Carey Organic Chemistry 10th Edition Pdf Free Download UPDATED
Carey Organic Chemistry 10th Edition Pdf Free Download
PDF 2016 – Mc Graw Colina – ISBN: 0073511218 – Organic Chemistry, 10th Editionpast Francis A Carey Dr., Robert 1000. Giuliano # 8556
2016 | | English | 1248 pages | PDF | 97 MB
For ten editions, Organic Chemical science has been designed to meet the needs of the "mainstream," two-semester, undergraduate organic chemistry course. This best-selling text gives students a solid understanding of organic chemistry by stressing how fundamental reaction mechanisms function and reactions occur.
i Structure Determines Backdrop 2
2 Alkanes and Cycloalkanes: Introduction to Hydrocarbons 52
3 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 94
4 Chirality 130
v Alcohols and Alkyl Halides: Introduction to Reaction Mechanisms 168
6 Nucleophilic Substitution 206
7 Structure and Preparation of Alkenes: Elimination Reactions 238
viii Improver Reactions of Alkenes 280
ix Alkynes 322
10 Introduction to Complimentary Radicals 348
eleven Conjugation in Alkadienes and Allylic Systems 376
12 Arenes and Aromaticity 414
13 Electrophilic and Nucleophilic Effluvious Substitution 464
14 Spectroscopy 518
xv Organometallic Compounds 584
sixteen Alcohols, Diols, and Thiols 620
17 Ethers, Epoxides, and Sulfides 656
eighteen Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 692
19 Carboxylic Acids 742
20 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 776
21 Enols and Enolates 826
22 Amines 864
23 Phenols 920
24 Carbohydrates 950
25 Lipids 996
26 Amino Acids, Peptides, and Proteins 1034
27 Nucleosides, Nucleotides, and Nucleic Acids 1088
28 Synthetic Polymers 1126
C H A P T Due east R 1
Structure Determines Backdrop 2
1.1 Atoms, Electrons, and Orbitals 2
Organic Chemistry: The Early Days 3
1.two Ionic Bonds 6
1.3 Covalent Bonds, Lewis Formulas, and the Octet Rule 8
1.4 Polar Covalent Bonds, Electronegativity, and Bond
Dipoles 10
Electrostatic Potential Maps 13
1.5 Formal Charge xiii
one.6 Structural Formulas of Organic Molecules: Isomers 15
1.vii Resonance and Curved Arrows 19
1.eight Sulfur and Phosphorus-Containing Organic Compounds
and the Octet Rule 23
one.nine Molecular Geometries 24
Molecular Models and Modeling 26
1.10 Molecular Dipole Moments 27
1.eleven Curved Arrows, Arrow Pushing, and Chemic
Reactions 28
one.12 Acids and Bases: The Bronsted.Lowry View 30
i.13 How Structure Affects Acid Force 35
1.fourteen Acid.Base of operations Equilibria 39
1.15 Acids and Bases: The Lewis View 42
1.16 Summary 43
Problems 46
Descriptive Passage and Interpretive Issues i:
Amide Lewis Structural Formulas 51
C H A P T Eastward R two
Alkanes and Cycloalkanes: Introduction
to Hydrocarbons 52
2.1 Classes of Hydrocarbons 53
2.2 Electron Waves and Chemical Bonds 53
2.3 Bonding in H2: The Valence Bond Model 54
2.4 Bonding in H2: The Molecular Orbital Model 56
2.5 Introduction to Alkanes: Methane, Ethane, and Propane 57
2.vi sp3 Hybridization and Bonding in Methyl hydride 58
Methyl hydride and the Biosphere 59
2.7 Bonding in Ethane threescore
two.eight sp2 Hybridization and Bonding in Ethylene 61
2.9 sp Hybridization and Bonding in Acetylene 62
2.10 Molecular Orbitals and Bonding in Marsh gas 64
ii.11 Isomeric Alkanes: The Butanes 65
2.12 College n-Alkanes 66
2.13 The C5H12 Isomers 66
two.xiv IUPAC Nomenclature of Unbranched Alkanes 68
two.15 Applying the IUPAC Rules: The Names of the C6H14
Isomers 69
Whatfs in a Name? Organic Nomenclature 70
2.16 Alkyl Groups 72
ii.17 IUPAC Names of Highly Branched Alkanes 73
two.xviii Cycloalkane Nomenclature 75
2.nineteen Introduction to Functional Groups 76
2.xx Sources of Alkanes and Cycloalkanes 76
2.21 Physical Backdrop of Alkanes and Cycloalkanes 78
ii.22 Chemical Properties: Combustion of Alkanes 80
Thermochemistry 82
2.23 Oxidation.Reduction in Organic Chemical science 83
2.24 Summary 85
Problems 89
Descriptive Passage and Interpretive Issues two:
