第一章 結構與鍵結 ................................................................................................. 1
1.1 混成的原子軌域 (Hybridized Atomic Orbitals) ........................................................ 1
1.2 預測分子的幾何形狀 ............................................................................................. 1
1.2.1 四面體 (Tetrahedral) ................................................................................. 2
1.2.2 三角錐狀 (Trigonal Pyramidal) ................................................................... 2
1.2.3 彎曲狀 (Bent) ............................................................................................ 2
1.2.4 三角平面 (Trigonal Planar)......................................................................... 3
1.2.5 直線 (Linear) ............................................................................................ 3
1.3 極性共價鍵 ......................................................................................................... 3
1.3.1 偶極矩和分子的極性 (Dipole Moment and Molecular Polarity) ....................... 3
1.4 分子之間的作用力與分子的物理性質 ........................................................................ 5
1.4.1 氫鍵 (Hydrogen Bonding) .......................................................................... 5
1.4.2 偶極 - 偶極作用力 (Dipole-Dipole Interactions) ............................................ 5
1.4.3 偶極 - 誘導偶極作用力 (Dipole-Induced Dipole Interactions) ......................... 5
1.4.4 倫敦分散力 (Fleeting Dipole-Dipole Interactions, London Dispersion Forces) 6
1.5 重點整理 ............................................................................................................ 7
1.6 習題 .................................................................................................................. 8

第二章 分子的表示方式 ........................................................................................... 9
2.1 有機分子的表示方式 ............................................................................................. 9
2.2 鍵 - 線結構式 (Bond-Line Structure) ..................................................................... 9
2.3 形式電荷 (Formal Charge) ................................................................................... 10
2.3.1 決定孤對電子的數目 ................................................................................... 10
2.4 鍵 - 線結構式的三維表示方式 ................................................................................. 11
2.5 共振和彎曲的箭頭 ................................................................................................ 11
2.6 評斷相對共振結構的重要性 .................................................................................... 12
2.7 共振混合 (Resonance Hybrid) .............................................................................. 13
2.8 非定域化的 (Delocalized) 與定域化的 (Localized) 孤對電子 ....................................... 13
2.8.1 非定域化的孤對電子 ................................................................................... 13
2.8.2 定域化的孤對電子 ...................................................................................... 14
2.9 重點整理 ............................................................................................................ 15
2.10 習題 ................................................................................................................. 15

第三章 碳氫化合物和有機化合物的分類 ....................................................................... 17
3.1 烷類 / 環烷類 (Alkanes/Cycloalkanes) ................................................................... 17
3.1.1 命名 ......................................................................................................... 17
3.2 烯類 (Alkenes) .................................................................................................... 21
3.2.1 布萊特規則 (Bredt’s Rule) ........................................................................... 22
3.2.2 命名......................................................................................................... 23
3.3 炔類 (Alkynes) .................................................................................................... 24
3.3.1 命名 ......................................................................................................... 25
3.3.2 乙炔的酸度和末端炔 ................................................................................... 26
3.4 官能基 (Functional Groups) ................................................................................. 27
3.5 重點整理 ............................................................................................................ 28
3.6 習題 .................................................................................................................. 28

第四章 酸和鹼 ....................................................................................................... 29
4.1 酸和鹼的定義 ...................................................................................................... 29
4.1.1 共軛酸和共軛鹼 ......................................................................................... 29
4.1.2 酸鹼的質子理論 ......................................................................................... 29
4.1.3 運用 pKa 數值比較鹼度 (Basicity) ................................................................. 30
4.1.4 運用 pKa 數值預測平衡的位置 ....................................................................... 31
4.1.5 酸鹼的電子理論 ......................................................................................... 32
4.2 布朗斯特酸的定量概念 .......................................................................................... 32
4.2.1 共軛鹼的穩定度 ......................................................................................... 32
4.2.2 影響負電荷的穩定度 ................................................................................... 33
4.3 平衡位置與試劑的選擇 .......................................................................................... 34
4.4 溶劑效應 ............................................................................................................ 35
4.5 重點整理 ............................................................................................................ 35
4.6 習題 .................................................................................................................. 36

第五章 構型 .......................................................................................................... 37
5.1 紐曼投影式 (Newman Projection) ......................................................................... 37
5.1.1 乙烷 ......................................................................................................... 37
5.1.2 丙烷 ......................................................................................................... 38
5.1.3 丁烷 ......................................................................................................... 38
5.2 環烷 .................................................................................................................. 39
5.3 環丙烷構型 ......................................................................................................... 39
5.4 環丁烷構型 ......................................................................................................... 39
5.5 環戊烷構型 ......................................................................................................... 40
5.6 環己烷構型 ......................................................................................................... 40
5.6.1 單取代環己烷構型 ...................................................................................... 40
5.6.2 雙取代環己烷構型 ...................................................................................... 41
5.7 重點整理 ............................................................................................................ 43
5.8 習題 .................................................................................................................. 43

第六章 立體異構性 ................................................................................................. 45
6.1 異構性 (Isomerism) ............................................................................................ 45
6.1.1 構型異構物 ............................................................................................... 46
6.2 立體異構性 (Stereoisomerism) ............................................................................. 46
6.2.1 掌性 (Chirality) ......................................................................................... 46
6.2.2 分子的掌性 ............................................................................................... 47
6.2.3 鏡像異構物 (Enantiomers) ......................................................................... 47
6.2.4 非鏡像異構物 (Diastereoisomers) ............................................................... 47
6.2.5 內消旋化合物 (Meso Compounds) ............................................................... 48
6.3 運用 Cahn-Ingold-Prelog 系統標示組態 (Configuration) .......................................... 48
6.3.1 命名 ......................................................................................................... 49
6.4 含有掌性中心的掌性分子 ....................................................................................... 49
6.4.1 費雪投影式 (Fischer Projection) ................................................................. 49
6.5 光學活性 (Optical Activity) ................................................................................... 51
6.5.1 比旋光度 (Specific Rotation)....................................................................... 51
6.5.2 鏡像異構物超越量 (Enantiomeric Excess, ee) ............................................... 52
6.6 不具掌性中心的掌性化合物 .................................................................................... 52
6.6.1 阻轉異構體 (Atropisomers) ........................................................................ 52
6.6.2 丙二烯 (Allenes) ........................................................................................ 53
6.6.3 含氮和含硫化合物 ...................................................................................... 53
6.7 鏡像異構物的解析 (Resolution of Enantiomers) ..................................................... 54
6.7.1 掌性解析試劑 ............................................................................................ 54
6.8 重點整理 ............................................................................................................ 55
6.9 習題 .................................................................................................................. 55

