Cr Chromium 51.9961 42 Mo Molybdenum 95.94 74 W Tungsten 183.84 106 Sg Seaborgium (271) 25 Mn Manganese 54.9380 43 Tc Technetium (98) 76 Os Osmium 190.2 107 Bh Bohrium (272) 26 Fe Iron 55.845 44 Ru Ruthenium 101.07 77 Ir Iridium 192.22 108 Hs Hassium (270) 27 Co Cobalt 58.9332 45 Rh Rhodium 102.9055 78 Pt Platinum 195.08 109 Mt Meitnerium (276) 28 Ni Nickel 58.693 46 Pd Palladium 106.42 79 Au Gold 196.9665 110 Ds Darmstadtium (281) 29 Cu Copper 63.546 47 Ag Silver 107.8682 80 Hg Mercury 200.59 111 Rg Roentgenium (280) 3A 4A 5A 6A 7A 8A 30 Zn Zinc 65.41 48 Cd Cadmium 112.411 81 Tl Thallium 204.3833 112 – — (285) 31 Ga Gallium 69.723 13 Al Aluminum 26.9815 49 In Indium 114.82 50 Sn Tin 118.710 82 Pb Lead 207.2 83 Bi Bismuth 208.9804 114 – — (289) 84 Po Polonium (209) 6 58 Ce Cerium 140.115 7 6 7 6 7 90 Th Thorium 232.0381 59 Pr Praseodymium 140.9076 91 Pa Protactinium 231.0359 60 Nd Neodymium 144.24 92 U Uranium 238.0289 61 Pm Promethium (145) 93 Np Neptunium (237) 62 Sm Samarium 150.36 94 Pu Plutonium (244) 63 Eu Europium 151.964 95 Am Americium (243) 64 Gd Gadolinium 157.25 96 Cm Curium (247) 65 Tb Terbium 158.9253 97 Bk Berkelium (247) 66 Dy Dysprosium 162.50 98 Cf Californium (251) 67 Ho Holmium 164.9303 99 Es Einsteinium (252) 68 Er Erbium 167.26 100 Fm Fermium (257) 69 Tm Thulium 168.9342 101 Md Mendelevium (258) 70 Yb Ytterbium 173.04 102 No Nobelium (259) 71 Lu Lutetium 174.967 103 Lr Lawrencium (260) 75 Re Rhenium 186.207 116 – — (293) 5 B Boron 10.811 14 Si Silicon 28.0855 32 Ge Germanium 72.64 33 As Arsenic 74.9216 51 Sb Antimony 121.760 52 Te Tellurium 127.60 85 At Astatine (210) 57 La Lanthanum 138.9055 89 Ac Actinium (227) 1A 2A Atomic number Name An element Symbol Atomic weight Periodic Table of the Elements 113 – — (284) 115 – — (288) smi75625_endppFRONT.indd 2 12/2/09 10:14:16 AM

COMMON FUNCTIONAL GROUPS ype of Compound General Structure Example Functional Group Type of Compound General Structure Example Functional Grour chiode Aromatic compound phenyl group R-OH nadoggoep cate eabS9op CH°ScH -COOR R-H CHaCHa R--R CHa-Q-CHa ao X Keton eat9rog .:D halo oup tril R-CaN CHa-CxN: gnSvop -CC- H-C=C-H R--R CHa--CH 8 R-别 Amine 品 am -COSR Anhydride ga具具