Some Biochemical Reactions of Alkanes 93
C H A P T E R 3
Alkanes and Cycloalkanes: Conformations and
cis.trans Stereoisomers 94
3.ane Conformational Assay of Ethane 95
3.ii Conformational Analysis of Butane 99
three.3 Conformations of Higher Alkanes 100
Computational Chemistry: Molecular Mechanics and
Breakthrough Mechanics 101
3.4 The Shapes of Cycloalkanes: Planar or Nonplanar? 102
three.5 Small Rings: Cyclopropane and Cyclobutane 103
3.6 Cyclopentane 104
three.7 Conformations of Cyclohexane 105
three.8 Axial and Equatorial Bonds in Cyclohexane 106
3.9 Conformational Inversion in Cyclohexane 107
iii.10 Conformational Analysis of Monosubstituted
Cyclohexanes 108
Enthalpy, Costless Free energy, and Equilibrium Abiding 111
iii.11 Disubstituted Cycloalkanes: cis.trans Stereoisomers 112
3.12 Conformational Analysis of Disubstituted
Cyclohexanes 113
iii.13 Medium and Large Rings 117
3.14 Polycyclic Band Systems 117
7
3.15 Heterocyclic Compounds 120
three.16 Summary 121
Problems 124
Descriptive Passage and Interpretive Problems iii:
Cyclic Forms of Carbohydrates 128
C H A P T E R 4
Chirality 130
iv.1 Introduction to Chirality: Enantiomers 130
four.2 The Chirality Center 133
iv.3 Symmetry in Achiral Structures 135
4.iv Optical Activeness 136
4.5 Absolute and Relative Configuration 138
4.6 Cahn.Inglod Prelog R.South Notation 139
Homochirality and Symmetry Breaking 142
4.vii Fischer Projections 143
four.eight Properties of Enantiomers 145
4.9 The Chirality Axis 146
Chiral Drugs 147
iv.10 Chiral Molecules with Ii Chirality Centers 148
4.11 Achiral Molecules with Two Chirality Centers 151
Chirality of Disubstituted Cyclohexanes 153
iv.12 Molecules with Multiple Chirality Centers 153
iv.13 Resolution of Enantiomers 155
4.14 Chirality Centers Other Than Carbon 157
four.15 Summary 158
Issues 161
Descriptive Passage and Interpretive Issues 4:
Prochirality 165
C H A P T E R 5
Alcohols and Alkyl Halides: Introduction to Reaction
Mechanisms 168
five.i Functional Groups 169
v.2 IUPAC Nomenclature of Alkyl Halides 170
5.3 IUPAC Nomenclature of Alcohols 171
5.4 Classes of Alcohols and Alkyl Halides 172
5.5 Bonding in Alcohols and Alkyl Halides 172
5.half-dozen Physical Properties of Alcohols and Alkyl Halides:
Intermolecular Forces 173
5.7 Training of Alkyl Halides from Alcohols and Hydrogen
Halides 177
5.eight Reaction of Alcohols with Hydrogen Halides: The SN1
Machinery 179
Mechanism 5.1 Germination of tert-Butyl Chloride from
tert-Butyl Alcohol and Hydrogen Chloride 180
5.9 Construction, Bonding, and Stability of Carbocations 185
5.x Effect of Alcohol Structure on Reaction Charge per unit 188
5.xi Stereochemistry and the SN1 Mechanism 189
five.12 Carbocation Rearrangements 191
Mechanism 5.two Carbocation Rearrangement in the
Reaction of 3,3-Dimethyl-ii-butanol with Hydrogen
Chloride 191
5.13 Reaction of Methyl and Primary Alcohols with Hydrogen
Halides: The SN2 Mechanism 193
Machinery 5.3 Formation of 1-Bromoheptane from
1-Heptanol and Hydrogen Bromide 194
5.xiv Other Methods for Converting Alcohols to Alkyl
Halides 195
v.15 Sulfonates as Alkyl Halide Surrogates 197
v.16 Summary 198
Bug 200
Descriptive Passage and Interpretive Problems 5:
More Virtually Potential Energy Diagrams 204
C H A P T E R six
Nucleophilic Commutation 206
6.1 Functional-Group Transformation by Nucleophilic
Substitution 206
six.ii Relative Reactivity of Halide Leaving Groups 209
half-dozen.3 The SN2 Mechanism of Nucleophilic Substitution 210
Mechanism six.1 The SN2 Machinery of Nucleophilic
Commutation 211
vi.4 Steric Effects and SN2 Reaction Rates 213
6.5 Nucleophiles and Nucleophilicity 215
Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl
Halides 217
6.six The SN1 Mechanism of Nucleophilic Exchange 217
Mechanism 6.ii The SN1 Mechanism of Nucleophilic
Substitution 218
vi.7 Stereochemistry of SN1 Reactions 220
half dozen.eight Carbocation Rearrangements in SN1 Reactions 221
Mechanism half dozen.3 Carbocation Rearrangement in the SN1