第七章 取代反應 .................................................................................................... 59
7.1 鹵烷 .................................................................................................................. 59
7.1.1 命名 ......................................................................................................... 59
7.1.2 鹵烷的物理性質 ......................................................................................... 59
7.1.3 鹵烷的製備 ............................................................................................... 60
7.2 SN2 反應 ............................................................................................................. 61
7.2.1 離去基...................................................................................................... 61
7.2.2 動力學...................................................................................................... 61
7.2.3 受質結構影響 SN2 的反應速率 ....................................................................... 62
7.2.4 親核劑的強度影響 SN2 的反應速率 ................................................................. 62
7.2.5 SN2 反應的立體專一性 ................................................................................. 63
7.2.6 溶劑影響 SN2 的反應速率 ............................................................................. 64
7.2.7 親核劑 vs 鹼 .............................................................................................. 65
7.3 SN1 反應 ............................................................................................................. 65
7.3.1 動力學...................................................................................................... 66
7.3.2 重排反應 .................................................................................................. 66
7.3.3 受質的影響 ............................................................................................... 67
7.3.4 SN1 反應的立體化學 .................................................................................... 67
7.3.5 溶劑的影響 ............................................................................................... 68
7.4 SN1 與 SN2 的離去基 ............................................................................................. 68
7.5 重點整理 ............................................................................................................ 69
7.6 習題 .................................................................................................................. 69 第八章 消除反應 .................................................................................................... 71
8.1 消除反應 ............................................................................................................ 71
8.2 烯類的穩定度 ...................................................................................................... 71
8.2.1 環烯的穩定度 ............................................................................................ 71
8.3 E2 反應機制 ........................................................................................................ 72
8.3.1 脫鹵氫反應 (Dehydrohalogenation) ............................................................ 72
8.3.2 動力學 ..................................................................................................... 72
8.3.3 結構影響 E2 反應的速率 .............................................................................. 72
8.3.4 E2 反應的位置選擇性 .................................................................................. 73
8.3.5 E2 反應的立體選擇性 .................................................................................. 73
8.3.6 E2 反應的立體專一性 .................................................................................. 73
8.4 E1 反應機制 ........................................................................................................ 74
8.4.1 動力學 ...................................................................................................... 74
8.4.2 重排反應 .................................................................................................. 75
8.5 E1 反應的速率 ..................................................................................................... 75
8.6 E1 反應的位置選擇性 ............................................................................................ 75
8.7 E1 反應的立體選擇性 ............................................................................................ 76
8.8 判別取代反應還是消除反應 .................................................................................... 76
8.9 重點整理 ............................................................................................................ 77
8.10 習題 ................................................................................................................. 78

第九章 加成反應 .................................................................................................... 81
9.1 加成反應的類型 ................................................................................................... 81
9.2 烯類的加成 - 熱力學的觀點 .................................................................................... 81
9.3 氫鹵化 - 位置選擇性 - 馬可尼可夫加成 (Markovnikov Addition).................................. 82
9.4 氫鹵化的重排反應 ................................................................................................ 83
9.4.1 氫負離子重排 (Hydride shift) 與甲基負離子重排 (Methyl shift) ........................ 83
9.5 酸催化水合反應 ................................................................................................... 83
9.6 氧汞化 - 去汞化 (Oxymercuration-Demercuration) ................................................. 83
9.7 氫化反應 (Hydrogenation) ................................................................................... 84
9.8 硼氫化 - 氧化作用 (Hydroboration-Oxidation) ........................................................ 84
9.9 鹵化 (Halogenation) 反應 .................................................................................... 85
9.10 鹵醇 (Halohydrin) 反應 ...................................................................................... 85
9.11 環氧化 (Epoxidation) ......................................................................................... 86
9.12 順式雙醇化作用 (syn Dihydroxylation) .................................................................. 86
9.13 炔類的加成反應 ................................................................................................. 87
9.14 炔類的氫鹵化反應 .............................................................................................. 87
9.15 炔類的水合反應 ................................................................................................. 88
9.16 炔類的硼氫化 - 氧化反應 ...................................................................................... 89
9.17 炔類的鹵化反應 ................................................................................................. 89
9.18 重點整理 ........................................................................................................... 90
9.19 習題 ................................................................................................................. 91
第十章 醇、酚、醚、環氧、硫和硫醇 .......................................................................... 93
10.1 醇的命名 ........................................................................................................... 93
10.1.1 醇的物理性質 ........................................................................................... 94
10.1.2 醇的製備 ................................................................................................. 94
10.1.3 有機金屬與醛的加成反應 ............................................................................ 95
10.1.4 有機金屬與酮和酯的加成反應 ..................................................................... 95
10.1.5 醛、酮、酯和酸的還原 ............................................................................... 95
10.2 醇的氧化 ........................................................................................................... 96
10.3 醇的反應 ........................................................................................................... 97
10.3.1 SN2 反應 ................................................................................................. 97
10.3.2 SN1 反應 ................................................................................................. 98
10.3.3 E2 反應 .................................................................................................. 98
10.3.4 E1 反應 .................................................................................................. 99
10.3.5 酯化反應 ................................................................................................. 99
10.4 酚的命名 ........................................................................................................... 99
10.4.1 酚的氧化 ................................................................................................. 100
10.5 醚的命名 ........................................................................................................... 100
10.5.1 醚的製備 ................................................................................................. 101
10.5.2 酸催化烯類與醇類的反應 ............................................................................ 101
10.5.3 烷氧汞化 - 去汞化 (Alkoxymercuration-Demercuration) .............................. 101
10.5.4 醚的反應 ................................................................................................. 102
10.5.5 醚的運用 ................................................................................................. 103
10.6 環氧的命名 ........................................................................................................ 104
10.6.1 環氧的製備 .............................................................................................. 105
10.6.2 環氧的反應 .............................................................................................. 105
10.7 硫和硫醇 ........................................................................................................... 106
10.7.1 硫化合物的命名 ........................................................................................ 106
10.7.2 硫衍生物的命名 ........................................................................................ 106
10.7.3 硫醚的合成 .............................................................................................. 107
10.7.4 硫化合物的反應 ........................................................................................ 107
10.8 重點整理 ...........................................................................................................108
10.9 習題 .................................................................................................................108