Acid chloride Alcohol R Cl O C CH3 NH2 O R N C H (or R) O C H (or R) HR O C 3 HCH O C –COCl Amide Anhydride –CONH2, –CONHR, –CONR2 –OH hydroxy group Carboxylic acid –COOH carboxy group –OR alkoxy group 3 ClCH O C Type of Compound General Structure Example Functional Group Type of Compound General Structure Example Functional Group R OH CH3 OH Alkane R H CH – – 3CH3 Ether Alkyl halide Alkene double bond Aromatic compound phenyl group Aldehyde carbonyl group C O carbonyl group C O cyano group –C N C C H H H H C C Alkyne C C CH C H triple bond Nitrile Amine –NH2 amino group (X = F, Cl, Br, I) R X –X halo group CH3 Br NH2 R or R2NH or R3N CH3 NH2 R R O C O C O O C O C CH3 CH3 O O C O C O OHR O C R R O CH3 O CH3 –SR alkylthio group Sulfide R R S CH3 O C OH Ester –COSR –COOR ORR O C CH3 O C OCH3 RR O Ketone C CH3 O C CH3 Thioester CR N CH3 S CH3 –SH mercapto group Thiol R SH R O C SR CH3 O C SCH3 CH3 SH 3 CCH N COMMON FUNCTIONAL GROUPS smi75625_endppFRONT.indd 3 12/2/09 10:14:16 AM

About the Author Janice Gorzynski Smith was bom in Schene sted in che ell Unive from Harvard Unive sity under the din gibberellic acid. Following her postdoctoral work.Jan joined the faculty of Mount Holyoke College where she was employed for 21 years.During this time she was active in teaching organic chemis try lecture and lab courses,conducting a research program in organic synthesis,and serving as department chair.Her organic chemistry class was named one of Mount Holyoke's "Don't miss courses"in a survey by Boston magazine.After spending two sabbaticals amidst the natu ral beauty and diversity in Hawal I in the n and her family move there permanently ntly a faculty member at the Unr received the Char r chemistry lecture and lab courses.In 2003 sides in Hawaii with her husband Dar four children:Matthew and Zacha eI6P.She a a.a student at Temple University's Beasley School of Law:and cy medicine physician and co-author of the Smudent Guide/Solutions Manual for this text.When not teaching,writing. or enjoying her family,Jan bikes,hikes,snorkels,and scuba dives in sunny Hawai'i,and time permitting.enjoys travel and Hawaiian quilting

iv About the Author Janice Gorzynski Smith was born in Schenectady, New York, and grew up following the Yankees, listening to the Beatles, and water skiing on Sacandaga Reservoir. She became interested in chemistry in high school, and went on to major in chemistry at Cornell University where she received an A.B. degree summa cum laude. Jan earned a Ph.D. in Organic Chemistry from Harvard University under the direction of Nobel Laureate E. J. Corey, and she also spent a year as a National Science Foundation National Needs Postdoctoral Fellow at Harvard. During her tenure with the Corey group she completed the total synthesis of the plant growth hormone gibberellic acid. Following her postdoctoral work, Jan joined the faculty of Mount Holyoke College where she was employed for 21 years. During this time she was active in teaching organic chemis￾try lecture and lab courses, conducting a research program in organic synthesis, and serving as department chair. Her organic chemistry class was named one of Mount Holyoke’s “Don’t￾miss courses” in a survey by Boston magazine. After spending two sabbaticals amidst the natu￾ral beauty and diversity in Hawai‘i in the 1990s, Jan and her family moved there permanently in 2000. She is currently a faculty member at the University of Hawai‘i at Ma-noa, where she teaches the two-semester organic chemistry lecture and lab courses. In 2003, she received the Chancellor’s Citation for Meritorious Teaching. Jan resides in Hawai‘i with her husband Dan, an emergency medicine physician. She has four children: Matthew and Zachary, age 14 (margin photo on page 163); Jenna, a student at Temple University’s Beasley School of Law; and Erin, an emergency medicine physician and co-author of the Student Study Guide/Solutions Manual for this text. When not teaching, writing, or enjoying her family, Jan bikes, hikes, snorkels, and scuba dives in sunny Hawai‘i, and time permitting, enjoys travel and Hawaiian quilting. The author (far right) and her family from the left: husband Dan, and children Zach, Erin, Jenna, and Matt. smi75625_fm_00i-xxxiv.indd iv 11/17/09 11:21:09 AM

