Organic Chemistry

Cover Page......Page 1
Periodic Table of Elements......Page 2
Common Functional Groups......Page 3
Organic ChemistryNow......Page 4
Title Page......Page 11
ISBN 0534389511......Page 12
About the Author......Page 14
Brief Contents......Page 15
3 Orbitals and Bonding......Page 16
6 Stereochemistry I: Cis–Trans Isomers and Conformations......Page 17
8 Nucleophilic Substitution Reactions: Reactions of Alkyl Halides, Alcohols, and Related Compounds......Page 18
10 Synthetic Uses of Substitution and Elimination Reactions: Interconverting Functional Groups......Page 19
12 Functional Groups and Nomenclature II......Page 20
15 Ultraviolet-Visible Spectroscopy and Mass Spectrometry......Page 21
18 Additions to the Carbonyl Group: Reactions of Aldehydes and Ketones......Page 22
20 Enolate and Other Carbon Nucleophiles......Page 23
22 Pericyclic Reactions......Page 24
25 Carbohydrates......Page 25
Appendix: Answers to In-Chapter Problems, Glossary, Index......Page 26
List of Mechanisms......Page 27
Preface......Page 30
Changes in This Edition......Page 31
Introducing Organic ChemistryNow......Page 32
Support Package......Page 34
Acknowledgments......Page 36
1.1 The Field of Organic Chemistry......Page 37
1.2 Simple Atomic Structure......Page 39
1.3 Ionic Bonding......Page 40
1.4 Covalent Bonding......Page 41
1.5 Lewis Structures......Page 42
1.7 Formal Charges......Page 47
1.8 Resonance......Page 51
1.9 Polar Bonds......Page 53
1.10 Shapes of Molecules......Page 54
1.11 Dipole Moments......Page 58
Review of Mastery Goals......Page 60
Additional Problems......Page 61
2.1 Common Bonding Situations......Page 66
2.2 Bond Strengths and Bond Lengths......Page 69
2.3 Constitutional Isomers......Page 70
2.4 Degree of Unsaturation......Page 75
2.5 Physical Properties and Molecular Structure......Page 80
2.6 Melting Points, Boiling Points, and Solubilities......Page 82
Focus On: Boiling Points of Fuels......Page 84
2.7 Introduction to Functional Groups......Page 86
Review of Mastery Goals......Page 88
Additional Problems......Page 89
3.1 Atomic Orbitals......Page 97
3.2 Molecular Orbitals......Page 101
3.3 Single Bonds and sp[sup(3)] Hybridization......Page 105
3.4 Double Bonds and sp[sup(2)] Hybridization......Page 107
3.5 Triple Bonds and sp Hybridization......Page 112
3.6 Resonance and Mo Theory......Page 114
3.7 Rules for Resonance Structures......Page 117
3.8 Types of Resonance Interactions......Page 122
Focus On: Resonance and the Bond Lengths of Naphthalene......Page 130
3.9 Molecular Orbital Energies......Page 131
Additional Problems......Page 133
4.1 Definitions......Page 139
4.2 The Acid-Base Equilibrium......Page 143
4.3 Rate of the Acid-Base Reaction......Page 147
4.4 Effect of the Atom Bonded to the Hydrogen on Acidity......Page 150
4.5 Inductive Effects......Page 152
4.6 Hydrogen Bonding......Page 155
4.8 Resonance......Page 156
Focus On: Calcium Carbide......Page 157
4.9 Tables of Acids and Bases......Page 164
4.10 Acidity and Basicity of Functional Groups and Solvents......Page 168
Additional Problems......Page 171
5.1 Alkanes......Page 178
5.2 Common Nomenclature of Alkanes......Page 181
Focus On: The Energy Content of Fuels......Page 182
5.4 Systematic Nomenclature of Cycloalkanes......Page 191
5.5 Alkenes......Page 193
5.6 Alkynes......Page 196
5.7 Alkyl Halides......Page 197
5.8 Alcohols......Page 198
Focus On Biological Chemistry: Chlorinated Organic Compounds......Page 200
5.9 Ethers......Page 203
5.10 Amines......Page 204
Review Of Mastery Goals......Page 207
Additional Problems......Page 208
6 STEREOCHEMISTRY I: CIS–TRANS ISOMERS AND CONFORMATIONS......Page 214
6.1 Cis-Trans Isomers......Page 215
6.2 Designating the Configuration of Cis-Trans Isomers......Page 219
6.3 Conformations......Page 222
6.4 Conformations of Cyclic Molecules......Page 229
6.5 Conformations of Cyclohexane......Page 232