第十一章 醛類和酮類 .............................................................................................. 111
11.1 醛類的命名 ........................................................................................................ 111
11.2 醛類的製備........................................................................................................ 112
11.2.1 氧化 ....................................................................................................... 112
11.2.2 臭氧氧化切斷 ........................................................................................... 112
11.2.3 硼氫化 - 氧化 ........................................................................................... 112
11.2.4 鄰二醇的氧化切斷 ..................................................................................... 112
11.2.5 氰的還原 ................................................................................................. 113
11.2.6 醯氯的還原 .............................................................................................. 113
11.3 酮類的命名........................................................................................................ 113
11.4 酮類的製備 ........................................................................................................ 114
11.4.1 二級醇的氧化 ........................................................................................... 114
11.4.2 臭氧氧化切斷 ........................................................................................... 114
11.4.3 酸催化水解末端的炔類 ............................................................................... 114
11.4.4 夫里德耳 - 夸夫特醯化作用 (Friedel-Crafts Acylation) ................................... 114
11.5 醛類和酮類中與羰基的反應 .................................................................................. 114
11.5.1 與水的反應 - 水合物的形成 (Hydrate Formation) .......................................... 114
11.5.2 半縮醛 (Hemiacetal) 的形成 ...................................................................... 115
11.5.3 縮醛的形成 .............................................................................................. 115
11.5.4 與胺類的反應 ........................................................................................... 116
11.5.5 沃夫 - 奇希諾還原 (Wolff-Kishner Reduction).............................................. 117
11.5.6 與硫醇的反應 ........................................................................................... 117
11.5.7 與有機金屬的反應 ..................................................................................... 118
11.5.8 與氰化氫 (HCN) 的反應 - 氰醇 (Cyanohydrin) 的合成 .................................... 119
11.5.9 威悌反應 (Wittig Reaction) ....................................................................... 120
11.5.10 與氫負離子的反應 ................................................................................... 121
11.5.11 拜耳 - 維立格氧化反應 (Baeyer-Villiger Oxidation) ..................................... 121
11.5.12 克萊門森還原作用 (Clemmensen Reduction) ............................................ 121
11.6 重點整理 ........................................................................................................... 122
11.7習題 ................................................................................................................. 123

第十二章、醛與酮的 α 位置碳的化學 .......................................................................... 125
12.1 烯醇和烯醇鹽 α 位置的鹵化 .................................................................................. 125
12.1.1 在酸性條件 .............................................................................................. 126
12.1.2 赫耳 - 華哈德 - 季林斯基反應 (Hell-Volhard-Zelinsky Reaction) ..................... 127
12.1.3 鹼性條件 ................................................................................................. 127
12.1.4 O- 烷基化或 C- 烷基化 (O-Alkylation and C-Alkylation) ................................ 127
12.1.5 鹵化 ....................................................................................................... 128
12.1.6 鹵仿反應 (Haloform Reaction) .................................................................. 128
12.2 醛醇反應與醛醇縮合 (Aldol Reactions and Aldol Condensations) ........................... 128
12.2.1 醛醇 ( 加成 ) 反應 ..................................................................................... 128
12.2.2 醛醇縮合 (Aldol Condensations) ............................................................... 129
12.2.3 交聯醛醇反應 (Crossed Aldol Reactions) .................................................... 129
12.2.4 克萊森 - 施密特縮合反應 (Claisen-Schmidt Condensations) .......................... 130
12.2.5 分子內的醛醇反應 (Intramolecular Aldol Reactions) ................................... 130
12.3 酯的縮合 ........................................................................................................... 130
12.3.1 克萊森縮合 (Claisen Condensations) ......................................................... 130
12.3.2 交聯克萊森縮合 (Crossed Claisen Condensations) ...................................... 131
12.3.3 狄克曼縮合反應 (Dieckmann Condensations) ............................................. 131
12.4 烯醇鹽 α 位置的烷基化 ........................................................................................ 132
12.4.1 乙醯乙酸酯合成 (Acetoacetic Ester Synthesis) ............................................ 132
12.4.2 丙二酸酯合成法 (Malonic Ester Synthesis) ................................................. 133
12.4.3 克腦文蓋爾縮合反應 (Knoevenagel Reaction) .............................................. 133
12.5 共軛加成反應 .................................................................................................... 133
12.5.1 魯賓遜成環反應 (The Robinson Annulation Reaction) ................................. 134
12.5.2 施托克烯胺反應 (Stork Enamine Reaction) ................................................. 134
12.5.3 曼尼赫反應 (The Mannich Reaction) ......................................................... 135
12.5.4  α,β- 不飽和酮的烷基化 .............................................................................. 135
12.6 重點整理 ........................................................................................................... 135
12.7 習題 ................................................................................................................. 136

第十三章 羧酸和羧酸的衍生物 ................................................................................... 139
13.1 羧酸的命名 ........................................................................................................ 139
13.1.1 單一個羧酸 .............................................................................................. 139
13.1.2 兩個 (雙) 羧酸 .......................................................................................... 139
13.2 羧酸的物理性質 ................................................................................................. 140
13.2.1 羧酸的酸度 .............................................................................................. 140
13.3 羧酸的製備........................................................................................................ 141
13.3.1 炔類的臭氧化 ........................................................................................... 141
13.3.2 一級醇的氧化 ........................................................................................... 142
13.3.3 烷基苯的氧化 ........................................................................................... 142
13.3.4 腈的水解 ................................................................................................. 142
13.3.5 格里納試劑的羰基化 .................................................................................. 142
13.4 羧酸的反應 ........................................................................................................ 142
13.5 羧酸衍生物的命名與製備 ..................................................................................... 143
13.5.1 醯鹵；鹵化醯基 (Acid Halides) .................................................................. 143
13.5.2 酯 .......................................................................................................... 143
13.5.3 酸酐 ....................................................................................................... 144
13.5.4 醯胺 ....................................................................................................... 145
13.5.5 腈 .......................................................................................................... 147
13.6 羧酸衍生物的反應性 ........................................................................................... 148
13.6.1 醯鹵 ....................................................................................................... 148
13.6.2 酯 .......................................................................................................... 148
13.6.3 酸酐 ....................................................................................................... 149
13.6.4 醯胺 ....................................................................................................... 149
13.6.5 腈 .......................................................................................................... 149
13.7 羧酸衍生物的重排反應 ........................................................................................ 150
13.8 重點整理 ...........................................................................................................
150 13.9 習題 ................................................................................................................. 151