Contents in Brief Prologue 1 1 Structure and Bonding 6 2 Acids and Bases 54 Introduction to Organic Molecules and Functional Groups 81 Alkanes 113 5 Stereochemistry 159 6 Understanding organic Reactions 196 1 Alkyl Halides and Nucleophilic Substitution 228 8 Alkyl Halides and Elimination Reactions 278 9 Alcohols,Ethers,and Epoxides 312 10 Alkenes 358 426 Mass Spectrometry and Infrared Spectroscopy 463 14 Nuclear Magnetic Resonance Spectroscopy 494 15 Radical Reactions 538 1617 Conjugation,Resonance,and Dienes 571 Benzene and Aromatic Compounds 607 18 Electrophilic Aromatic Substitution 641 19 Carboxylic Acids and the Acidity of the O-H Bond 688 20 batcenncateelc I Ch mistry;Organometallic Reagents Aldehydes and Keto -Nucleophilic Addition 774 22 Carboxylic Acids and Their Derivatives-Nucleophilic Acyl Substitution 82 2 Substitution Reactions of Carbonyl Compounds at the a Carbon 880 24 Carbonyl Condensation Reactions 916 Amines 949 Carbon-Carbon Bond-Forming Reactions in Organic Synthesis 1002 Carbohydrates 1027 28 Amino Acids and Proteins 1074 29 Lipids 1119 30 Synthetic Polymers 1148 Appendices A-1 Glossary G-1 Credits C-1 Index 1-1

v Contents in Brief Prologue 1 1 Structure and Bonding 6 2 Acids and Bases 54 3 Introduction to Organic Molecules and Functional Groups 81 4 Alkanes 113 5 Stereochemistry 159 6 Understanding Organic Reactions 196 7 Alkyl Halides and Nucleophilic Substitution 228 8 Alkyl Halides and Elimination Reactions 278 9 Alcohols, Ethers, and Epoxides 312 10 Alkenes 358 11 Alkynes 399 12 Oxidation and Reduction 426 13 Mass Spectrometry and Infrared Spectroscopy 463 14 Nuclear Magnetic Resonance Spectroscopy 494 15 Radical Reactions 538 16 Conjugation, Resonance, and Dienes 571 17 Benzene and Aromatic Compounds 607 18 Electrophilic Aromatic Substitution 641 19 Carboxylic Acids and the Acidity of the O–H Bond 688 20 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction 721 21 Aldehydes and Ketones—Nucleophilic Addition 774 22 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution 825 23 Substitution Reactions of Carbonyl Compounds at the α Carbon 880 24 Carbonyl Condensation Reactions 916 25 Amines 949 26 Carbon–Carbon Bond-Forming Reactions in Organic Synthesis 1002 27 Carbohydrates 1027 28 Amino Acids and Proteins 1074 29 Lipids 1119 30 Synthetic Polymers 1148 Appendices A-1 Glossary G-1 Credits C-1 Index I-1 smi75625_fm_00i-xxxiv.indd v 11/17/09 11:21:09 AM

Contents Prologue 1 What Is Organic Chemistry?1 Some Representative Organic Molecules 2 Ginkgolide B-A Complex Organic Compound from the Ginkgo Tree 4 1 Structure and Bonding 6 The Periodic Table 7 订123415 Bonding 70 Lewis Structures 12 1.7 6gO2Mgsr2a 8 Hybridization 32 1.9 Ethane,Ethylene,and Acetylene 36 1.10 Bond Length and Bond Strength 40 1.11 Electronegativity and Bond Polarity 42 1.12 Polarity of Molecules 44 1.13 L-Dopa resentative Organic Molecule 45 Acids and Bases 54 Bronsted-Lowry Acids and Bases 55 2.2 Reactions of Brensted-Lowry Acids and Bases 56 2.3 Acid Strength and pK,58 Predicting the Outcome of Acid-Base Reactions 61 Factors That Determine Acid Strength 62 2.6 Common Acids and Bases 70 Aspirin 71 28 Lewis Acids and Bases 72 ems