Hydrolysis of 2-Bromo-iii-methylbutane 222
6.ix Event of Solvent on the Rate of Nucleophilic
Substitution 223
vi.x Nucleophilic Substitution of Alkyl Sulfonates 226
6.11 Introduction to Organic Synthesis: Retrosynthetic
Analysis 229
6.12 Commutation versus Elimination: A Look Alee 230
6.13 Summary 230
Problems 232
Descriptive Passage and Interpretive Bug 6:
Nucleophilic Substitution 236
C H A P T Due east R 7
Structure and Training of Alkenes: Emptying
Reactions 238
7.1 Alkene Nomenclature 238
7.2 Structure and Bonding in Alkenes 240
Ethylene 241
viii Contents
viii
7.3 Isomerism in Alkenes 242
vii.4 Naming Stereoisomeric Alkenes by the Eastward.Z Notational
Organization 243
7.v Physical Properties of Alkenes 244
7.6 Relative Stabilities of Alkenes 246
7.7 Cycloalkenes 248
vii.viii Training of Alkenes: Emptying Reactions 249
7.9 Dehydration of Alcohols 250
seven.x Regioselectivity in Alcohol Dehydration: The Zaitsev
Dominion 251
7.11 Stereoselectivity in Alcohol Aridity 252
7.12 The E1 and E2 Mechanisms of Alcohol Aridity 253
Mechanism 7.one The E1 Mechanism for Acrid-Catalyzed
Dehydration of tert-Butyl Alcohol 253
7.13 Rearrangements in Alcohol Dehydration 255
Machinery 7.2 Carbocation Rearrangement in
Dehydration of iii,three-Dimethyl-two-butanol 256
Mechanism 7.iii Hydride Shift in Aridity of
1-Butanol 257
7.14 Dehydrohalogenation of Alkyl Halides 258
7.15 The E2 Mechanism of Dehydrohalogenation of Alkyl
Halides 259
Mechanism seven.four E2 Elimination of
1-Chlorooctadecane 260
7.16 Anti Elimination in E2 Reactions: Stereoelectronic
Effects 262
7.17 Isotope Effects and the E2 Mechanism 264
vii.18 The E1 Mechanism of Dehydrohalogenation of Alkyl
Halides 265
Machinery seven.5 The E1 Mechanism for
Dehydrohalogenation of 2-Bromo-ii-methylbutane 266
7.nineteen Substitution and Emptying as Competing
Reactions 267
7.twenty Emptying Reactions of Sulfonates 270
7.21 Summary 271
Problems 274
Descriptive Passage and Interpretive Problems 7:
A Mechanistic Preview of Addition Reactions 279
C H A P T E R eight
Addition Reactions of Alkenes 280
8.one Hydrogenation of Alkenes 280
8.2 Stereochemistry of Alkene Hydrogenation 281
Mechanism eight.i Hydrogenation of Alkenes 282
viii.3 Heats of Hydrogenation 283
8.4 Electrophilic Addition of Hydrogen Halides to
Alkenes 285
Machinery viii.ii Electrophilic Addition of Hydrogen
Bromide to 2-Methylpropene 287
Rules, Laws, Theories, and the Scientific Method 289
8.5 Carbocation Rearrangements in Hydrogen Halide
Improver to Alkenes 290
8.six Acid-Catalyzed Hydration of Alkenes 290
Mechanism 8.3 Acid-Catalyzed Hydration of
2-Methylpropene 291
8.7 Thermodynamics of Improver.Elimination Equilibria 292
eight.viii Hydroboration.Oxidation of Alkenes 295
viii.9 Mechanism of Hydroboration.Oxidation 297
Machinery eight.4 Hydroboration of
ane-Methylcyclopentene 297
viii.10 Add-on of Halogens to Alkenes 298
Mechanism 8.5 Oxidation of an Organoborane 299
Mechanism 8.6 Bromine Improver to Cyclopentene 301
8.11 Epoxidation of Alkenes 303
Mechanism 8.7 Epoxidation of Bicyclo[two.2.1]-
two-heptene 305
viii.12 Ozonolysis of Alkenes 305
8.13 Enantioselective Addition to Alkenes 306
8.14 Retrosynthetic Assay and Alkene Intermediates 308
8.15 Summary 309
Problems 312
Descriptive Passage and Interpretive Problems 8:
Oxymercuration 319
C H A P T Due east R nine
Alkynes 322
ix.one Sources of Alkynes 322
nine.2 Classification 324
9.3 Concrete Properties of Alkynes 324
9.4 Structure and Bonding in Alkynes: sp Hybridization 325
9.5 Acidity of Acetylene and Terminal Alkynes 327
9.6 Preparation of Alkynes past Alkylation of Acetylene
and Terminal Alkynes 329
ix.7 Preparation of Alkynes by Elimination Reactions 330
9.eight Reactions of Alkynes 331
9.9 Hydrogenation of Alkynes 332
ix.10 Addition of Hydrogen Halides to Alkynes 334
9.11 Hydration of Alkynes 335
Mechanism 9.1 Conversion of an Enol to a Ketone 336
ix.12 Add-on of Halogens to Alkynes 337
Some Things That Tin can Be Made from Acetylene . . .