第十四章 芳香族化合物 ........................................................................................... 153
14.1 芳香族衍生物的命名 ........................................................................................... 153
14.1.1 單取代芳香族衍生物的命名......................................................................... 153
14.1.2 雙取代芳香族衍生物的命名......................................................................... 154
14.1.3 多取代苯環衍生物 ..................................................................................... 154
14.2 苯環的結構........................................................................................................ 155
14.3 苯環的穩定性 .................................................................................................... 155
14.4 其它芳香族化合物 .............................................................................................. 156
14.4.1 輪烯 (Annulene) ..................................................................................... 157
14.4.2 芳香族的離子 ........................................................................................... 157
14.5 芳香族化合物的反應 ........................................................................................... 158
14.5.1 苄位的氧化 .............................................................................................. 158
14.5.2 苄位的游離基反應 ..................................................................................... 158
14.5.3 苄位的取代反應 ........................................................................................ 159
14.5.4 苄位的消除反應 ........................................................................................ 159
14.6 親電子性芳香族取代反應 ..................................................................................... 159
14.6.1 鹵化 (Halogenation) ................................................................................ 160
14.6.2 硝基化 (Nitration) ................................................................................... 160
14.6.3 硫酸化 (Sulfonation) ................................................................................ 160
14.6.4 夫里德耳 - 夸夫特烷化作用 (Friedel-Crafts Alkylation) .................................. 161
14.6.5 夫里德耳 - 夸夫特醯基化作用 (Friedel-Crafts Acylation) ................................ 161
14.7 親電子芳香族取代反應速率和位置選擇性 ................................................................ 162
14.7.1 活化基團 (Activating Groups, Activators) ................................................... 162
14.7.2 去活化基團 (Deactivating Groups, Deactivators) ......................................... 163
14.7.3 鹵素 ....................................................................................................... 163
14.8 合成方法的運用 ................................................................................................. 164
14.8.1 定向效應 (Directing Effects) ..................................................................... 164
14.8.2 立體效應 (Steric Effects) ........................................................................... 165
14.8.3 保護基 (Protecting Groups) 的運用 ............................................................ 165
14.9 親核性芳香族取代反應 (Nucleophilic Aromatic Substitution Reactions) ..........166
14.10 芳香族取代和消除反應 ....................................................................................... 166
14.11 苯環的還原 ...................................................................................................... 167
14.11.1 伯奇還原反應 (Birch Reduction) .............................................................. 167
14.12 芳香族雜環的酸度 ............................................................................................. 167
14.13 重點整理 ......................................................................................................... 169
14.14 習題 ............................................................................................................... 169

第十五章 共軛系統與周環反應 ................................................................................... 173
15.1 共軛雙鍵 ........................................................................................................... 173
15.2 共軛雙鍵的加成 ................................................................................................. 173
15.2.1 共軛雙鍵的合成 ........................................................................................ 173
15.2.2 熱力學與動力學 ........................................................................................ 174
15.3 分子軌域理論 (Molecular Orbital Theory) ............................................................ 174
15.3.1 1,3-Butadiene 的分子軌域理論 .................................................................. 174
15.3.2 1,3,5-Hexatriene 的分子軌域理論 .............................................................. 175
15.4 周環反應 (Pericyclic Reactions) .......................................................................... 175
15.4.1 環化加成反應 (Cycloaddition Reactions) .................................................... 175
15.4.2 電子環化反應 (Electrocyclic Reactions) ..................................................... 178
15.4.3 σ 遷移反應 (Sigmatropic Reactions) .......................................................... 180
15.5 重點整理 ........................................................................................................... 182
15.6 習題 ................................................................................................................. 183

第十六章 胺類化合物 .............................................................................................. 185
16.1 胺類的命名 ........................................................................................................ 185
16.1.1 一級胺的命名 ........................................................................................... 185
16.1.2 二級胺的命名 ........................................................................................... 186
16.1.3 三級胺的命名 ........................................................................................... 186
16.1.4 四級胺鹽的命名 ........................................................................................ 186
16.2 胺類的物理性質 ................................................................................................. 186
16.2.1 胺類的幾何形狀 ........................................................................................ 186
16.2.2 胺類的溶解度和沸點 .................................................................................. 187
16.2.3 胺類的鹼度 .............................................................................................. 187
16.2.4 非定域化的效應 ........................................................................................ 189
16.3 胺類的製備 ........................................................................................................ 190
16.3.1 氨的烷基化 .............................................................................................. 190
16.3.2 疊氮化合物 (Azide，-N3) 的還原 ................................................................. 191
16.3.3 加柏利合成 (Gabriel Synthesis) ................................................................. 191
16.3.4 還原胺化反應 (Reductive Amination) ......................................................... 191
16.3.5 還原腈 .................................................................................................... 192
16.3.6 由羧酸轉變成醯胺後再還原......................................................................... 192
16.3.7 還原硝基 (NO2) ........................................................................................ 192
16.4 胺類的反應 ........................................................................................................ 192
16.4.1 醯化反應 ................................................................................................. 193
16.4.2 霍夫曼消除作用 (Hofmann Elimination) .................................................... 194
16.4.3 亞硝化 (Nitrosation) ................................................................................ 194
16.4.4 與一級胺反應的重氮化 ............................................................................... 195
16.4.5 桑德邁爾反應 (Sandmeyer Reactions) ........................................................ 195
16.4.6 重氮偶合反應 (Azo Coupling) .................................................................... 195
16.4.7 與二級胺反應 ........................................................................................... 196
16.5 吡啶 (Pyridine)、吡咯 (Pyrrole) 與咪唑 (Imidazole) .............................................. 196
16.6 磺胺類藥物 (Sulfonamides) ................................................................................ 197
16.7 重點整理 ........................................................................................................... 197
16.8 習題 ................................................................................................................. 198