6.6 Conformations of Other Rings......Page 237
6.7 Conformations of Cyclohexanes with One Substituent......Page 238
6.8 Conformations of Cyclohexanes with Two or More Substituents......Page 241
Focus On: How Much Strain Is Too Much?......Page 242
Additional Problems......Page 250
7.1 Chiral Molecules......Page 255
7.2 Recognizing Chiral Molecules......Page 257
7.3 Designating Configuration of Enantiomers......Page 260
7.4 Properties of Enantiomers......Page 263
7.5 Molecules with Multiple Chirality Centers......Page 266
7.6 Stereoisomers and Cyclic Compounds......Page 270
7.7 Resolution: Separating Enantiomers......Page 272
7.8 Fischer Projections......Page 273
Focus On: The Historical Development of Understanding Stereochemistry......Page 274
7.9 Reactions That Produce Enantiomers......Page 278
Focus On: Pharmaceuticals and Chirality......Page 279
7.10 Other Chiral Compounds......Page 280
Review of Mastery Goals......Page 283
Visual Summary of Isomers......Page 284
Additional Problems......Page 285
8.1 The General Reaction......Page 293
8.3 Bimolecular Nucleophilic Substitution......Page 295
8.4 Stereochemistry of the SN[sup[2]) Reaction......Page 297
8.5 Effect of Substituents on the Rate of the SN[sup(2)] Reaction......Page 300
8.6 Unimolecular Nucleophilic Substitution......Page 304
8.7 Effect of Substituents on the Rate of the SN[sup(1)] Reaction......Page 308
Focus On: The Triphenylmethyl Carbocation......Page 310
8.8 Stereochemistry of the SN[sup(1)] Reaction......Page 312
8.9 Leaving Groups......Page 315
8.10 Nucleophiles......Page 320
8.11 Effect of Solvent......Page 322
8.12 Competition Between SN[sup(1)] And SN[(2)] Reactions......Page 325
8.13 Intramolecular Reactions......Page 328
8.14 Competing Reactions......Page 330
Focus On: Carbocation Rearrangements in Superacids......Page 335
Visual Summary of Key Reactions......Page 337
Additional Problems......Page 338
9.1 The General Reaction......Page 349
9.2 Biomolecular Elimination......Page 350
9.3 Stereochemistry of the E2 Reaction......Page 352
9.4 Direction of Elimination......Page 359
9.5 Unimolecular Elimination......Page 365
9.6 Regiochemistry and Stereochemistry of the E1 Reaction......Page 367
Focus On: The E1cb Mechanism......Page 369
9.7 The Competition Between Elimination and Substitution......Page 370
Focus On Biological Chemistry: Biological Elimination Reactions......Page 376
Additional Problems......Page 377
10.1 Substitution Reactions......Page 384
10.2 Preparation of Alcohols......Page 385
10.3 Preparation of Ethers......Page 388
10.4 Preparation of Esters......Page 393
10.5 Preparation of Alkyl Halides......Page 394
10.6 Preparation of Amines......Page 398
Focus On Biological Chemistry: Biological Alkylations and Poisons......Page 401
10.7 Preparation of Hydrocarbons......Page 404
10.8 Formation of Carbon-Carbon Bonds......Page 405
10.9 Phosphorus and Sulfur Nucleophiles......Page 407
10.10 Ring Opening of Epoxides......Page 408
Focus On: Uses of Epoxides in Industry......Page 411
10.11 Elimination of Hyderogen Halide (Dehydrahalogenation)......Page 412
10.12 Preparation of Alkynes......Page 413
10.13 Dehydration......Page 414
10.14 Eliminations to Form Carbon-oxygen Double Bonds; Oxidation Reactions......Page 416
Focus On: Environmentally Friendly Chemistry (Green Chemistry)......Page 420
10.15 The Strategy of Organic Synthesis......Page 421
Review of Mastery Goals......Page 425
Visual Summary of Key Reactions......Page 426
Integrated Practice Problem......Page 430
Additional Problems......Page 431
11 ADDITIONS TO CARBON–CARBON DOUBLE AND TRIPLE BONDS: REACTIONS OF ALKENES AND ALKYNES......Page 440
11.1 The General Mechanism......Page 441
11.2 Addition of Hydrogen Halides......Page 442
11.3 Addition of Water (hydration)......Page 448
11.4 Addition of Halogens......Page 449
11.5 Halohydrin Formation......Page 455
Focus On: Industrial Addition Reactions......Page 457