vi Contents Preface xviii Acknowledgments xxiii List of How To’s xxv List of Mechanisms xxvii List of Selected Applications xxx Prologue 1 What Is Organic Chemistry? 1 Some Representative Organic Molecules 2 Ginkgolide B—A Complex Organic Compound from the Ginkgo Tree 4 1 Structure and Bonding 6 1.1 The Periodic Table 7 1.2 Bonding 10 1.3 Lewis Structures 12 1.4 Lewis Structures Continued 17 1.5 Resonance 18 1.6 Determining Molecular Shape 23 1.7 Drawing Organic Structures 27 1.8 Hybridization 32 1.9 Ethane, Ethylene, and Acetylene 36 1.10 Bond Length and Bond Strength 40 1.11 Electronegativity and Bond Polarity 42 1.12 Polarity of Molecules 44 1.13 L-Dopa—A Representative Organic Molecule 45 Key Concepts 46 Problems 47 2 Acids and Bases 54 2.1 Brønsted–Lowry Acids and Bases 55 2.2 Reactions of Brønsted–Lowry Acids and Bases 56 2.3 Acid Strength and pKa 58 2.4 Predicting the Outcome of Acid–Base Reactions 61 2.5 Factors That Determine Acid Strength 62 2.6 Common Acids and Bases 70 2.7 Aspirin 71 2.8 Lewis Acids and Bases 72 Key Concepts 74 Problems 75 smi75625_fm_00i-xxxiv.indd vi 11/17/09 11:21:09 AM

Contents 3 Introduction to Organic Molecules and Functional Groups 81 31 Functional groups 82 An Overview of Functional Groups 83 3.3 Intermolecular Forces 87 3.4 3.5 Application:Vitamins 97 9 Application:The Cell mbrane 82 Biomolecules Key Concepts 105 Problems 106 4 Alkanes 113 4.1 Alkanes-An Introduction 114 4.2 Cycloalkanes 118 4.3 Introduction to Nomenclature 119 120 Naming Cy 125 Physical Properties of Alkanes 129 4.9 Conformations of Acyclic Alkanes-Ethane 129 4.10 Conformations of Butane 134 4.11 An Introduction to Cycloalkanes 137 4.12 Cyclohexane 138 4.13 Substituted Cycloalkanes 141 4.14 Oxidation of Alkanes 147 4.15 Lipids-Part 1 149 5 Stereochemistry 159 Starch and Cellulose 160 The Two Major Classes of Isomers 162 Looking Glass Chemistry- -Chiral and Achiral Molecules 163 5.4 Stereogenic Centers 166 5.5 Stereogenic Centers in Cyclic Compounds 168 Labeling Stereogenic Centers with Ror S 170 Diastereomers 175 Rand s Ampounds 177 Compounds with More Ster 5.10 Disubstituted Cycloalkanes 180

