Joseph M. Hornback - GBV
19
Organic Chemistry Joseph M. Hornback University of Denver 5t Brooks/Cole Publishing Company I(T)P® An International Thomson Publishing Company Pacific Grove 'Albany • Belmont • Bonn • Boston • Cincinnati • Detroit • Johannesburg • London • Madrid • Melbourne • Mexico City • New York • Paris • Singapore • Mjo • Toronto • Washington
Transcript of Joseph M. Hornback - GBV
Organic Chemistry
Joseph M. Hornback University of Denver
5t Brooks/Cole Publishing Company
I(T)P® An International Thomson Publishing Company
Pacific Grove 'Albany • Belmont • Bonn • Boston • Cincinnati • Detroit • Johannesburg • London • Madrid • Melbourne • Mexico City • New York • Paris • Singapore • M j o • Toronto • Washington
Brief Contents
JL A Simple Mode l for Chemical Bonds 1
/iL Organic Compounds: A First Look 29
J ) Orbitals and Bonding 59
Ah Proton Transfer: A Simple Reaction 105
J) Functional Groups and Nomenclature I 147
lu) Stereochemistry 183
II Nucleophilic Substitution Reactions 257
Elimination Reactions 309
j) Synthetic Uses of Substitution and Elimination Reactions 345
1(0) Additions to Carbon-Carbon Double and Triple Bonds 401
Functional Groups and Nomenclature II 461
Structure Determination by Spectroscopy I: Infrared and Nuclear Magnetic
Resonance Spectroscopy 497
VÜi Brief Contents
13 Structure Determination by Spectroscopy II: Ultraviolet-Visible Spectroscopy and
Mass Spectrometry 607
14 Additions to the Carbonyl Group 635
15 Substitutions at the Carbonyl Group 693
J L O Enolate and Other Carbon Nucleophiles 757
17 Benzene and Aromatic Compounds 807
1(0) Aromatic Substitution Reactions 837
19 The Chemistry of Radicals 903
2(0) Pericyclic Reactions 943
21 The Synthesis of Organic Compounds 7007
Industrial Organic Chemistry 1041
2 3 5 Synthetic Polymers 7069
24 Carbohydrates 7705
25 Amino Acids, Peptides, and Proteins 1145
26 Nucleotides and Nucleic Acids 77S7
27/ Other Natural Products 7279
Contents
1 A Simple Model for Chemical Bonds 1.1 Introduction 1 1.2 The Field of Organic Chemistry 1
Elaboration: The Death of the Vital Force Theory
1.3 Simple Atomic Structure 3 1.4 Ionic Bonding 4 1.5 Covalent Bonding 6 1.6 Lewis Structures 7 1.7 Covalent Ions 10 1.8 Formal Charges 12 1.9 Resonance 16 1.10 Polar Bonds 17 1.11 Shapes of Molecules 19 1.12 Dipole Moments 22 1.13 Summary 24
End-of-Chapter Problems 25
JL Organic Compounds: A First Look 29 2.1 Introduction 29 2.2 Common Bonding Situations 29 2.3 Bond Strengths and Bond Lengths 32 2.4 Structural Isomers 33
Elaboration: Life Based on Silicon? 34
2.5 Degree of Unsaturation 39
Elaboration: Enumerating Structural Isomers 43
ix
•• '•
Contents
2.6 Physical Properties and Molecular Structure 44
2.7 Melting Points, Boiling Points, and Solubilities 46
Elaboration: Melting Point of Cubane 47
Elaboration: Boiling Points of Fuels 48
Elaboration: A Chemical Handwarmer 49 2.8 Introduction to Functional Croups 50 2.9 Summary 53
End-of-Chapter Problems 53
3) Orbitals and Bonding 59 3.1 Introduction 59 3.2 Atomic Orbitals 59
Elaboration: Quantum Numbers 60
3.3 Molecular Orbitals 64 3.4 Single Bonds and sp3 Hybridization 67 3.5 Double Bonds and sp2 Hybridization 70 3.6 Triple Bonds and sp Hybridization 74 3.7 Resonance and MO Theory 77 3.8 Rules for Resonance Structures 80 3.9 Types of Resonance Interactions 84
Elaboration: Resonance Stabilization of theAllyl Radical 88
Elaboration: Resonance and the Bond Lengths of Naphthalene 92
3.10 Molecular Orbital Energies 94