But Arenft 338
9.xiii Ozonolysis of Alkynes 338
nine.14 Alkynes in Synthesis and Retrosynthesis 339
9.xv Summary 339
Bug 342
Descriptive Passage and Interpretive Issues nine:
Thinking Mechanistically About Alkynes 346
C H A P T E R 10
Introduction to Complimentary Radicals 348
10.one Structure, Bonding, and Stability of Alkyl Radicals 349
10.2 Halogenation of Alkanes 353
From Bail Enthalpies to Heats of Reaction 353
10.3 Machinery of Methane Chlorination 354
Contents ix
Machinery ten.one Gratuitous-Radical Chlorination of
Marsh gas 355
10.4 Halogenation of Higher Alkanes 356
10.v Costless-Radical Addition of Hydrogen Bromide to Alkenes
and Alkynes 360
Mechanism 10.2 Free-Radical Add-on of Hydrogen
Bromide to i-Butene 361
10.half dozen Metal-Ammonia Reduction of Alkynes 363
Mechanism 10.3 Sodium.Ammonia Reduction of an
Alkyne 364
10.7 Free Radicals and Retrosynthesis of Alkyl Halides 364
ten.viii Free-Radical Polymerization of Alkenes 365
Mechanism 10.4 Gratis-Radical Polymerization of
Ethylene 366
Ethylene and Propene: The Well-nigh Important Industrial
Organic Chemicals 367
10.nine Summary 369
Problems 370
Descriptive Passage and Interpretive Bug 10: Free-
Radical Reduction of Alkyl Halides 373
C H A P T E R xi
Conjugation in Alkadienes and Allylic Systems 376
eleven.1 The Allyl Group 377
xi.2 SN1 and SN2 Reactions of Allylic Halides 380
Mechanism 11.1 SN1 Hydrolysis of an Allylic Halide 381
11.3 Allylic Complimentary-Radical Halogenation 383
Mechanism 11.2 Allylic Chlorination of Propene 385
11.4 Allylic Anions 386
11.five Classes of Dienes: Conjugated and Otherwise 387
11.6 Relative Stabilities of Dienes 388
11.vii Bonding in Conjugated Dienes 389
11.8 Bonding in Allenes 391
11.9 Preparation of Dienes 392
Diene Polymers 393
xi.10 Addition of Hydrogen Halides to Conjugated Dienes 394
Mechanism 11.3 Add-on of Hydrogen Chloride to
one,iii-Cyclopentadiene 394
11.11 Element of group vii Addition to Dienes 396
xi.12 The Diels.Alder Reaction 397
11.13 Intramolecular Diels-Alder Reactions 400
11.14 Retrosynthetic Analysis and the Diels.Alder
Reaction 401
11.xv Molecular Orbital Analysis of the Diels.Alder
Reaction 402
11.xvi The Cope and Claisen Rearrangements 403
11.17 Summary 404
Bug 407
Descriptive Passage and Interpretive Problems 11:
one,3-Dipolar Cycloaddition 411
C H A P T East R 12
Arenes and Aromaticity 414
12.1 Benzene 415
12.two The Construction of Benzene 415
12.iii The Stability of Benzene 417
12.four Bonding in Benzene 418
12.5 Substituted Derivatives of Benzene and Their
Nomenclature 420
12.half-dozen Polycyclic Effluvious Hydrocarbons 422
Fullerenes, Nanotubes, and Graphene 424
12.7 Physical Backdrop of Arenes 425
12.8 The Benzyl Group 426
12.9 Nucleophilic Substitution in Benzylic Halides 427
Triphenylmethyl Radical Yes, Hexaphenylethane No 430
12.10 Benzylic Free-Radical Halogenation 431
12.11 Benzylic Anions 431
12.12 Oxidation of Alkylbenzenes 432
12.13 Alkenylbenzenes 434
12.14 Polymerization of Styrene 436
Mechanism 12.1 Free-Radical Polymerization of
Styrene 436
12.15 The Birch Reduction 437
Mechanism 12.two The Birch Reduction 438
12.xvi Benzylic Side Chains and Retrosynthetic Assay 439
12.17 Cyclobutadiene and Cyclooctatetraene 440
12.18 Huckelfs Rule 441
12.nineteen Annulenes 443
12.twenty Effluvious Ions 445
12.21 Heterocyclic Aromatic Compounds 448
12.22 Heterocyclic Aromatic Compounds and Huckelfs Dominion 450
12.23 Summary 452
Bug 456
Descriptive Passage and Interpretive Bug 12:
Substituent Effects on Reaction Rates and Equilibria 461
C H A P T E R thirteen
Electrophilic and Nucleophilic Aromatic
Commutation 464
13.i Representative Electrophilic Effluvious Substitution
Reactions of Benzene 465
13.2 Mechanistic Principles of Electrophilic Aromatic
Commutation 466
13.3 Nitration of Benzene 467
Mechanism 13.i Nitration of Benzene 468
xiii.iv Sulfonation of Benzene 469
Mechanism 13.2 Sulfonation of Benzene 469
xiii.v Halogenation of Benzene 470
Machinery 13.3 Bromination of Benzene 471
Biosynthetic Halogenation 472
thirteen.6 Friedel.Crafts Alkylation of Benzene 473
Mechanism 13.four Friedel.Crafts Alkylation 473
10 Contents
13.7 Friedel.Crafts Acylation of Benzene 475
Mechanism 13.5 Friedel.Crafts Acylation 476
xiii.8 Synthesis of Alkylbenzenes by Acylation.Reduction 477
xiii.9 Charge per unit and Regioselectivity in Electrophilic Effluvious
Substitution 478
13.10 Rate and Regioselectivity in the Nitration of Toluene 480
xiii.11 Rate and Regioselectivity in the Nitration of
(Trifluoromethyl)benzene 482