第十七章 有機金屬 ................................................................................................. 201
17.1 有機金屬化合物 ................................................................................................. 201
17.2 有機金屬化合物的命名 ........................................................................................ 201
17.3 有機鋰試劑 (Organolithium Reagents)................................................................. 202
17.4 有機鎂試劑 (Organomagnesium Reagents) .......................................................... 202
17.5 有機銅試劑 (Organocopper Reagents) ................................................................. 203
17.5.1 偶合反應 (Corey-Posner/Whitesides-House) .............................................. 203
17.5.2 立體專一性 .............................................................................................. 204
17.6 有機錫試劑 (Organotin Reagents) ....................................................................... 204
17.6.1 有機錫化合物的製備 .................................................................................. 204
17.6.2 立體專一性 .............................................................................................. 204
17.7 有機硼試劑 (Organoboron Reagents) ................................................................... 205
17.7.1 立體專一性 .............................................................................................. 206
17.7.2 有機硼試劑與有機錫試劑的優點與缺點 ......................................................... 206
17.8 有機鋅試劑 (Organozinc Reagents) ..................................................................... 206
17.8.1 環丙烷化反應 (Cyclopropanation Reaction)................................................ 206             西蒙斯 - 史密斯反應 (Simmons-Smith Reaction) .......................................... 206
17.8.2 立體專一性 .............................................................................................. 207
17.9 根岸偶聯反應 (Negishi Reaction) ........................................................................ 207
17.9.1 有機鋅試劑的製備 ..................................................................................... 207
17.9.2 立體專一性 .............................................................................................. 208
17.10 赫克反應 (The Heck Reaction) .......................................................................... 208
17.10.1 立體專一性 ............................................................................................ 208
17.11 有機矽試劑 (檜山偶聯反應，Hiyama Coupling) .................................................... 209
17.11.1 立體專一性 ............................................................................................ 209
17.12 薗頭偶合反應 (Sonogashira Coupling) ............................................................... 209
17.13 歧化反應 (Metathesis) ...................................................................................... 210
17.14 重點整理 ......................................................................................................... 210
17.15 習題 ............................................................................................................... 211

第十八章 游離基反應 .............................................................................................. 213
18.1 何謂游離基 ........................................................................................................ 213
18.1.1 游離基的結構 ........................................................................................... 213
18.1.2 游離基的穩定性 ........................................................................................ 213
18.1.3 游離基的共振結構 ..................................................................................... 213
18.2 甲烷的氯化........................................................................................................ 214
18.2.1 游離基起始劑 ........................................................................................... 214
18.2.2 游離基抑制劑 ........................................................................................... 214
18.3 鹵化的選擇性 .................................................................................................... 215
18.4 鹵化的立體選擇性 .............................................................................................. 216
18.4.1 掌性中心的產生 ........................................................................................ 216
18.4.2 掌性的消失 .............................................................................................. 216
18.5 烯丙位的溴化..................................................................................................... 216
18.6 游離基溴化氫的加成 - 反馬克尼可夫的產物 ............................................................. 217
18.7 重點整理 ........................................................................................................... 218
18.8 習題 ................................................................................................................. 219

第十九章 合成聚合物 .............................................................................................. 221
19.1 聚合物的命名..................................................................................................... 221
19.2 聚合物反應型態的分類 ........................................................................................ 221
19.2.1 同元聚合物 (Homopolymer) ..................................................................... 221
19.2.2 共聚合物 (Copolymer).............................................................................. 222
19.2.3 縮合聚合物 (Condensation Polymer) ......................................................... 222
19.3 聚合物的分類 .................................................................................................... 223
19.3.1 鏈增長聚合物 (Chain-growth Polymers) ..................................................... 223
19.3.2 逐步增長聚合物 (Step-growth Polymers) .................................................... 223
19.4 聚合物結構的分類 .............................................................................................. 223
19.4.1 線型 (Linear) .......................................................................................... 223 19.4.2
支鏈 (Branched) ...................................................................................... 223
19.4.3 交聯 (Cross-Linked) ................................................................................ 223
19.5 聚合物的性質..................................................................................................... 224
19.5.1 熱塑性橡膠 (Thermoplastic Polymers)....................................................... 224
19.5.2 熱固性橡膠 (Thermosetting Polymers) ...................................................... 224
19.5.3 彈性體 (Elastomer) .................................................................................. 224
19.6 游離基聚合 ........................................................................................................ 225
19.7 陰離子聚合 (Anionic Polymerization) .................................................................. 226
19.8 陽離子聚合 (Cationic Polymerization) ................................................................. 227
19.9 聚醯胺 (Polyamides) .......................................................................................... 227
19.10 聚酯 (Polyesters) ............................................................................................. 227
19.11 聚氨酯 (Polyurethanes, PU) .............................................................................. 228
19.12 聚碳酸酯 (Polycarbonate, PC) ........................................................................... 228
19.13 聚合物的立體化學 - 齊格勒 - 納他催化劑 ............................................................... 229
19.14 合成橡膠 ......................................................................................................... 229
19.15 可回收的聚合物 ................................................................................................ 229
19.16 生物可分解的聚合物 .......................................................................................... 230
19.17 重點整理 ......................................................................................................... 230
19.18 習題 ............................................................................................................... 231