Contents vii 3 Introduction to Organic Molecules and Functional Groups 81 3.1 Functional Groups 82 3.2 An Overview of Functional Groups 83 3.3 Intermolecular Forces 87 3.4 Physical Properties 90 3.5 Application: Vitamins 97 3.6 Application of Solubility: Soap 98 3.7 Application: The Cell Membrane 100 3.8 Functional Groups and Reactivity 102 3.9 Biomolecules 104 Key Concepts 105 Problems 106 4 Alkanes 113 4.1 Alkanes—An Introduction 114 4.2 Cycloalkanes 118 4.3 An Introduction to Nomenclature 119 4.4 Naming Alkanes 120 4.5 Naming Cycloalkanes 125 4.6 Common Names 127 4.7 Fossil Fuels 128 4.8 Physical Properties of Alkanes 129 4.9 Conformations of Acyclic Alkanes—Ethane 129 4.10 Conformations of Butane 134 4.11 An Introduction to Cycloalkanes 137 4.12 Cyclohexane 138 4.13 Substituted Cycloalkanes 141 4.14 Oxidation of Alkanes 147 4.15 Lipids—Part 1 149 Key Concepts 151 Problems 153 5 Stereochemistry 159 5.1 Starch and Cellulose 160 5.2 The Two Major Classes of Isomers 162 5.3 Looking Glass Chemistry—Chiral and Achiral Molecules 163 5.4 Stereogenic Centers 166 5.5 Stereogenic Centers in Cyclic Compounds 168 5.6 Labeling Stereogenic Centers with R or S 170 5.7 Diastereomers 175 5.8 Meso Compounds 177 5.9 R and S Assignments in Compounds with Two or More Stereogenic Centers 179 5.10 Disubstituted Cycloalkanes 180 smi75625_fm_00i-xxxiv.indd vii 11/17/09 11:21:11 AM

Contents 5.11 Isomers-A Summary 181 5.12 Physical Properties of Stereoisomers 182 5.13 Chemical Properties of Enantiomers 186 genpt 188 Understanding Organic Reactions 196 刘記的 197 Bond Dissociation Energy 203 Thermodynamics 206 6.6 Enthalpy and Entropy 209 6.7 Energy Diagrams 210 6.8 Energy Diagram for a Two-Step Reaction Mechanism 213 6.9 Kinetics 215 6.10 Catalysts 218 611 Enzymes 219 Alkyl Halides and Nucleophilic Substitution 228 Introduction to Alkyl Halides 229 7233 Nomenclature 230 Physical Properties 231 Interesting Alkyl Halides 232 The Polar Carbon-Halogen Bond 234 治 General Features of Nucleophilic Substitution 235 The Leaving Gr 236 The nucle 238 242 Mechanisms for N The 2 sm Application:Useful SN2 Reactions 250 The SN1 Mechanism 252 7.14 Carbocation Stability 256 7.15 The Hammond Postulate 258 7.16 Application:SN1 Reactions,Nitrosamines,and Cancer 261 7.17 When Is the Mechanism SN1 or SN2?262 7.18 Vinyl Halides and Aryl Halides 267 7.19 rganic Synthesis 267

5.11 Isomers—A Summary 181 5.12 Physical Properties of Stereoisomers 182 5.13 Chemical Properties of Enantiomers 186 Key Concepts 188 Problems 190 6 Understanding Organic Reactions 196 6.1 Writing Equations for Organic Reactions 197 6.2 Kinds of Organic Reactions 198 6.3 Bond Breaking and Bond Making 200 6.4 Bond Dissociation Energy 203 6.5 Thermodynamics 206 6.6 Enthalpy and Entropy 209 6.7 Energy Diagrams 210 6.8 Energy Diagram for a Two-Step Reaction Mechanism 213 6.9 Kinetics 215 6.10 Catalysts 218 6.11 Enzymes 219 Key Concepts 220 Problems 222 7 Alkyl Halides and Nucleophilic Substitution 228 7.1 Introduction to Alkyl Halides 229 7.2 Nomenclature 230 7.3 Physical Properties 231 7.4 Interesting Alkyl Halides 232 7.5 The Polar Carbon–Halogen Bond 234 7.6 General Features of Nucleophilic Substitution 235 7.7 The Leaving Group 236 7.8 The Nucleophile 238 7.9 Possible Mechanisms for Nucleophilic Substitution 242 7.10 Two Mechanisms for Nucleophilic Substitution 243 7.11 The SN2 Mechanism 244 7.12 Application: Useful SN2 Reactions 250 7.13 The SN1 Mechanism 252 7.14 Carbocation Stability 256 7.15 The Hammond Postulate 258 7.16 Application: SN1 Reactions, Nitrosamines, and Cancer 261 7.17 When Is the Mechanism SN1 or SN2? 262 7.18 Vinyl Halides and Aryl Halides 267 7.19 Organic Synthesis 267 Key Concepts 270 Problems 271 viii Contents smi75625_fm_00i-xxxiv.indd viii 11/17/09 11:21:13 AM