thirteen.12 Substituent Effects in Electrophilic Effluvious Commutation:
Activating Substituents 484
13.thirteen Substituent Effects in Electrophilic Aromatic Exchange:
Strongly Deactivating Substituents 488
13.14 Substituent Effects in Electrophilic Effluvious Substitution:
Halogens 490
13.15 Multiple Substituent Effects 492
13.16 Retrosynthetic Assay and the Synthesis of Substituted
Benzenes 494
13.17 Substitution in Naphthalene 496
13.18 Exchange in Heterocyclic Effluvious Compounds 497
13.nineteen Nucleophilic Aromatic Substitution 498
13.20 The Addition.Elimination Machinery of Nucleophilic
Aromatic Substitution 500
Mechanism 13.6 Nucleophilic Aromatic Substitution
in p-Fluoronitrobenzene past the Addition.Elimination
Mechanism 501
13.21 Related Nucleophilic Effluvious Substitutions 502
13.22 Summary 504
Problems 508
Descriptive Passage and Interpretive Problems 13:
Benzyne 515
C H A P T E R 14
Spectroscopy 518
fourteen.ane Principles of Molecular Spectroscopy: Electromagnetic
Radiation 519
fourteen.2 Principles of Molecular Spectroscopy: Quantized Free energy
States 520
14.iii Introduction to 1H NMR Spectroscopy 520
xiv.4 Nuclear Shielding and 1H Chemical Shifts 522
14.5 Effects of Molecular Structure on 1H Chemical Shifts 525
Band Currents: Aromatic and Antiaromatic 530
14.six Interpreting 1H NMR Spectra 531
14.seven Spin.Spin Splitting and 1H NMR 533
14.8 Splitting Patterns: The Ethyl Group 536
14.9 Splitting Patterns: The Isopropyl Group 537
14.ten Splitting Patterns: Pairs of Doublets 538
14.11 Complex Splitting Patterns 539
xiv.12 1H NMR Spectra of Alcohols 542
Magnetic Resonance Imaging (MRI) 543
14.xiii NMR and Conformations 543
fourteen.14 13C NMR Spectroscopy 544
fourteen.15 13C Chemic Shifts 545
14.16 13C NMR and Peak Intensities 548
14.17 13C.1H Coupling 549
14.18 Using DEPT to Count Hydrogens 549
fourteen.19 2D NMR: COSY and HETCOR 551
fourteen.xx Introduction to Infrared Spectroscopy 553
Spectra by the Thousands 554
14.21 Infrared Spectra 555
14.22 Characteristic Absorption Frequencies 557
xiv.23 Ultraviolet-Visible Spectroscopy 561
14.24 Mass Spectrometry 563
14.25 Molecular Formula as a Clue to Construction 568
14.26 Summary 569
Problems 572
Descriptive Passage and Interpretive Problems fourteen:
More on Coupling Constants 581
C H A P T E R 15
Organometallic Compounds 584
fifteen.one Organometallic Nomenclature 585
15.2 Carbon.Metal Bonds 585
15.3 Preparation of Organolithium and Organomagnesium
Compounds 587
15.4 Organolithium and Organomagnesium Compounds as
Bronsted Bases 588
15.five Synthesis of Alcohols Using Grignard and Organolithium
Reagents 589
15.6 Synthesis of Acetylenic Alcohols 592
15.7 Retrosynthetic Analysis and Grignard and Organolithium
Reagents 592
15.8 An Organozinc Reagent for Cyclopropane Synthesis 593
15.nine Transition-Metal Organometallic Compounds 595
An Organometallic Compound That Occurs Naturally:
Coenzyme B12 597
15.10 Organocopper Reagents 598
15.eleven Palladium-Catalyzed Cross-Coupling Reactions 601
15.12 Homogeneous Catalytic Hydrogenation 603
Mechanism 15.1 Homogeneous Catalysis of Alkene
Hydrogenation 605
fifteen.xiii Olefin Metathesis 606
Mechanism 15.2 Olefin Cross-Metathesis 608
xv.fourteen Ziegler.Natta Catalysis of Alkene Polymerization 609
Machinery xv.3 Polymerization of Ethylene in the
Presence of Ziegler.Natta Catalyst 611
fifteen.15 Summary 612
Problems 614
Descriptive Passage and Interpretive
Problems 15: Cyclobutadiene and
(Cyclobutadiene)tricarbonyliron 618
C H A P T Due east R sixteen
Alcohols, Diols, and Thiols 620
16.ane Sources of Alcohols 621
16.2 Preparation of Alcohols by Reduction of Aldehydes and
Ketones 623
Contents xi
xvi.three Preparation of Alcohols by Reduction of Carboxylic
Acids 626
16.4 Preparation of Alcohols from Epoxides 626
16.five Training of Diols 627
16.vi Reactions of Alcohols: A Review and a Preview 629
xvi.7 Conversion of Alcohols to Ethers 630
Mechanism 16.1 Acrid-Catalyzed Formation of Diethyl
Ether from Ethyl Alcohol 630
sixteen.viii Esterification 631
xvi.ix Oxidation of Alcohols 633
Sustainability and Organic Chemistry 636
16.10 Biological Oxidation of Alcohols 637
16.11 Oxidative Cleavage of Vicinal Diols 639
16.12 Thiols 640
16.13 Spectroscopic Analysis of Alcohols and Thiols 643
sixteen.14 Summary 645
Problems 648
Descriptive Passage and Interpretive Problems 16:
The Pinacol Rearrangement 653
C H A P T Due east R 17
Ethers, Epoxides, and Sulfides 656
17.i Nomenclature of Ethers, Epoxides, and Sulfides 656
17.2 Construction and Bonding in Ethers and Epoxides 658
17.3 Concrete Backdrop of Ethers 658