第二十章 碳水化合物 .............................................................................................. 233
20.1 單醣的分類........................................................................................................ 233
20.1.1 D- 醣和 L- 醣 ........................................................................................... 233
20.1.2 醛醣 (Aldoses) ........................................................................................ 234
20.1.3 酮醣 (Ketoses) ......................................................................................... 235
20.2 單醣的環形結構 ................................................................................................. 236
20.2.1 哌喃醣 (Pyranoses) .................................................................................. 236
20.2.2 呋喃糖 (Furanoses) .................................................................................. 237
20.3 單醣的反應........................................................................................................ 237
20.3.1 酯化和醚化 .............................................................................................. 237
20.3.2 醣苷的形成 .............................................................................................. 238
20.3.3 差向異構作用 (Epimerization) ................................................................... 239
20.3.4 單醣的氧化 .............................................................................................. 239
20.3.5 單醣的還原 .............................................................................................. 240
20.3.6 單醣鏈的加長 (The Kiliani-Fischer Synthesis) ............................................ 240
20.3.7 單醣鏈的縮短 (The Wohl Degradation 和 Ruff Degradation) ........................ 241
20.4 雙醣 ................................................................................................................. 241
20.4.1 麥芽糖 (Maltose) ..................................................................................... 241
20.4.2 纖維雙醣 (Cellobiose) .............................................................................. 242
20.4.3 乳糖 (Lactose) ......................................................................................... 242
20.4.4 蔗糖 (Sucrose) ........................................................................................ 242
20.5 多醣 ................................................................................................................. 243
20.5.1 澱粉 (Starch) ........................................................................................... 243
20.5.2 纖維素 (Cellulose) ................................................................................... 243
20.6 胺醣 (Amino Sugars) ......................................................................................... 244
20.6.1 N- 醣苷 ................................................................................................... 244
20.7 重點整理 ........................................................................................................... 245
20.8 習題 ................................................................................................................. 246
中英文字詞解釋 ..................................................................................................... 249
習題簡答 .............................................................................................................. 259

第一章 結構與鍵結 ................................................................................................. 1
1.1 混成的原子軌域 (Hybridized Atomic Orbitals) ........................................................ 1
1.2 預測分子的幾何形狀 ............................................................................................. 1
1.2.1 四面體 (Tetrahedral) ................................................................................. 2
1.2.2 三角錐狀 (Trigonal Pyramidal) ................................................................... 2
1.2.3 彎曲狀 (Bent) ............................................................................................ 2
1.2.4 三角平面 (Trigonal Planar)......................................................................... 3
1.2.5 直線 (Linear) ............................................................................................ 3
1.3 極性共價鍵 ......................................................................................................... 3
1.3.1 偶極矩和分子的極性 (Dipole Moment and Molecular Polarity) ....................... 3
1.4 分子之間的作用力與分子的物理性質 ........................................................................ 5
1.4.1 氫鍵 (Hydrogen Bonding) .......................................................................... 5
1.4.2 偶極 - 偶極作用力 (Dipole-Dipole Interactions) ............................................ 5
1.4.3 偶極 - 誘導偶極作用力 (Dipole-Induced Dipole Interactions) ......................... 5
1.4.4 倫敦分散力 (Fleeting Dipole-Dipole Interactions, London Dispersion Forces) 6
1.5 重點整理 ............................................................................................................ 7
1.6 習題 .................................................................................................................. 8

第二章 分子的表示方式 ........................................................................................... 9
2.1 有機分子的表示方式 ............................................................................................. 9
2.2 鍵 - 線結構式 (Bond-Line Structure) ..................................................................... 9
2.3 形式電荷 (Formal Charge) ................................................................................... 10
2.3.1 決定孤對電子的數目 ................................................................................... 10
2.4 鍵 - 線結構式的三維表示方式 ................................................................................. 11
2.5 共振和彎曲的箭頭 ................................................................................................ 11
2.6 評斷相對共振結構的重要性 .................................................................................... 12
2.7 共振混合 (Resonance Hybrid) .............................................................................. 13
2.8 非定域化的 (Delocalized) 與定域化的 (Localized) 孤對電子 ....................................... 13
2.8.1 非定域化的孤對電子 ................................................................................... 13
2.8.2 定域化的孤對電子 ...................................................................................... 14
2.9 重點整理 ............................................................................................................ 15
2.10 習題 ................................................................................................................. 15

第三章 碳氫化合物和有機化合物的分類 ....................................................................... 17
3.1 烷類 / 環烷類 (Alkanes/Cycloalkanes) ................................................................... 17
3.1.1 命名 ......................................................................................................... 17
3.2 烯類 (Alkenes) .................................................................................................... 21
3.2.1 布萊特規則 (Bredt’s Rule) ........................................................................... 22
3.2.2 命名......................................................................................................... 23
3.3 炔類 (Alkynes) .................................................................................................... 24
3.3.1 命名 ......................................................................................................... 25
3.3.2 乙炔的酸度和末端炔 ................................................................................... 26
3.4 官能基 (Functional Groups) ................................................................................. 27
3.5 重點整理 ............................................................................................................ 28
3.6 習題 .................................................................................................................. 28

第四章 酸和鹼 ....................................................................................................... 29
4.1 酸和鹼的定義 ...................................................................................................... 29
4.1.1 共軛酸和共軛鹼 ......................................................................................... 29
4.1.2 酸鹼的質子理論 ......................................................................................... 29
4.1.3 運用 pKa 數值比較鹼度 (Basicity) ................................................................. 30
4.1.4 運用 pKa 數值預測平衡的位置 ....................................................................... 31
4.1.5 酸鹼的電子理論 ......................................................................................... 32
4.2 布朗斯特酸的定量概念 .......................................................................................... 32
4.2.1 共軛鹼的穩定度 ......................................................................................... 32
4.2.2 影響負電荷的穩定度 ................................................................................... 33
4.3 平衡位置與試劑的選擇 .......................................................................................... 34
4.4 溶劑效應 ............................................................................................................ 35
4.5 重點整理 ............................................................................................................ 35
4.6 習題 .................................................................................................................. 36

第五章 構型 .......................................................................................................... 37
5.1 紐曼投影式 (Newman Projection) ......................................................................... 37
5.1.1 乙烷 ......................................................................................................... 37
5.1.2 丙烷 ......................................................................................................... 38
5.1.3 丁烷 ......................................................................................................... 38
5.2 環烷 .................................................................................................................. 39
5.3 環丙烷構型 ......................................................................................................... 39
5.4 環丁烷構型 ......................................................................................................... 39
5.5 環戊烷構型 ......................................................................................................... 40
5.6 環己烷構型 ......................................................................................................... 40
5.6.1 單取代環己烷構型 ...................................................................................... 40
5.6.2 雙取代環己烷構型 ...................................................................................... 41
5.7 重點整理 ............................................................................................................ 43
5.8 習題 .................................................................................................................. 43