Elaboration: Reaction of Formaldehyde with Sodium 96
3.11 Summary 97
End-of-Chapter Problems 99
4 Proton Transfer: A Simple Reaction 105 4.1 Introduction 105 4.2 Definitions 105 4.3 The Acid-Base Equilibrium 109
Elaboration: Base Dissociation Constants 111
4.4 Rate of the Acid-Base Reaction 115 4.5 Effect of the Atom Bonded to the Hydrogen
on Acidity 117
Contents
4.6 Inductive Effects 119 4.7 Hydrogen Bonding 122 4.8 Hybridization 123
Elaboration: Calcium Carbide 124
4.9 Resonance 125 4.10 Tables of Acids and Bases 131
4.11 Substitution Reactions 134
Elaboration: Acidic and Basic Functional Groups 136
Elaboration: TheAcidity of Solvents 138
Elaboration: Superacids 139 4.12 Summary 140
End-of-Chapter Problems 141
J) Functional Groups and Nomenclature I 147 5.1 Introduction 147 5.2 Alkanes 147 5.3 Common Nomenclature of Alkanes 150
Elaboration: Energy Content of Fuels 151
5.4 Systematic Nomenclature of Alkanes 153 5.5 Systematic Nomenclature of Cycloalkanes 161 5.6 Alkenes 162 5.7 Alkynes 165 5.8 Alkyl Halides 166 5.9 Alcohols 168
Elaboration: Chlorinated Organic Compounds and the Environment 169
Elaboration: Chlorofluorocarbons and the Ozone Hole 171
5.10 Ethers 173 5.11 Amines 175 5.12 Summary 178
End-of-Chapter Problems 178
(6) Stereochemistry 183 6.1 Introduction 183 6.2 Geometricai Isomers 184 6.3 Designating the Connguration of Geometricai
Isomers 188 6.4 Conformations 192
6.5 Conformations of Cyclic Molecules 199 6.6 Conformations of Cyclohexane 203 6.7 Conformations of Other Rings 208 6.8 Conformations of Cyclohexanes with One
Substituent 208
Elaboration: How Much Strain Is Too Much? 209
6.9 Conformations of Cyclohexanes with Two or More Substituents 214
6.10 Chiral Molecules 219 6.11 Recognizing Chiral Molecules 221 6.12 Designating Configuration of Enantiomers 223 6.13 Properties of Enantiomers 227
Elaboration: The D, L Methodfor Designating Absolute Configuration 230
6.14 Molecules with Multiple Chiral Centers 232 6.15 Stereoisomers and Cyclic Compounds 236 6.16 Resolution: Separating Enantiomers 238 6.17 Fischer Projections 239
Elaboration: History of the Development of an Understanding of Stereochemistry 242
6.18 Reactions That Produce Enantiomers 244
Elaboration: Thalidomide and Chiral Synthesis 245
Elaboration: Other Chiral Compounds 246
6.19 Summary 249
End-of-Chapter Problems 250
Nucleophilic Substitution Reactions 257 7.1 Introduction 257 7.2 The General Reaction 258 7.3 Reaction Mechanisms 258 7.4 Bimolecular Nucleophilic Substitution 259 7.5 Stereochemistry of the SN2 Reaction 260 7.6 Effect of Substitutents on the Rate of the
SN2 Reaction 263 7.7 Unimolecular Nucleophilic Substitution 267 7.8 Stereochemistry of the SN1 Reaction 271 7.9 Effects of Substituents on the Rate of the
SN1 Reaction 274
Elaboration: The Triphenylmethyl Carbocation 276
7.10 Leaving Groups 277
Elaboration: Experimental Evidencefor Inversion of Configuration in SN2 Reactions 281
Contents xiii
7.11 Nucleophiles 282 7.12 Effect of Solvent 285 7.13 Competition Between SN1 and SN2 Reactions 288
Elaboration: Chemical Tests Involving SN1 and SN2 Reactions 291
7.14 Intramolecular Reactions 292 7.15 Competing Reactions 293
Elaboration: Carbocation Rearrangements in Superacids 297
7.16 Summary 299
End-of-Chapter Problems 300
o Elimination Reactions 309 8.1 Introduction 309 8.2 The General Reaction 309 8.3 Bimolecular Elimination 310
Elaboration: Investigating Mechanisms I: Kinetic Isotope Effects 311
Elaboration: DDT-Resistant Insects 312 8.4 Stereochemistry of the E2 Reaction 313 8.5 Direction of Elimination 318
