Organic Chemistry II

274 Pages·2000·1.77 MB·English

by  Frank Pellegrini

CLIFFSQuICKREVIEW
Organic Chemistry II
by Frank Pellegrini,Ph.D.
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CONTENTS
FUNDAMENTAL IDEAS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
CHAPTER 1:AROMATIC COMPOUNDS . . . . . . . . . . . . . . .3
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Structure of the benzene molecule . . . . . . . . . . . . . . . . . . . . 3
Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Orbital picture of benzene . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Hückel’s Rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Reactions of benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Other Aromatic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Heterocyclic Aromatic Compounds . . . . . . . . . . . . . . . . . . . . 15
CHAPTER 2:REACTIONS OF
AROMATIC COMPOUNDS . . . . . . . . . . . . . . . . . . . . . . . . . .17
Electrophilic Aromatic Substitution Reactions . . . . . . . . . . . . 17
The bromination of benzene . . . . . . . . . . . . . . . . . . . . . . . . 18
The nitration of benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
The sulfonation of benzene . . . . . . . . . . . . . . . . . . . . . . . . 22
The Birch Reduction of Benzene . . . . . . . . . . . . . . . . . . . . . . 24
Friedel-Crafts Alkylation Reaction . . . . . . . . . . . . . . . . . . . . . 25
Friedel-Crafts Acylation Reaction . . . . . . . . . . . . . . . . . . . . . 28
Directing Group Influence . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Halogen atom influence . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Predicting second group position . . . . . . . . . . . . . . . . . . . . 32
Theory of Substitution Effects (Directing Group Influence). . . 33
Ring Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Ring Deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
CHAPTER 3:ALKYL HALIDES . . . . . . . . . . . . . . . . . . . . . .37
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Nucleus and Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Nucleophilic Substitution Reactions . . . . . . . . . . . . . . . . . . . . 40
Leaving Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
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Mechanisms of Nucleophilic Substitution Reactions . . . . . . . 42
S 2 mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
N
Steric hindrance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Solvent effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
S 1 mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
N
S 1 versus S 2 Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
N N
Nature of the carbon skeleton . . . . . . . . . . . . . . . . . . . . . . . 47
Nature of the solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Nature of the leaving group . . . . . . . . . . . . . . . . . . . . . . . . 48
Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Mechanism of Elimination Reactions . . . . . . . . . . . . . . . . . . . 50
E1 mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
E2 mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Grignard Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Preparation of Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Hydrogen halide addition to an alkene . . . . . . . . . . . . . . . . 53
Reaction of alcohols with sulfur and phosphorous halides. . . 54
CHAPTER 4:PHENOLS AND ARYL HALIDES . . . . . . . . .55
Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Acidity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Resonance structures of phenol . . . . . . . . . . . . . . . . . . . . . 58
Synthesis of Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Pyrolysis of sodium benzene sulfonate . . . . . . . . . . . . . . . 59
Dow process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Air oxidation of cumene . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Reactions of Phenolic Hydrogen . . . . . . . . . . . . . . . . . . . . . . 63
Reactions with bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Esterification of phenol . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Williamson ether synthesis . . . . . . . . . . . . . . . . . . . . . . . . . 65
Reactions of Phenolic Benzene Rings . . . . . . . . . . . . . . . . . . 65
Halogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Nitration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Sulfonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Kolbe reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
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Aryl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Properties of aryl halides . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Synthesis of Aryl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Halogenation of benzene . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Sandmeyer reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Reactions of Aryl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Grignard reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Substitution reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
S AR reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
N
S AR mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
N
Elimination-addition reactions . . . . . . . . . . . . . . . . . . . . . . 75
Mechanism for aniline formation . . . . . . . . . . . . . . . . . . . . 76
CHAPTER 5:ALCOHOLS AND ETHERS . . . . . . . . . . . . . .79
Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Synthesis of Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Hydration of alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Reduction of aldehydes and ketones . . . . . . . . . . . . . . . . . 82
Reduction of carboxylic acids . . . . . . . . . . . . . . . . . . . . . . 84
Reduction of esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Grignard reaction with aldehydes and ketones . . . . . . . . . . 85
Reactions of Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Metal salt formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Alkyl halide formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Ester formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Synthesis of Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Sulfuric acid process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Williamson method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Reactions of Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
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CHAPTER 6:ALDEHYDES AND KETONES . . . . . . . . . .103
Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Structure of the carbonyl group . . . . . . . . . . . . . . . . . . . . 105
Synthesis of Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
The oxidation of primary alcohols . . . . . . . . . . . . . . . . . . 106