11.6 Oxymercuration-reduction......Page 459
11.7 Hydroboration-oxidation......Page 462
Focus On: Chiral Boranes in Organic Synthesis......Page 469
11.8 Addition Of Carbenes......Page 471
11.9 Epoxidation......Page 474
11.10 Hydroxylation......Page 475
11.11 Ozonolysis......Page 477
11.12 Catalytic Hydrogenation......Page 480
11.13 Additions to Conjugated Dienes......Page 482
Focus On: Asymmetric Hydrogenation......Page 485
11.14 Synthesis......Page 487
Review Of Mastery Goals......Page 489
Visual Summary of Key Reactions......Page 490
Integrated Practice Problem......Page 493
Additional Problems......Page 494
12.1 Aromatic Hydrocarbons......Page 502
Focus On: Structure Proof by the Number of Isomers......Page 505
12.2 Phenols......Page 508
12.3 Aldehydes and Ketones......Page 509
12.4 Carboxylic Acids......Page 513
12.5 Derivatives of Carboxylic Acids......Page 515
Focus On: Fragrant Organic Compounds......Page 522
12.6 Sulfur and Phosphorus Compounds......Page 524
12.7 Nomenclature of Compounds with Several Functional Groups......Page 527
Additional Problems......Page 530
13 INFRARED SPECTROSCOPY......Page 536
13.1 Electromagnetic Radiation......Page 537
13.2 Interaction of Electromagnetic Radiation with Molecules......Page 538
13.3 The Electromagnetic Spectrum......Page 539
13.4 Infrared Spectroscopy......Page 541
13.5 Generalizations......Page 543
13.6 The Hydrogen Region......Page 544
13.7 The Triple-bond Region......Page 551
Focus On: Remote Sensing of Automobile Pollutants......Page 552
13.8 The Double-bond Region......Page 554
13.9 The Fingerprint Region......Page 556
13.10 Interpretation of Ir Spectra......Page 557
Additional Problems......Page 569
14.1 Proton Magnetic Resonance Spectroscopy......Page 579
14.2 Theory of [sup[1])H-NMR......Page 581
14.3 The Chemical Shift......Page 583
14.4 Spin Coupling......Page 592
14.5 Complex Coupling......Page 598
14.7 Deuterium......Page 599
Focus On: NMR Spectroscopy of Carbocations in Superacid......Page 601
14.8 Interpretation of [sup[1])H-NMR Spectra......Page 602
Focus On: Magnetic Resonance Imaging......Page 608
14.9 Carbon-13 Magnetic Resonance Spectroscopy......Page 610
14.10 Solved Problems Employing IR And NMR Spectra......Page 619
Review Of Mastery Goals......Page 631
Additional Problems......Page 632
15.1 Ultraviolet-visible Spectroscopy......Page 645
15.2 Types of Electronic Transitions......Page 648
15.3 UV-Visible Spectroscopy In Structure Determination......Page 651
Focus On: Ozone, Ultraviolet Radiation, and Sunscreens......Page 652
15.4 Mass Spectrometry......Page 653
15.5 Determining the Molecular Formula......Page 655
15.6 Fragmentation Of The Molecualr Ion......Page 660
Focus On: Gas Chromatography and Mass Spectrometry......Page 669
Additional Problems......Page 670
16.1 Benzene......Page 678
16.2 Resonance Energy Of Benzene......Page 680
16.3 Molecular Orbital Model For Cyclic Conjugated Molecules......Page 682
16.4 Cyclobutadiene......Page 685
16.5 Huckel\'s Rule......Page 687
16.6 Cyclooctatetraene......Page 688
16.7 Heterocyclic Aromatic Compounds......Page 689
16.8 Polycyclic Aromatic Hydrocarbons......Page 691
16.9 Nmr And Aromaticity......Page 693
16.10 Annulenes......Page 695
16.11 Aromatic And Antiaromatic Ions......Page 697
Focus On: Buckminsterfullerene, a New Form of Carbon......Page 699
Additional Problems......Page 701
17.1 Mechanism for Electrophilic Aromatic Substitution......Page 707
17.2 Effect of Substituents......Page 710
17.3 Effect of Multiple Substituents......Page 718
17.4 Nitration......Page 719
17.5 Halogenation......Page 722
17.6 Sulfonation......Page 725
17.7 Friedel-Crafts Alkylation......Page 726
Focus On: Synthetic Detergents, BHT, and BHA......Page 730
17.8 Friedel-Crafts Acylation......Page 732
17.9 Electrophilic Substitutions of Polycyclic Aromatic Compounds......Page 735
17.10 Nucleophilic Aromatic Substitution: Diazonium Ions......Page 736