Elaboration: Syn Eliminations 319 8.6 Unimolecular Elimination 326
Elaboration: Investigating Mechanisms II: The Competition Between the SN1 and El Pathways 328
8.7 Regiochemistry and Stereochemistry of the El Reaction 329
Elaboration: The Elcb Mechanism 330 8.8 The Competition Between Elimination and
Substitution 332
Elaboration: Biological Elimination Reactions 337 8.9 Summary 338
End-of-Chapter Problems 339
9 Synthetic Uses of Substitution and Elimination Reactions 345 9.1 Introduction 345 9.2 Substitution Reactions 345
xiv Contents
9.3 Preparation of Alcohols 346 9.4 Preparation of Ethers 349
Elaboration: Poisonous A Ikylating Agents 354
9.5 Preparation of Esters 356 9.6 Preparation of Alkyl Halides 357 9.7 Preparation of Amines 361
Elaboration: Biological Methylations 365
9.8 Preparation of Hydrocarbons 366 9.9 Formation of Carbon-Carbon Bonds 367 9.10 Phosphorus and Sulfur Nucleophiles 369 9.11 Ring Opening of Epoxides 370
Elaboration: Sulfur Nucleophiles in Biochemistry 370
9.12 Elimination Reactions 373
Elaboration: Uses of Epoxides in Industry 374
9.13 Elimination of Hydrogen Halides (Dehydrohalogenation) 375
9.14 Preparation of Alkynes 376 9.15 Dehydration 377 9.16 Eliminations to Form Carbon-Oxygen Double Bonds;
Oxidation Reactions 380 9.17 The Strategy of Organic Synthesis 383
Elaboration: Environmental^ Friendly Chemistry (Green Chemistry) 384
Elaboration: Cancer Chemotherapy 388
9.18 Summary 389
End-of-Chapter Problems 394
11(0) Additions to Carbon-Carbon Double and Triple Bonds 401 10.1 Introduction 401 10.2 The General Mechanism 402 10.3 Addition of Hydrogen Halides 403 10.4 Addition of Halogens 409
Elaboration: Formation of Carbocations in Halogen Additions 413
10.5 Halohydrin Formation 415 10.6 Addition of Water (Hydration) 417
Elaboration: Industrial Addition Reactions 419
10.7 Oxymercuration-Reduction 420
Contents XV
10.8 Hydroboration-Oxidation 424
Elaboration: Chiral Boranes in Organic Synthesis 430
10.9 Addition of Carbenes 433
Elaboration: Singlet and Triplet Carbenes 436
10.10 Epoxidation 437 10.11 Hydroxylation 439 10.12 Ozonolysis 440 10.13 Catalytic Hydrogenation 443 10.14 Additions to Conjugated Dienes 446
Elaboration: Asymmetrie Hydrogenation 447
10.15 Summary 449
End-of-Chapter Problems 454
I I Functional Groups and Nomenclature II 461 11.1 Introduction 461 11.2 Aromatic Hydrocarbons 461
Elaboration: Structure Proof by the Number of Isomers 465
11.3 Phenols 466 11.4 Aldehydes and Ketones 469 11.5 Carboxylic Acids 473 11.6 Derivatives of Carboxylic Acids 475
Elaboration: Fragrant Organic Compounds 483
11.7 Sulfur and Phosphorus Compounds 485 11.8 Nomenclature of Compounds with Several Functional
Groups 488
Elaboration: Medicinal Uses of DMSO 488
11.9 Summary 491
End-of-Chapter Problems 492
12! Structure Determination by Spectroscopy I: Infrared and Nuclear Magnetic Resonance Spectroscopy 497 12.1 Introduction 497 12.2 Electromagnetic Radiation 498 12.3 Interaction of Electromagnetic Radiation with
Molecules 499 12.4 The Electromagnetic Spectrum 501
12.5 Infrared Spectroscopy 503 12.6 Generalizations 505 12.7 The Hydrogen Region 506 12.8 The Triple Bond Region 514
Elaboration: Remote Sensing of Automobile Pollutants 516
12.9 The Double-Bond Region 518 12.10 The Fingerprint Region 520 12.11 Interpretation of IR Spectra 522
Elaboration: The Greenhouse Effect 537
12.12 Nuclear Magnetic Resonance Spectroscopy 538 12.13 Theory of ^-NMR 540 12.14 The Chemical Shift 541 12.15 Spin Coupling 551 12.16 Complex Coupling 556 12.17 Chemical Exchange 557 12.18 Deuterium 558