The reduction of acyl chlorides,esters,and nitriles . . . . . 106
Acyl chloride reduction. . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Ester and nitrile reduction. . . . . . . . . . . . . . . . . . . . . . . . . 108
Ozonolysis of alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Hydroboration of terminal alkynes. . . . . . . . . . . . . . . . . . 110
Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
Synthesis of Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Oxidation of secondary alcohols. . . . . . . . . . . . . . . . . . . . 112
Hydration of alkynes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Ozonolysis of alkynes. . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Friedel-Crafts acylation. . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Lithium dialkylcuprates. . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Grignard reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Reactions of Aldehydes and Ketones . . . . . . . . . . . . . . . . . . 114
Reactions of carbonyl groups . . . . . . . . . . . . . . . . . . . . . . 114
Addition of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Addition of alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Stability of acetals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Addition of hydrogen cyanide . . . . . . . . . . . . . . . . . . . . . 120
Addition of ylides (the Wittig reaction) . . . . . . . . . . . . . . 121
Addition of organometallic reagents . . . . . . . . . . . . . . . . 122
Addition of ammonia derivatives . . . . . . . . . . . . . . . . . . . 122
Oxidations of aldehydes and ketones . . . . . . . . . . . . . . . . 125
Aldol reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Halogenation of ketones . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Aldol condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Cross-aldol condensation . . . . . . . . . . . . . . . . . . . . . . . . . 130
Ketonic aldol condensation . . . . . . . . . . . . . . . . . . . . . . . 131
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Cyclizations via aldol condensation . . . . . . . . . . . . . . . . . 132
The benzoin condensation . . . . . . . . . . . . . . . . . . . . . . . . 134
CHAPTER 7:CARBOXYLIC ACIDS AND
THEIR DERIVATIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . .137
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Nomenclature of carboxylic acids . . . . . . . . . . . . . . . . . . 138
Naming carboxylic acid salts . . . . . . . . . . . . . . . . . . . . . . 139
Acidity of carboxylic acids . . . . . . . . . . . . . . . . . . . . . . . . 139
Preparation of Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . 140
Oxidation of alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Ozonolysis of alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
The oxidation of primary alcohols and aldehydes . . . . . . 141
The oxidation of alkyl benzenes . . . . . . . . . . . . . . . . . . . . 141
Hydrolysis of nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
The carbonation of Grignard reagents . . . . . . . . . . . . . . . 145
Synthesis of substituted aceticacidsvia acetoacetic ester. . . 146
Synthesis of substituted acetic acid via malonic ester . . . 150
a halo acids,a hydroxyacids,anda ,b unsaturated acids. . . 153
Reactions of Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . 154
Ester formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Nonreversible ester formation . . . . . . . . . . . . . . . . . . . . . 157
Methyl ester formation . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
Amide formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
Acid halide formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Acid anhydride formation . . . . . . . . . . . . . . . . . . . . . . . . 162
Decarboxylation reaction . . . . . . . . . . . . . . . . . . . . . . . . . 163
Hunsdiecker reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Kolbe electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Reduction of Carboxylic Acids and Acid Derivatives . . . . . 164
Reductions of carboxylic acid derivatives . . . . . . . . . . . . 164
Reduction of esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Reduction of acid halides . . . . . . . . . . . . . . . . . . . . . . . . . 166
Reduction of amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
Reactions of carboxylic acid derivatives . . . . . . . . . . . . . 166
Reactivity of carboxylic acid derivatives . . . . . . . . . . . . . 169
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CHAPTER 8:AMINES . . . . . . . . . . . . . . . . . . . . . . . . . . . . .171
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Classification and nomenclature of amines . . . . . . . . . . . 171
Basicity of amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Preparation of Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
Alkylation of ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
Reduction of alkylazides . . . . . . . . . . . . . . . . . . . . . . . . . 175
Reduction of nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Reduction of amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Reduction of nitrocompounds . . . . . . . . . . . . . . . . . . . . . 177
Reductive amination of aldehydes and ketones . . . . . . . . 178
Reactions of Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Reaction with acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Reaction with acid halides . . . . . . . . . . . . . . . . . . . . . . . . 179
Reaction with aldehydes and ketones . . . . . . . . . . . . . . . . 179
Reaction with sulfonyl chlorides . . . . . . . . . . . . . . . . . . . 180
The Hinsberg test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
Reaction with nitrous acid . . . . . . . . . . . . . . . . . . . . . . . . 182
Reactions of aromatic diazonium salts . . . . . . . . . . . . . . . 184
CHAPTER 9:SPECTROSCOPY AND STRUCTURE . . . .187
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Mass Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Integral molecular weight . . . . . . . . . . . . . . . . . . . . . . . . . 187
Fragment and rearrangement ions . . . . . . . . . . . . . . . . . . 189
Nuclear Magnetic Resonance (NMR) Spectra . . . . . . . . . . . 189
Deshielded and shielded protons . . . . . . . . . . . . . . . . . . . 190
Chemical shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
Mapping nonequivalent hydrogens . . . . . . . . . . . . . . . . . 191
Peak areas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Peak splitting:Spin-spin coupling . . . . . . . . . . . . . . . . . . 193
Coupling constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
Ultraviolet and Visible Spectra . . . . . . . . . . . . . . . . . . . . . . . 194
Infrared Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
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