17.11 Nucleophilic Aromatic Substitution: Addition–Elimination......Page 739
17.12 Nucleophilic Aromatic Substitution: Elimination–Addition......Page 741
Focus On: Experimental Evidence for the Benzyne Mechanism......Page 744
17.13 Some Additional Useful Reactions......Page 745
17.14 Synthesis of Aromatic Compounds......Page 749
Visual Summary of Key Reactions......Page 755
Integrated Practice Problem......Page 759
Additional Problems......Page 760
18 ADDITIONS TO THE CARBONYL GROUP: REACTIONS OF ALDEHYDES AND KETONES......Page 775
18.1 General Mechanisms......Page 776
18.2 Addition of Hydride; Reduction of Aldehydes and Ketones......Page 778
18.3 Addition of Water......Page 780
18.4 Addition of Hydrogen Cyanide......Page 784
18.5 Preparation and Properties of Organometallic Nucleophiles......Page 787
18.6 Addition of Organometallic Nucleophiles......Page 789
18.7 Addition of Phosphorus Ylides; The Wittig Reaction......Page 794
Focus On: Synthesis of Vitamin A......Page 799
18.8 Addition of Nitrogen Nucleophiles......Page 801
Focus On Biological Chemistry: Imines in Living Organisms......Page 809
18.9 Addition of Alcohols......Page 811
18.10 Conjugate Additions......Page 815
18.11 Synthesis......Page 820
Visual Summary of Key Reactions......Page 823
Integrated Practice Problem......Page 825
Additional Problems......Page 826
19.1 The General Mechanism......Page 839
19.2 Preparation of Acyl Chlorides......Page 844
19.3 Preparation of Anhydrides......Page 846
19.4 Preparation of Esters......Page 847
19.5 Preparation of Carboxylic Acids......Page 851
Focus On: The Preparation of Soap......Page 855
19.6 Preparation of Amides......Page 860
19.7 Reaction with Hydride Nucleophiles......Page 862
19.8 Reduction of Acid Derivatives to Aldehydes......Page 866
19.9 Reactions with Organometallic Nucleophiles......Page 868
19.10 Preparation of Ketones......Page 870
19.11 Derivatives of Sulfur and Phosphorus Acids......Page 872
Focus On Biological Chemistry: Nerve Gases and Pesticides......Page 874
Visual Summary of Key Reactions......Page 876
Additional Problems......Page 879
20 ENOLATE AND OTHER CARBON NUCLEOPHILES......Page 894
20.1 Enols and Enolate Anions......Page 895
20.2 Halogenation of the  -Carbon......Page 898
20.3 Alkylation of Enolate Anions......Page 900
20.4 Alkylation of More Stabilized Anions......Page 903
20.5 The Aldol Condensation......Page 909
20.6 Ester Condensations......Page 916
Focus On: An Industrial Aldol Reaction......Page 922
20.7 Carbon and Hydrogen Leaving Groups......Page 923
20.8 Enamines......Page 925
20.9 Other Carbon Nucleophiles......Page 927
20.10 Conjugate Additions......Page 930
20.11 Synthesis......Page 934
Visual Summary of Key Reactions......Page 938
Integrated Practice Problem......Page 940
Additional Problems......Page 941
21.1 Radicals......Page 954
21.2 Stability of Radicals......Page 955
21.3 Geometry of Carbon Radicals......Page 957
21.4 Generation of Radicals......Page 958
21.5 General Radical Reactions......Page 959
Focus On: The Triphenylmethyl Radical......Page 962
21.6 Halogenation......Page 963
21.7 Dehalogenation......Page 970
21.8 Autoxidation......Page 971
Focus On Biological Chemistry: Vitamin E and Lipid Autoxidation......Page 973
21.9 Radical Additions to Alkenes......Page 975
21.10 Reductions and Radical Anions......Page 977
Review of Mastery Goals......Page 982
Visual Summary of Key Reactions......Page 983
Additional Problems......Page 984
22.1 Pericyclic Reactions......Page 992
22.2 MO Theory for Conjugated Molecules......Page 995
22.3 Electrocyclic Reactions......Page 1001
22.4 Examples of Electrocyclic Reactions......Page 1006
Focus On: Dewar Benzene......Page 1009
22.5 Cycloaddition Reactions......Page 1011
22.6 The Diels-Alder Reaction......Page 1013
22.7 Other Cycloaddition Reactions......Page 1020
22.8 Sigmatropic Rearrangements......Page 1022