Elaboration: NMR Spectroscopy of Carbocations in Superacid 558
12.19 Interpretation of 'H-NMR Spectra 560
Elaboration: Magnetic Resonance Imaging 566
12.20 Carbon-13 Magnetic Resonance Spectroscopy 567 12.21 Solved Problems Employing IR and NMR
Spectra 575
Elaboration: Use of NMR to Study Reactions 586
12.22 Summary 587
End-of-Chapter Problems 588
Structure Determination by Spectroscopy II: Ultraviolet-Visible Spectroscopy and Mass Spectrometry 601 13.1 Introduction 601 13.2 Ultraviolet-Visible Spectroscopy 601 13.3 Types of Electronic Transitions 604 13.4 UV-Visible Spectroscopy in Structure
Determination 607 13.5 Mass Spectrometry 608
Elaboration: Ozone and Ultraviolet Radiation 609
13.6 Determining the Molecular Formula 610 13.7 Fragmentation of the Molecular Ion 616
Contents xvii
13.8 Summary 626
Elaboration: Gas Chromatography and Mass Spectrometry 626
End-of-Chapter Problems 627
14 Additions to the Carbonyl Group 635 14.1 Introduction 635 14.2 General Mechanisms 636 14.3 Addition of Hydride; Reduction of Aldehydes and
Ketones 638 14.4 Addition of Water 640 14.5 Addition of Hydrogen Cyanide 644 14.6 Preparation and Properties of Organometallic
Nucleophiles 646 14.7 Addition of Organometallic Nucleophiles 649 14.8 Addition of Phosphorus Ylides;
The Wittig Reaction 653
Elaboration: Synthesis of Vitamin A 657
14.9 Addition of Nitrogen Nucleophiles 659
Elaboration: Removal of Water 661
Elaboration: Methamphetamine 667 14.10 Addition of Alcohols 667
Elaboration: Imines in Living Organisms 668
14.11 Conjugate Additions 674
14.12 Summary 678
End-of-Chapter Problems 682
Spectroscopy Problems 691
15 Substitutions at the Carbonyl Group 693 15.1 Introduction 693 15.2 The General Mechanism 693 15.3 Preparation of Acyl Chlorides 699 15.4 Preparation of Anhydrides 701 15.5 Preparation of Esters 702 15.6 Preparation of Carboxylic Acids 705
Elaboration: The Preparation of Soap 708
Elaboration: Establishing the Mechanism of Saponification 710
15.7 Preparation of Amides 715
*
Elaboration: Reaction Conditions 716
15.8 Reaction with Hydride Nucleophiles 718 15.9 Reduction of Acid Derivatives to Aldehydes 722 15.10 Reactions with Organometallic Nucleophiles 724 15.11 Preparation of Ketones 726 15.12 Derivatives of Sulfur and Phosphorus Acids 728
Elaboration: Nerve Gases and Pesticides 730
Elaboration: ATP as an Energy Carrier 732
15.13 Summary 734
End-of-Chapter Problems 739
Problems Involving Spectroscopy 747
11(6 Enolate and Other Carbon Nucleophiles 751 16.1 Introduction 751 16.2 Enols and Enolate Anions 752 16.3 Alkylation of Enolate Anions 755
Elaboration: Isomerization of Sugars 756
16.4 Alkylation of More Stabilized Anions 759 16.5 The Aldol Condensation 765
Elaboration: The Reverse Aldol Reaction in Metabolism 772
16.6 Ester Condensations 772
Elaboration: A n Industrial A Idol Reaction 774
16.7 Enamines 779 16.8 Other Carbon Nucleophiles 780 16.9 Conjugate Additions 784 16.10 Synthesis 787
16.11 Summary 792
End-of-Chapter Problems 796
Problems Involving Spectroscopy 803
1 7 Benzene and Aromatic Compounds 807 17.1 Introduction 807 17.2 Benzene 807 17.3 Resonance Energy of Benzene 809 17.4 Molecular Orbital Model for Cyclic Conjugated
Molecules 811 17.5 Cyclobutadiene 814 17.6 Hückel's Rule 816
Contents xix
17.7 Cyclooctatetraene 817
Elaboration: Isomeric Cyclooctatetraenes 818
17.8 Heterocyclic Aromatic Compounds 819 17.9 Polycyclic Aromatic Hydrocarbons 822