17.4 Crown Ethers 660
17.5 Grooming of Ethers 661
Polyether Antibiotics 662
17.6 The Williamson Ether Synthesis 663
17.7 Reactions of Ethers: A Review and a Preview 664
17.eight Acid-Catalyzed Cleavage of Ethers 665
Machinery 17.one Cleavage of Ethers by Hydrogen
Halides 666
17.9 Preparation of Epoxides 666
17.10 Conversion of Vicinal Halohydrins to Epoxides 667
17.11 Reactions of Epoxides with Anionic Nucleophiles 668
Mechanism 17.2 Nucleophilic Ring Opening of an
Epoxide 670
17.12 Acid-Catalyzed Ring Opening of Epoxides 671
Mechanism 17.3 Acrid-Catalyzed Ring Opening of an
Epoxide 672
17.13 Epoxides in Biological Processes 673
17.14 Preparation of Sulfides 673
17.xv Oxidation of Sulfides: Sulfoxides and Sulfones 674
17.16 Alkylation of Sulfides: Sulfonium Salts 675
17.17 Spectroscopic Analysis of Ethers, Epoxides, and
Sulfides 676
17.xviii Summary 678
Bug 681
Descriptive Passage and Interpretive Problems 17:
Epoxide Rearrangements and the NIH Shift 688
C H A P T E R eighteen
Aldehydes and Ketones: Nucleophilic Addition to
the Carbonyl Group 692
18.1 Nomenclature 693
xviii.2 Structure and Bonding: The Carbonyl Grouping 695
18.3 Physical Backdrop 697
18.4 Sources of Aldehydes and Ketones 697
18.five Reactions of Aldehydes and Ketones: A Review and a
Preview 701
18.6 Principles of Nucleophilic Addition: Hydration of
Aldehydes and Ketones 702
Mechanism eighteen.one Hydration of an Aldehyde or Ketone
in Bones Solution 705
Machinery 18.2 Hydration of an Aldehyde or Ketone
in Acid Solution 706
18.7 Cyanohydrin Formation 706
Mechanism 18.three Cyanohydrin Formation 707
18.eight Reaction with Alcohols: Acetals and Ketals 709
Machinery eighteen.4 Acetal Formation from Benzaldehyde
and Ethanol 711
18.ix Acetals and Ketals every bit Protecting Groups 712
18.10 Reaction with Main Amines: Imines 713
Mechanism xviii.5 Imine Formation from Benzaldehyde and
Methylamine 715
18.11 Reaction with Secondary Amines: Enamines 716
Imines in Biological Chemistry 717
Mechanism 18.6 Enamine Formation 719
xviii.12 The Wittig Reaction 720
eighteen.thirteen Stereoselective Add-on to Carbonyl Groups 722
xviii.14 Oxidation of Aldehydes 724
18.15 Spectroscopic Analysis of Aldehydes and Ketones 724
xviii.16 Summary 727
Problems 730
Descriptive Passage and Interpretive Problems 18:
The Baeyer.Villiger Oxidation 738
C H A P T East R 19
Carboxylic Acids 742
19.ane Carboxylic Acid Classification 743
19.2 Structure and Bonding 745
19.3 Physical Properties 745
19.four Acidity of Carboxylic Acids 746
19.5 Substituents and Acid Force 748
19.6 Ionization of Substituted Benzoic Acids 750
19.7 Salts of Carboxylic Acids 751
19.eight Dicarboxylic Acids 753
19.9 Carbonic Acrid 754
nineteen.10 Sources of Carboxylic Acids 755
xix.11 Synthesis of Carboxylic Acids past the Carboxylation of
Grignard Reagents 757
xii Contents
19.12 Synthesis of Carboxylic Acids by the Preparation and
Hydrolysis of Nitriles 758
19.thirteen Reactions of Carboxylic Acids: A Review and a
Preview 759
nineteen.14 Mechanism of Acid-Catalyzed Esterification 760
Mechanism 19.ane Acrid-Catalyzed Esterification of Benzoic
Acrid with Methanol 760
19.15 Intramolecular Ester Formation: Lactones 763
19.xvi Decarboxylation of Malonic Acid and Related
Compounds 764
19.17 Spectroscopic Analysis of Carboxylic Acids 766
xix.18 Summary 767
Problems 769
Descriptive Passage and Interpretive Problems 19:
Lactonization Methods 774
C H A P T E R 20
Carboxylic Acrid Derivatives: Nucleophilic Acyl
Substitution 776
twenty.i Nomenclature of Carboxylic Acid Derivatives 777
xx.2 Structure and Reactivity of Carboxylic Acrid
Derivatives 778
20.3 Nucleophilic Acyl Substitution Mechanisms 781
20.4 Nucleophilic Acyl Substitution in Acyl Chlorides 782
20.5 Nucleophilic Acyl Substitution in Acrid Anhydrides 784
Mechanism 20.one Nucleophilic Acyl Substitution in an
Anhydride 786
xx.six Concrete Backdrop and Sources of Esters 786
20.7 Reactions of Esters: A Preview 787
xx.8 Acid-Catalyzed Ester Hydrolysis 789
Mechanism xx.ii Acid-Catalyzed Ester Hydrolysis 790
twenty.ix Ester Hydrolysis in Base: Saponification 792
Mechanism twenty.3 Ester Hydrolysis in Basic Solution 795
xx.x Reaction of Esters with Ammonia and Amines 796
20.11 Reaction of Esters with Grignard and Organolithium
Reagents and Lithium Aluminum Hydride 797
20.12 Amides 798
20.13 Hydrolysis of Amides 802
Machinery 20.iv Amide Hydrolysis in Acid Solution 803
Mechanism 20.v Amide Hydrolysis in Basic
Solution 805
20.xiv Lactams 806
ƒÀ-Lactam Antibiotics 806
twenty.15 Preparation of Nitriles 808