22.9 Examples of Sigmatropic Rearrangements......Page 1026
Focus On Biological Chemistry: Pericyclic Reactions and Vitamin D......Page 1029
22.10 Rearrangements to Electron-Deficient Centers......Page 1030
Visual Summary of Key Reactions......Page 1035
Additional Problems......Page 1037
23.1 Protecting Groups for Alcohols......Page 1047
23.2 Protecting Groups for Aldehydes and Ketones......Page 1051
23.3 Protecting Groups for Carboxylic......Page 1052
23.4 Protecting Groups for Amines......Page 1054
23.5 Retrosynthetic Analysis......Page 1056
Focus On Biological Chemistry: Pheromones......Page 1061
23.6 Examples of Syntheses......Page 1062
23.7 Reactions That Form Carbon–Carbon Bonds......Page 1065
23.8 Preparation of Functional Groups......Page 1066
Review of Mastery Goals......Page 1081
Additional Problems......Page 1082
24.1 Radical Chain Polymerization......Page 1089
24.2 Structures of Polymers......Page 1093
24.3 Ionic Polymerization......Page 1096
24.4 Coordination Polymerization......Page 1098
24.5 Physical Properties of Polymers......Page 1100
24.6 Major Thermoplastic Addition Polymers......Page 1102
24.7 Elastomers......Page 1104
24.8 Condensation Polymers......Page 1106
24.9 Thermoset Polymers......Page 1111
24.10 Chemical Properties of Polymers......Page 1113
Focus On: Recycling Plastics......Page 1116
Additional Problems......Page 1117
25.1 Structures of Carbohydrates......Page 1121
25.2 Stereochemistry of Carbohydrates......Page 1122
25.3 Cyclization of Monosaccharides......Page 1126
25.4 Reactions of Monosaccharides......Page 1130
Focus On: The Determination of Anomer Configuration......Page 1131
Focus On: Artificial Sweeteners......Page 1139
25.5 Fischer’s Structure Proof for Glucose......Page 1141
25.6 Disaccharides......Page 1146
25.7 Polysaccharides......Page 1147
25.8 Other Carbohydrate-Containing Compounds......Page 1149
Focus On Biological Chemistry: Blood Groups......Page 1151
Review of Mastery Goals......Page 1152
Additional Problems......Page 1153
26.1 Amino Acids......Page 1159
26.2 Acid–Base Chemistry of Amino Acids......Page 1162
26.3 Chemical Reactions of Amino Acids......Page 1166
26.4 Laboratory Synthesis of Amino Acids......Page 1167
Focus On: Asymmetric Synthesis of Amino Acids......Page 1171
26.5 Peptides and Proteins......Page 1173
26.6 Sequencing Peptides......Page 1176
26.7 Laboratory Synthesis of Peptides......Page 1184
26.8 Protein Structure......Page 1191
26.9 Enzymes......Page 1192
Additional Problems......Page 1194
27.1 Nucleosides and Nucleotides......Page 1198
27.2 Structure of DNA and RNA......Page 1201
Focus On: Tautomers of Guanine and Thymine......Page 1206
27.3 Replication, Transcription, and Translation......Page 1207
Focus On Biological Chemistry: Treatment of AIDS with AZT......Page 1210
27.4 Sequencing DNA......Page 1211
27.5 Laboratory Synthesis of DNA......Page 1214
Review of Mastery Goals......Page 1216
Additional Problems......Page 1217
28.1 Terpenes......Page 1220
28.2 Monoterpenes......Page 1222
28.3 Sesquiterpenes......Page 1226
28.4 Larger Terpenes......Page 1230
28.5 Steroids......Page 1232
Focus On: Syntheses That Mimic Nature......Page 1236
28.6 Synthesis of Steroids......Page 1238
Focus On: The Birth Control Pill......Page 1240
28.7 Alkaloids......Page 1242
28.8 Fats and Related Compounds......Page 1244
Focus On: Partially Hydrogenated Vegetable Oil......Page 1246
28.9 Prostaglandins......Page 1247
Additional Problems......Page 1249
APPENDIX: ANSWERS TO IN-CHAPTER PROBLEMS......Page 1256
GLOSSARY......Page 1308
A......Page 1314
B......Page 1316
C......Page 1317
D......Page 1319
E......Page 1321
G......Page 1322
H......Page 1323
L......Page 1324
M......Page 1325
O......Page 1326
P......Page 1327
S......Page 1329
T......Page 1331
Z......Page 1332
Important Absorption Bands in the Infrared Spectral Region......Page 1333
Approximate Chemical Shifts of Hydrogens in 1H-NMR Spectra......Page 1334