Elaboration: Carcinogenic Polycyclic Aromatic Hydrocarbons 823
Elaboration: Buckminsterfullerene, A New Form of Carbon 824
17.10 NMR and Aromaticity 824 17.11 Annulenes 827 17.12 Aromatic and Antiaromatic Ions 828
17.13 Summary 830
End-of-Chapter Problems 831
Problems Involving Spectroscopy 834
l o Aromatic Substitution Reactions 837 18.1 Introduction 837 18.2 Mechanism for Electrophilic Aromatic
Substitution 837 18.3 Effect of Substitutents 840 18.4 Effect of Multiple Substituents 848 18.5 Nitration 849 18.6 Halogenation 852 18.7 Sulfonation 854 18.8 Friedel-Crafts Alkylation 855
Elaboration: Synthetic Detergents 859
18.9 Friedel-Crafts Acylation 860
Elaboration: Preparation of BHT and BHA 862
18.10 Electrophilic Substitutions of Polycyclic Aromatic Compounds 865
18.11 Nucleophilic Aromatic Substitution; Diazonium Ions 866
18.12 Nucleophilic Aromatic Substitution; Addition-Elimination 869
18.13 Nucleophilic Aromatic Substitution; Elimination-Addition 872
Elaboration: Experimental Evidencefor the Benzyne Mechanism 874
Elaboration: Herbicides, Disinfectants, Dioxin, and Agent Orange 875
Some Additional Useful Reactions 876 Synthesis of Aromatic Compounds 881 Summary 885
End-of-Chapter Problems 890
Problems Invoiving Spectroscopy 900
119 The Chemistry of Radicals 903 19.1 Introduction 903 19.2 Radicals 903 19.3 Stability of Radicals 904 19.4 Geometry of Carbon Radicals 906 19.5 Generation of Radicals 907 19.6 General Radical Reactions 909
Elaboration: The Triphenylmethyl Radical 911
19.7 Kolbe Electrolysis 912 19.8 Halogenation 913 19.9 Dehalogenation 920 19.10 Autoxidation 921
Elaboration: The Industrial Preparation of Phenol 922
Elaboration: Vitamin E and Lipid Autoxidation 924
19.11 Radical Additions to Alkenes 926 19.12 Reductions and Radical Anions 929 19.13 Summary 934
End-of-Chapter Problems 936
Problems Invoiving Spectroscopy 941
2(0) Pericyclic Reactions 20.1 Introduction 943 20.2 Pericyclic Reactions 943 20.3 MO Theory for Conjugated Molecules 20.4 Electrocyclic Reactions 951 20.5 Examples of Electrocyclic Reactions
Elaboration: Dewar Benzene 957
20.6 Cycloaddition Reactions 961 20.7 The Diels-Alder Reaction 963
Elaboration: Diels-Alder Adducts as Pesticides 968
20.8 Other Cycloaddition Reactions 971 20.9 Sigmatropic Rearrangements 972 20.10 Examples of Sigmatropic Rearrangements 977
18.14 18.15 18.16
943
946
956
Contents xxi
Elaboration: Degenerate Rearrangements 979
Elaboration: Suprafacial and Antarafacial Reactions 982
Elaboration: Pericyclic Reactions and Vitamin D 983
20.11 Rearrangements to Electron Deficient Centers 986
20.12 Summary 989
End-of-Chapter Problems 991
Problems Involving Spectroscopy 998
211 The Synthesis of Organic Compounds 1001 21.1 Introduction 1001 21.2 Protective Groups for Alcohols 1001 21.3 Protective Groups for Aldehydes and Ketones 1006 21.4 Protective Groups for Carboxylic Acids 1006 21.5 Protective Groups for Amines 1008 21.6 Retrosynthetic Analysis 1010
Elaboration: Pheromones 1014
21.7 Examples of Syntheses 1016 21.8 Reactions That Form Carbon-Carbon Bonds 1019 21.9 Preparation of Functional Groups 1020 21.10 Summary 1035
End-of-Chapter Problems 1035
22 Industrial Organic Chemistry 1041 22.1 Introduction 1041 22.2 The Organic Chemical Industry 1041 22.3 Important Industrial Organic Chemicals 1042 22.4 Sources of Organic Chemicals 1043 22.5 Chemicals from Ethylene 1046
Elaboration: Carbonylation Reactions 1048
22.6 Chemicals from Propylene 1050
Elaboration: The Metathesis Reaction 1052