20.16 Hydrolysis of Nitriles 809
Mechanism 20.half dozen Nitrile Hydrolysis in Basic Solution 810
20.17 Addition of Grignard Reagents to Nitriles 811
20.18 Spectroscopic Analysis of Carboxylic Acid
Derivatives 811
20.19 Summary 813
Problems 816
Descriptive Passage and Interpretive Problems twenty:
Thioesters 822
C H A P T E R 21
Enols and Enolates 826
21.1 Enol Content and Enolization 827
Mechanism 21.1 Acid-Catalyzed Enolization of
2-Methylpropanal 829
21.2 Enolates 830
Mechanism 21.2 Base of operations-Catalyzed Enolization of
2-Methylpropanal 832
21.3 The Aldol Condensation 834
Mechanism 21.3 Aldol Addition of Butanal 834
21.iv Mixed and Directed Aldol Reactions 837
From the Mulberry Tree to Cancer Chemotherapy 838
21.v Acylation of Enolates: The Claisen and Related
Condensations 839
Mechanism 21.4 Claisen Condensation of Ethyl
Propanoate 840
21.6 Alkylation of Enolates: The Acetoacetic Ester and Malonic
Ester Syntheses 843
21.seven The Haloform Reaction 846
The Haloform Reaction and the Biosynthesis of
Trihalomethanes 847
Mechanism 21.5 The Haloform Reaction 848
21.8 Conjugation Effects in ƒ¿,ƒÀ-Unsaturated Aldehydes and
Ketones 849
21.9 Summary 853
Problems 855
Descriptive Passage and Interpretive Problems 21:
The Enolate Chemical science of Dianions 861
C H A P T Due east R 22
Amines 864
22.i Amine Nomenclature 865
22.2 Construction and Bonding 867
22.3 Concrete Properties 868
22.4 Basicity of Amines 869
Amines as Natural Products 874
22.five Tetraalkylammonium Salts every bit Phase-Transfer
Catalysts 875
22.6 Reactions That Lead to Amines: A Review and a
Preview 876
22.seven Grooming of Amines by Alkylation of Ammonia 878
22.eight The Gabriel Synthesis of Primary Alkylamines 879
22.9 Preparation of Amines by Reduction 880
Mechanism 22.i Lithium Aluminum Hydride Reduction
of an Amide 883
22.10 Reductive Amination 884
22.xi Reactions of Amines: A Review and a Preview 885
22.12 Reaction of Amines with Alkyl Halides 887
22.xiii The Hofmann Elimination 887
22.14 Electrophilic Effluvious Substitution in Arylamines 889
Contents xiii
22.15 Nitrosation of Alkylamines 891
22.xvi Nitrosation of Arylamines 893
22.17 Synthetic Transformations of Aryl Diazonium Salts 894
22.18 Azo Coupling 898
From Dyes to Sulfa Drugs 899
22.19 Spectroscopic Assay of Amines 899
22.xx Summary 902
Issues 908
Descriptive Passage and Interpretive Issues 22:
Synthetic Applications of Enamines 916
C H A P T E R 23
Phenols 920
23.1 Nomenclature 920
23.two Structure and Bonding 922
23.three Physical Properties 922
23.4 Acidity of Phenols 923
23.5 Substituent Effects on the Acerbity of Phenols 924
23.vi Sources of Phenols 925
23.seven Naturally Occurring Phenols 926
23.eight Reactions of Phenols: Electrophilic Aromatic
Exchange 927
23.ix Reactions of Phenols: O-Alkylation and O-Acylation 930
23.ten Carboxylation of Phenols: Aspirin and the Kolbe.Schmitt
Reaction 932
James Bond, Oxidative Stress, and Antioxidant
Phenols 933
23.eleven Cleavage of Aryl Ethers by Hydrogen Halides 935
23.12 Claisen Rearrangement of Allyl Aryl Ethers 936
23.13 Oxidation of Phenols: Quinones 937
23.14 Spectroscopic Analysis of Phenols 938
23.fifteen Summary 939
Issues 941
Descriptive Passage and Interpretive Problems 23:
Directed Metalation of Aryl Ethers 947
C H A P T East R 24
Carbohydrates 950
24.1 Classification of Carbohydrates 951
24.2 Fischer Projections and d,l Notation 951
24.three The Aldotetroses 952
24.4 Aldopentoses and Aldohexoses 954
24.5 A Mnemonic for Carbohydrate Configurations 956
24.6 Circadian Forms of Carbohydrates: Furanose Forms 956
24.7 Cyclic Forms of Carbohydrates: Pyranose Forms 960
24.viii Mutarotation 962
Machinery 24.1 Acid-Catalyzed Mutarotation of
d-Glucopyranose 963
24.9 Carbohydrate Conformation: The Anomeric Effect 964
24.ten Ketoses 966
24.11 Deoxy Sugars 967
24.12 Amino Sugars 968
24.13 Branched-Chain Carbohydrates 969
24.14 Glycosides: The Fischer Glycosidation 969
Mechanism 24.2 Preparation of Methyl
d-Glucopyranosides past Fischer Glycosidation 971
24.15 Disaccharides 973
24.16 Polysaccharides 975
How Sugariness It Is! 976
24.17 Application of Familiar Reactions to
Monosaccharides 977
24.18 Oxidation of Monosaccharides 980
24.19 Glycosides: Synthesis of Oligosaccharides 982
Machinery 24.three Silver-Assisted Glycosidation 984
24.20 Glycobiology 985
24.21 Summary 987
Problems 988
Descriptive Passage and Interpretive Problems 24:
Emil Fischer and the Structure of (one)-Glucose 993
C H A P T East R 25
Lipids 996
25.one Acetyl Coenzyme A 997
25.two Fats, Oils, and Fat Acids 998