Contents 8 Alkyl Halides and Elimination Reactions 278 82 General Features of Elimination 279 Alkenes-The Products of Elimination Reactions 281 8 The Mechanisms of Elimination 285 8.4 The E2 Mechanism 285 8.5 The Zaitsev Rule 288 8.6 The E1 Mechanism 291 8.7 SN1 and E1 Reactions 294 9 Stereochemistry of the E2 Reaction 295 When Is the Me mE1orE2？298 8.10 E2 Reactions and Alky thesis 299 811 When Is the Read ction SN1. 2,E1,0rE2?300 Pro ems Alcohols,Ethers,and Epoxides 312 Introduction 313 Structure and Bonding 314 9.3 Nomenclature 314 5 Physical Properties 318 Interesting alcohols.Ethe and Ep oxides 319 Preparatio of Alcohols.Ethe d ER ides 321 ral Featur -Rea .Ethers s,and Epoxides 323 Dehydration of Alco A 324 arbocation Rearrangemen 34 9.10 Dehydration Using POCl3 and Pyridine 330 9.11 Conversion of Alcohols to Alkyl Halides with HX 331 9.12 Conversion of Alcohols to Alkyl Halides with SOCl2 and PBr3 335 9.13 Tosvlate-Another Good Leaving Group 338 9.14 Reaction of Ethers with Strong Acid 341 9.15 Reactions of Epoxides 343 9.16 Application:Epoxides.Leukotrienes.and Asthma 347 9.17 Application:Benzo[alpyrene,Epoxides,and Cancer 349 349 Alkenes 358 101 Introduction 359 10.2 Calculating Degrees of Unsaturation 360 10.3 Nomenclature 362 10.4 Physical Properties 365 10.5 Interesting Alkenes 366 10.6 Lipids-Part 2 366 10.7 Preparation of Alkenes 369 10.8 Introduction to Addition Reactions 370

Contents ix 8 Alkyl Halides and Elimination Reactions 278 8.1 General Features of Elimination 279 8.2 Alkenes—The Products of Elimination Reactions 281 8.3 The Mechanisms of Elimination 285 8.4 The E2 Mechanism 285 8.5 The Zaitsev Rule 288 8.6 The E1 Mechanism 291 8.7 SN1 and E1 Reactions 294 8.8 Stereochemistry of the E2 Reaction 295 8.9 When Is the Mechanism E1 or E2? 298 8.10 E2 Reactions and Alkyne Synthesis 299 8.11 When Is the Reaction SN1, SN2, E1, or E2? 300 Key Concepts 304 Problems 305 9 Alcohols, Ethers, and Epoxides 312 9.1 Introduction 313 9.2 Structure and Bonding 314 9.3 Nomenclature 314 9.4 Physical Properties 318 9.5 Interesting Alcohols, Ethers, and Epoxides 319 9.6 Preparation of Alcohols, Ethers, and Epoxides 321 9.7 General Features—Reactions of Alcohols, Ethers, and Epoxides 323 9.8 Dehydration of Alcohols to Alkenes 324 9.9 Carbocation Rearrangements 328 9.10 Dehydration Using POCl3 and Pyridine 330 9.11 Conversion of Alcohols to Alkyl Halides with HX 331 9.12 Conversion of Alcohols to Alkyl Halides with SOCl2 and PBr3 335 9.13 Tosylate—Another Good Leaving Group 338 9.14 Reaction of Ethers with Strong Acid 341 9.15 Reactions of Epoxides 343 9.16 Application: Epoxides, Leukotrienes, and Asthma 347 9.17 Application: Benzo[a]pyrene, Epoxides, and Cancer 349 Key Concepts 349 Problems 351 10 Alkenes 358 10.1 Introduction 359 10.2 Calculating Degrees of Unsaturation 360 10.3 Nomenclature 362 10.4 Physical Properties 365 10.5 Interesting Alkenes 366 10.6 Lipids—Part 2 366 10.7 Preparation of Alkenes 369 10.8 Introduction to Addition Reactions 370 smi75625_fm_00i-xxxiv.indd ix 11/17/09 11:21:19 AM