第六章 立體異構性 ................................................................................................. 45
6.1 異構性 (Isomerism) ............................................................................................ 45
6.1.1 構型異構物 ............................................................................................... 46
6.2 立體異構性 (Stereoisomerism) ............................................................................. 46
6.2.1 掌性 (Chirality) ......................................................................................... 46
6.2.2 分子的掌性 ............................................................................................... 47
6.2.3 鏡像異構物 (Enantiomers) ......................................................................... 47
6.2.4 非鏡像異構物 (Diastereoisomers) ............................................................... 47
6.2.5 內消旋化合物 (Meso Compounds) ............................................................... 48
6.3 運用 Cahn-Ingold-Prelog 系統標示組態 (Configuration) .......................................... 48
6.3.1 命名 ......................................................................................................... 49
6.4 含有掌性中心的掌性分子 ....................................................................................... 49
6.4.1 費雪投影式 (Fischer Projection) ................................................................. 49
6.5 光學活性 (Optical Activity) ................................................................................... 51
6.5.1 比旋光度 (Specific Rotation)....................................................................... 51
6.5.2 鏡像異構物超越量 (Enantiomeric Excess, ee) ............................................... 52
6.6 不具掌性中心的掌性化合物 .................................................................................... 52
6.6.1 阻轉異構體 (Atropisomers) ........................................................................ 52
6.6.2 丙二烯 (Allenes) ........................................................................................ 53
6.6.3 含氮和含硫化合物 ...................................................................................... 53
6.7 鏡像異構物的解析 (Resolution of Enantiomers) ..................................................... 54
6.7.1 掌性解析試劑 ............................................................................................ 54
6.8 重點整理 ............................................................................................................ 55
6.9 習題 .................................................................................................................. 55

第七章 取代反應 .................................................................................................... 59
7.1 鹵烷 .................................................................................................................. 59
7.1.1 命名 ......................................................................................................... 59
7.1.2 鹵烷的物理性質 ......................................................................................... 59
7.1.3 鹵烷的製備 ............................................................................................... 60
7.2 SN2 反應 ............................................................................................................. 61
7.2.1 離去基...................................................................................................... 61
7.2.2 動力學...................................................................................................... 61
7.2.3 受質結構影響 SN2 的反應速率 ....................................................................... 62
7.2.4 親核劑的強度影響 SN2 的反應速率 ................................................................. 62
7.2.5 SN2 反應的立體專一性 ................................................................................. 63
7.2.6 溶劑影響 SN2 的反應速率 ............................................................................. 64
7.2.7 親核劑 vs 鹼 .............................................................................................. 65
7.3 SN1 反應 ............................................................................................................. 65
7.3.1 動力學...................................................................................................... 66
7.3.2 重排反應 .................................................................................................. 66
7.3.3 受質的影響 ............................................................................................... 67
7.3.4 SN1 反應的立體化學 .................................................................................... 67
7.3.5 溶劑的影響 ............................................................................................... 68
7.4 SN1 與 SN2 的離去基 ............................................................................................. 68
7.5 重點整理 ............................................................................................................ 69
7.6 習題 .................................................................................................................. 69 第八章 消除反應 .................................................................................................... 71
8.1 消除反應 ............................................................................................................ 71
8.2 烯類的穩定度 ...................................................................................................... 71
8.2.1 環烯的穩定度 ............................................................................................ 71
8.3 E2 反應機制 ........................................................................................................ 72
8.3.1 脫鹵氫反應 (Dehydrohalogenation) ............................................................ 72
8.3.2 動力學 ..................................................................................................... 72
8.3.3 結構影響 E2 反應的速率 .............................................................................. 72
8.3.4 E2 反應的位置選擇性 .................................................................................. 73
8.3.5 E2 反應的立體選擇性 .................................................................................. 73
8.3.6 E2 反應的立體專一性 .................................................................................. 73
8.4 E1 反應機制 ........................................................................................................ 74
8.4.1 動力學 ...................................................................................................... 74
8.4.2 重排反應 .................................................................................................. 75
8.5 E1 反應的速率 ..................................................................................................... 75
8.6 E1 反應的位置選擇性 ............................................................................................ 75
8.7 E1 反應的立體選擇性 ............................................................................................ 76
8.8 判別取代反應還是消除反應 .................................................................................... 76
8.9 重點整理 ............................................................................................................ 77
8.10 習題 ................................................................................................................. 78

