Organic Chemistry Maitland Jones Jr., Steven A. Fleming really hard course

1855 Pages·2022·15.106 MB·English

by  Maitland Jones Jr., Steven A. Fleming

Organic Chemistry

O rg a n i c C h e m i s t r y
FIFTH EDITION
Maitland Jones, Jr.
NEW YORK UNIVERSITY
Steven A. Fleming
TEMPLE UNIVERSITY
W. W. Norton & Company
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1 2 3 4 5 6 7 8 9 0
Brief Contents
1 Atoms and Molecules; Orbitals and Bonding 1
2 Alkanes 52
3 Alkenes and Alkynes 101
4 Stereochemistry 151
5 Rings 190
6 Substituted Alkanes: Alkyl Halides, Alcohols, Amines, Ethers,
Thiols, and Thioethers 229
7 Substitution Reactions: T he S 2 and S 1 Reactions 267
N N
8 Elimination Reactions: T he E1 and E2 Reactions 331
9 Analytical Chemistry: Spectroscopy 367
10 Electrophilic Additions to Alkenes 441
11 More Additions to (cid:300) Bonds 487
12 Radical Reactions 544
13 Dienes and the Allyl System: 2p Orbitals in Conjugation 588
14 Aromaticity 641
15 Substitution Reactions of Aromatic Compounds 693
16 Carbonyl Chemistry 1: Addition Reactions 765
17 Carboxylic Acids 833
18 Derivatives of Carboxylic Acids: Acyl Compounds 878
19 Carbonyl Chemistry 2: Reactions at the (cid:284) Position 929
20 Carbohydrates 1026
21 Special Topic: Bioorganic Chemistry 1076
22 Special Topic: Amino Acids and Polyamino Acids
(Peptides and Proteins) 1104
23 Special Topic: Reactions Controlled by Orbital Symmetry 1153
24 Special Topic: Intramolecular Reactions and Neighboring
Group Participation 1203
v

Contents
Selected Applications xix
Organic Reaction Animations xxi
Preface to the Fifth Edition xxiii
Introduction xxxi
1 Atoms and Molecules; Orbitals and Bonding 1
1.1 Preview 2
1.2 Atoms and Atomic Orbitals 4
1.3 Covalent Bonds and Lewis Structures 13
1.4 Formal Charges 20
1.5 Resonance Forms and the Curved Arrow Formalism 23
1.6 Hydrogen (H ): Molecular Orbitals 32
2
1.7 Bond Strength 37
1.8 An Introduction to Reactivity: Acids and Bases 44
1.9 Special Topic: Quantum Mechanics and Babies 45
1.10 Summary 45
1.11 Additional Problems 47
2 Alkanes 52
2.1 Preview 53
2.2 Hybrid Orbitals: Making a Model for Methane 54
2.3 T he Methyl Group (CH ) and Methyl Compounds (CH X) 63
3 3
2.4 T he Methyl Cation ((cid:224)CH ), Anion ((cid:377)(cid:4)CH ), and Radical ((cid:5)CH ) 65
3 3 3
2.5 Ethane (C H ), Ethyl Compounds (C H X),
2 6 2 5
and Newman Projections 67
2.6 Structure Drawings 74
2.7 Propane (C H ) and Propyl Compounds (C H X) 75
3 8 3 7
vii
viii CONTENTS
2.8 Butanes (C H ), Butyl Compounds (C H X),
4 10 4 9
and Conformational Analysis 77
2.9 Pentanes (C H ) and Pentyl Compounds (C H X) 80
5 12 5 11
2.10 T he Naming Conventions for Alkanes 82
2.11 Drawing Isomers 85
2.12 Cycloalkanes 87
2.13 Physical Properties of Alkanes and Cycloalkanes 90
2.14 Nuclear Magnetic Resonance Spectra of Alkanes 91
2.15 Acids and Bases Revisited: More Chemical Reactions 94
2.16 Special Topic: Alkanes as Biomolecules 95
2.17 Summary 96
2.18 Additional Problems 97
3 Alkenes and Alkynes 101
3.1 Preview 102
3.2 Alkenes: Structure and Bonding 103
3.3 Derivatives and Isomers of Alkenes 111
3.4 Nomenclature 115
3.5 T he Cahn–Ingold–Prelog Priority System 116
3.6 Relative Stability of Alkenes: Heats of Formation 119
3.7 Double Bonds in Rings 122
3.8 Physical Properties of Alkenes 127
3.9 Alkynes: Structure and Bonding 127
3.10 Relative Stability of Alkynes: Heats of Formation 130
3.11 Derivatives and Isomers of Alkynes 130
3.12 Triple Bonds in Rings 132
3.13 Physical Properties of Alkynes 133
3.14 Acidity of Alkynes 133
3.15 Molecular Formulas and Degrees of Unsaturation 134
3.16 An Introduction to Addition Reactions of Alkenes and Alkynes 135
3.17 Mechanism of the Addition of Hydrogen Halides to Alkenes 136
3.18 T he Energetics of the Addition Reaction: Energy Diagrams 139
3.19 T he Regiochemistry of the Addition Reaction 141
3.20 A Catalyzed Addition to Alkenes: Hydration 144
3.21 Synthesis: A Beginning 145
3.22 Special Topic: Alkenes and Biology 146