Contents 10.9 Hydrohalogenation-Electrophilic Addition of HX 371 10.10 Markovnikov's Rule 374 10.11 Stereochemistry of Electrophilic Addition of HX 376 10.12 Hydration-Electrophilic Addition of Water 378 10.13 Halogenation-Addition of Halogen 379 10.14 Stere ochemistry of Halogenation 381 10.15 Halohydrin Fo ation 383 385 Keeping Track of Rec 39 9 Key Concepts 393 Problems 394 11 Alkynes 399 11.1 Introduction 400 11.2 Nomenclature 401 11.3 402 114 Interesti e5402 11.5 4 n to Alkyne Rea ions 11.8 Addition of Halogen 11.9 Addition of Water 11.10 Hydroboration-Oxidation 412 11.11 Reaction of Acetylide Anions 414 11.12 Synthesis 417 Key Concepts 419 Problems 421 12 Oxidation and Reduction 426 educing Ag 428 428 Application:Hydrogenation of Oils 432 12.5 Reduction of Alkynes 434 12.6 The Reduction of Polar C-X o Bonds 437 12.7 Oxidizing Agents 438 12.8 Epoxidation 439 12.9 Dihydroxylation 442 12.10 Oxidative Cleavage of Alkenes 444 12.11 Oxidative Cleavage of Alkynes 446 12.12 Oxidation of Alcc nols 447 12.13 Greer Ch y t on:Th Oxidat of Ethanol 451 451 Key Concepts 454 Problems 457

x Contents 10.9 Hydrohalogenation—Electrophilic Addition of HX 371 10.10 Markovnikov’s Rule 374 10.11 Stereochemistry of Electrophilic Addition of HX 376 10.12 Hydration—Electrophilic Addition of Water 378 10.13 Halogenation—Addition of Halogen 379 10.14 Stereochemistry of Halogenation 381 10.15 Halohydrin Formation 383 10.16 Hydroboration–Oxidation 385 10.17 Keeping Track of Reactions 390 10.18 Alkenes in Organic Synthesis 391 Key Concepts 393 Problems 394 11 Alkynes 399 11.1 Introduction 400 11.2 Nomenclature 401 11.3 Physical Properties 402 11.4 Interesting Alkynes 402 11.5 Preparation of Alkynes 404 11.6 Introduction to Alkyne Reactions 405 11.7 Addition of Hydrogen Halides 406 11.8 Addition of Halogen 409 11.9 Addition of Water 409 11.10 Hydroboration–Oxidation 412 11.11 Reaction of Acetylide Anions 414 11.12 Synthesis 417 Key Concepts 419 Problems 421 12 Oxidation and Reduction 426 12.1 Introduction 427 12.2 Reducing Agents 428 12.3 Reduction of Alkenes 428 12.4 Application: Hydrogenation of Oils 432 12.5 Reduction of Alkynes 434 12.6 The Reduction of Polar C–X σ Bonds 437 12.7 Oxidizing Agents 438 12.8 Epoxidation 439 12.9 Dihydroxylation 442 12.10 Oxidative Cleavage of Alkenes 444 12.11 Oxidative Cleavage of Alkynes 446 12.12 Oxidation of Alcohols 447 12.13 Green Chemistry 450 12.14 Application: The Oxidation of Ethanol 451 12.15 Sharpless Epoxidation 451 Key Concepts 454 Problems 457 smi75625_fm_00i-xxxiv.indd x 11/17/09 11:21:23 AM