22.7 Chemicals from Benzene and Other Aromatic Compounds 1053
Elaboration: Industrial Electrophilic Aromatic Substitution Reactions 1056
Elaboration: Dioctyl Phthalate Plasticizer 1060
22.8 Chemicals from Butylene 1061 22.9 Chemicals from Other Sources 1063
<
xxii Contents
22.10 Summary 1064
End-of-Chapter Problems 1065
Problems Involving Spectroscopy 1068
23] Synthetic Polymers 1069 23.1 Introduction 1069 23.2 Radical Chain Polymerization 1069 23.3 Structures of Polymers 1073 23.4 Ionic Polymerization 1076
Elaboration: Super Glue 1076 23.5 Coordination Polymerization 1078 23.6 Physical Properties of Polymers 1079 23.7 Major Thermoplastic Addition Polymers 1081
Elaboration: Teflon 1082 23.8 Elastomers 1084
Elaboration: Charles Goodyear and Vulcanization 1085 23.9 Condensation Polymers 1087 23.10 Thermoset Polymers 1092
Elaboration: Polybenzimidazole 1092 23.11 Chemical Properties of Polymers 1095
Elaboration: Recycling Plastics 1097 23.12 Summary 1098
End-of-Chapter Problems 1099
2 4 Carbohydrates 1103 24.1 Introduction 1103 24.2 Structures of Carbohydrates 1103 24.3 Stereochemistry of Carbohydrates 1104
Elaboration: R and S Nomenclature Applied to Sugars 1106
24.4 Cyclization of Monosaccharides 1108 24.5 Reactions of Monosaccharides 1113
Elaboration: Determination of Anomer Configuration 1114
Elaboration: A rtificial Sweeteners 1117 24.6 Fischer's Structure Proof for Glucose 1124
Elaboration: Emil Fischer 1130
Contents
24.7 Disaccharides 1130 24.8 Polysaccharides 1132 24.9 Other Carbohydrate-Containing Compounds 1134
Elaboration: Blood Groups 1136
24.10 Summary 1137
End-of-Chapter Problems 1138
Problems Involving Spectroscopy 1143
Amino Acids, Peptides, and Proteins 1145 25.1 Introduction 1145 25.2 Amino Acids 1145 25.3 Acid-Base Chemistry of Amino Acids 1148 25.4 Chemical Reactions of Amino Acids 1152 25.5 Laboratory Synthesis of Amino Acids 1153
Elaboration: Asymmetrie Synthesis of Amino Acids 1157
25.6 Peptides and Proteins 1159
Elaboration: Biosynthesis of Amino Acids from a-Ketoacids 1160
Elaboration: NMR Spectra of Amides 1164
25.7 Sequencing Peptides 1165 25.8 Laboratory Synthesis of Peptides 1170
Elaboration: Frederick Sanger and the Sequence of Insulin 1171
25.9 Protein Structure 1180 25.10 Enzymes 1180 25.11 Summary 1182
End-of-Chapter Problems 1184
26 Nucleotides and Nucleic Acids 1187 26.1 Introduction 1187 26.2 Nucleosides and Nucleotides 1187 26.3 Structure of DNA and RNA 1190
Elaboration: Tautomers of Guanine and Thymine 1193
26.4 Replication, Transcription, and Translation 1196
Elaboration: Base-Catalyzed Hydrolysis of RNA 1196
Elaboration: The Treatment of AIDS with AZT 1199 26.5 Sequencing DNA 1200
xxiv Contents
26.6 Laboratory Synthesis of DNA 1207
Elaboration: Automated DNA Sequencing 1207
Elaboration: DNA Fingerprinting 1208
26.7 Summary 1212
End-of-Chapter Problems 1212
27/ Other Natural Products 1219 27.1 Introduction 1219 27.2 Terpenes 1219 27.3 Monoterpenes 1221 27.4 Sesquiterpenes 1225 27.5 Larger Terpenes 1228
Elaboration: Conformations of Decalin 1228
27.6 Steroids 1233
Elaboration: Syntheses That Mimic Nature 1235
27.7 Synthesis of Steroids 1237
Elaboration: The Birth Control Pill 1239
27.8 Alkaloids 1241 27.9 Fats and Related Compounds 1243
Elaboration: Partialfy Hydrogenated Vegetable Oil 1245
27.10 Prostaglandins 1246
Elaboration: Laboratory Synthesis of Prostaglandins 1248
27.11 Summary 1248
End-of-Chapter Problems 1249
Problems Involving Spectroscopy 1256
Appendix: Answers to Selected In-Chapter Problems AI
Glossary Gl
Index II