25.three Fat Acid Biosynthesis 1001
25.4 Phospholipids 1003
25.five Waxes 1005
25.half dozen Prostaglandins 1006
Nonsteroidal Antiinflammatory Drugs (NSAIDs) and
COX-2 Inhibitors 1008
25.7 Terpenes: The Isoprene Dominion 1009
25.8 Isopentenyl Diphosphate: The Biological Isoprene
Unit 1012
25.9 Carbon.Carbon Bail Formation in Terpene
Biosynthesis 1012
25.10 The Pathway from Acetate to Isopentenyl
Diphosphate 1015
25.11 Steroids: Cholesterol 1017
Mechanism 25.1 Biosynthesis of Cholesterol from
Squalene 1019
25.12 Vitamin D 1020
Good Cholesterol? Bad Cholesterol? Whatfs the
Deviation? 1020
25.13 Bile Acids 1021
25.14 Corticosteroids 1021
25.15 Sexual activity Hormones 1022
25.16 Carotenoids 1023
Crocuses Make Saffron from Carotenes 1024
25.17 Summary 1025
Problems 1026
Descriptive Passage and Interpretive Problems 25:
Polyketides 1031
fourteen Contents
C H A P T East R 26
Amino Acids, Peptides, and Proteins 1034
26.1 Classification of Amino Acids 1035
26.2 Stereochemistry of Amino Acids 1039
26.3 Acid.Base Behavior of Amino Acids 1040
Electrophoresis 1043
26.4 Synthesis of Amino Acids 1044
26.5 Reactions of Amino Acids 1045
26.6 Some Biochemical Reactions of Amino Acids 1047
Mechanism 26.i Pyridoxal 5Œ-Phosphate-Mediated
Decarboxylation of an ƒ¿-Amino Acid 1048
Machinery 26.2 Transamination: Biosynthesis of
l-Alanine from l-Glutamic Acrid and Pyruvic Acid 1051
26.7 Peptides 1053
26.8 Introduction to Peptide Construction Determination 1056
26.nine Amino Acrid Analysis 1056
26.10 Partial Hydrolysis and Terminate Grouping Analysis 1057
26.11 Insulin 1059
26.12 Edman Degradation and Automated Sequencing of
Peptides 1060
Machinery 26.three The Edman Degradation 1061
Peptide Mapping and MALDI Mass Spectrometry 1062
26.xiii The Strategy of Peptide Synthesis 1063
26.xiv Amino and Carboxyl Group Protection and
Deprotection 1064
26.15 Peptide Bond Formation 1065
Mechanism 26.four Amide Bond Germination Between a
Carboxylic Acid and an Amine Using
N,N9-Dicyclohexylcarbodiimide 1067
26.16 Solid-Phase Peptide Synthesis: The Merrifield
Method 1068
26.17 Secondary Structures of Peptides and Proteins 1070
26.18 Tertiary Structure of Polypeptides and Proteins 1073
Mechanism 26.5 Carboxypeptidase-Catalyzed
Hydrolysis 1076
26.19 Coenzymes 1077
Oh NO! Itfs Inorganic! 1078
26.twenty Protein Quaternary Construction: Hemoglobin 1078
26.21 Chiliad-Poly peptide-Coupled Receptors 1079
26.22 Summary 1080
Problems 1082
Descriptive Passage and Interpretive Bug 26:
Amino Acids in Enantioselective Synthesis 1085
C H A P T Due east R 27
Nucleosides, Nucleotides, and Nucleic Acids 1088
27.1 Pyrimidines and Purines 1089
27.ii Nucleosides 1092
27.three Nucleotides 1094
27.4 Bioenergetics 1095
27.5 ATP and Bioenergetics 1096
27.6 Phosphodiesters, Oligonucleotides, and
Polynucleotides 1098
27.seven Nucleic Acids 1099
27.8 Secondary Structure of Deoxyribonucleic acid: The Double Helix 1100
gIt Has Not Escaped Our Discover . . .h 1100
27.ix Third Structure of Dna: Supercoils 1102
27.10 Replication of DNA 1104
27.11 Ribonucleic Acids 1106
27.12 Poly peptide Biosynthesis 1108
27.13 AIDS 1109
27.fourteen Dna Sequencing 1110
27.fifteen The Human Genome Projection 1112
27.sixteen Deoxyribonucleic acid Profiling and the Polymerase Chain Reaction 1112
27.17 Recombinant Dna Technology 1115
27.18 Summary 1116
Problems 1119
Descriptive Passage and Interpretive Bug 27:
Oligonucleotide Synthesis 1121
C H A P T East R 28
Synthetic Polymers 1126
28.one Some Background 1126
28.2 Polymer Classification 1127
28.3 Nomenclature of Polymers: Reaction Type 1128
28.4 Classification of Polymers: Chain Growth and Step
Growth 1130
28.v Classification of Polymers: Construction 1131
28.six Classification of Polymers: Properties 1134
28.7 Add-on Polymers: A Review and a Preview 1134
28.8 Chain Branching in Gratis-Radical Polymerization 1137
Machinery 28.1 Branching in Polyethylene Caused by
Intramolecular Hydrogen Transfer 1138
Mechanism 28.2 Branching in Polyethylene Caused by
Intermolecular Hydrogen Transfer 1139
28.ix Anionic Polymerization: Living Polymers 1139
Machinery 28.3 Anionic Polymerization of Styrene 1140
28.10 Cationic Polymerization 1141
Mechanism 28.4 Cationic Polymerization of
2-Methylpropene 1142
28.xi Polyamides 1143
28.12 Polyesters 1144
28.thirteen Polycarbonates 1145
28.14 Polyurethanes 1145
28.fifteen Copolymers 1146
Conducting Polymers 1148
28.16 Summary 1149
Bug 1152
Descriptive Passage and Interpretive Problems 28:
Chemically Modified Polymers 1153
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