第九章 加成反應 .................................................................................................... 81
9.1 加成反應的類型 ................................................................................................... 81
9.2 烯類的加成 - 熱力學的觀點 .................................................................................... 81
9.3 氫鹵化 - 位置選擇性 - 馬可尼可夫加成 (Markovnikov Addition).................................. 82
9.4 氫鹵化的重排反應 ................................................................................................ 83
9.4.1 氫負離子重排 (Hydride shift) 與甲基負離子重排 (Methyl shift) ........................ 83
9.5 酸催化水合反應 ................................................................................................... 83
9.6 氧汞化 - 去汞化 (Oxymercuration-Demercuration) ................................................. 83
9.7 氫化反應 (Hydrogenation) ................................................................................... 84
9.8 硼氫化 - 氧化作用 (Hydroboration-Oxidation) ........................................................ 84
9.9 鹵化 (Halogenation) 反應 .................................................................................... 85
9.10 鹵醇 (Halohydrin) 反應 ...................................................................................... 85
9.11 環氧化 (Epoxidation) ......................................................................................... 86
9.12 順式雙醇化作用 (syn Dihydroxylation) .................................................................. 86
9.13 炔類的加成反應 ................................................................................................. 87
9.14 炔類的氫鹵化反應 .............................................................................................. 87
9.15 炔類的水合反應 ................................................................................................. 88
9.16 炔類的硼氫化 - 氧化反應 ...................................................................................... 89
9.17 炔類的鹵化反應 ................................................................................................. 89
9.18 重點整理 ........................................................................................................... 90
9.19 習題 ................................................................................................................. 91
第十章 醇、酚、醚、環氧、硫和硫醇 .......................................................................... 93
10.1 醇的命名 ........................................................................................................... 93
10.1.1 醇的物理性質 ........................................................................................... 94
10.1.2 醇的製備 ................................................................................................. 94
10.1.3 有機金屬與醛的加成反應 ............................................................................ 95
10.1.4 有機金屬與酮和酯的加成反應 ..................................................................... 95
10.1.5 醛、酮、酯和酸的還原 ............................................................................... 95
10.2 醇的氧化 ........................................................................................................... 96
10.3 醇的反應 ........................................................................................................... 97
10.3.1 SN2 反應 ................................................................................................. 97
10.3.2 SN1 反應 ................................................................................................. 98
10.3.3 E2 反應 .................................................................................................. 98
10.3.4 E1 反應 .................................................................................................. 99
10.3.5 酯化反應 ................................................................................................. 99
10.4 酚的命名 ........................................................................................................... 99
10.4.1 酚的氧化 ................................................................................................. 100
10.5 醚的命名 ........................................................................................................... 100
10.5.1 醚的製備 ................................................................................................. 101
10.5.2 酸催化烯類與醇類的反應 ............................................................................ 101
10.5.3 烷氧汞化 - 去汞化 (Alkoxymercuration-Demercuration) .............................. 101
10.5.4 醚的反應 ................................................................................................. 102
10.5.5 醚的運用 ................................................................................................. 103
10.6 環氧的命名 ........................................................................................................ 104
10.6.1 環氧的製備 .............................................................................................. 105
10.6.2 環氧的反應 .............................................................................................. 105
10.7 硫和硫醇 ........................................................................................................... 106
10.7.1 硫化合物的命名 ........................................................................................ 106
10.7.2 硫衍生物的命名 ........................................................................................ 106
10.7.3 硫醚的合成 .............................................................................................. 107
10.7.4 硫化合物的反應 ........................................................................................ 107
10.8 重點整理 ...........................................................................................................108
10.9 習題 .................................................................................................................108

第十一章 醛類和酮類 .............................................................................................. 111
11.1 醛類的命名 ........................................................................................................ 111
11.2 醛類的製備........................................................................................................ 112
11.2.1 氧化 ....................................................................................................... 112
11.2.2 臭氧氧化切斷 ........................................................................................... 112
11.2.3 硼氫化 - 氧化 ........................................................................................... 112
11.2.4 鄰二醇的氧化切斷 ..................................................................................... 112
11.2.5 氰的還原 ................................................................................................. 113
11.2.6 醯氯的還原 .............................................................................................. 113
11.3 酮類的命名........................................................................................................ 113
11.4 酮類的製備 ........................................................................................................ 114
11.4.1 二級醇的氧化 ........................................................................................... 114
11.4.2 臭氧氧化切斷 ........................................................................................... 114
11.4.3 酸催化水解末端的炔類 ............................................................................... 114
11.4.4 夫里德耳 - 夸夫特醯化作用 (Friedel-Crafts Acylation) ................................... 114
11.5 醛類和酮類中與羰基的反應 .................................................................................. 114
11.5.1 與水的反應 - 水合物的形成 (Hydrate Formation) .......................................... 114
11.5.2 半縮醛 (Hemiacetal) 的形成 ...................................................................... 115
11.5.3 縮醛的形成 .............................................................................................. 115
11.5.4 與胺類的反應 ........................................................................................... 116
11.5.5 沃夫 - 奇希諾還原 (Wolff-Kishner Reduction).............................................. 117
11.5.6 與硫醇的反應 ........................................................................................... 117
11.5.7 與有機金屬的反應 ..................................................................................... 118
11.5.8 與氰化氫 (HCN) 的反應 - 氰醇 (Cyanohydrin) 的合成 .................................... 119
11.5.9 威悌反應 (Wittig Reaction) ....................................................................... 120
11.5.10 與氫負離子的反應 ................................................................................... 121
11.5.11 拜耳 - 維立格氧化反應 (Baeyer-Villiger Oxidation) ..................................... 121
11.5.12 克萊門森還原作用 (Clemmensen Reduction) ............................................ 121
11.6 重點整理 ........................................................................................................... 122
11.7習題 ................................................................................................................. 123

第十二章、醛與酮的 α 位置碳的化學 .......................................................................... 125
12.1 烯醇和烯醇鹽 α 位置的鹵化 .................................................................................. 125
12.1.1 在酸性條件 .............................................................................................. 126
12.1.2 赫耳 - 華哈德 - 季林斯基反應 (Hell-Volhard-Zelinsky Reaction) ..................... 127
12.1.3 鹼性條件 ................................................................................................. 127
12.1.4 O- 烷基化或 C- 烷基化 (O-Alkylation and C-Alkylation) ................................ 127
12.1.5 鹵化 ....................................................................................................... 128
12.1.6 鹵仿反應 (Haloform Reaction) .................................................................. 128
12.2 醛醇反應與醛醇縮合 (Aldol Reactions and Aldol Condensations) ........................... 128
12.2.1 醛醇 ( 加成 ) 反應 ..................................................................................... 128
12.2.2 醛醇縮合 (Aldol Condensations) ............................................................... 129
12.2.3 交聯醛醇反應 (Crossed Aldol Reactions) .................................................... 129
12.2.4 克萊森 - 施密特縮合反應 (Claisen-Schmidt Condensations) .......................... 130
12.2.5 分子內的醛醇反應 (Intramolecular Aldol Reactions) ................................... 130
12.3 酯的縮合 ........................................................................................................... 130
12.3.1 克萊森縮合 (Claisen Condensations) ......................................................... 130
12.3.2 交聯克萊森縮合 (Crossed Claisen Condensations) ...................................... 131
12.3.3 狄克曼縮合反應 (Dieckmann Condensations) ............................................. 131
12.4 烯醇鹽 α 位置的烷基化 ........................................................................................ 132
12.4.1 乙醯乙酸酯合成 (Acetoacetic Ester Synthesis) ............................................ 132
12.4.2 丙二酸酯合成法 (Malonic Ester Synthesis) ................................................. 133
12.4.3 克腦文蓋爾縮合反應 (Knoevenagel Reaction) .............................................. 133
12.5 共軛加成反應 .................................................................................................... 133
12.5.1 魯賓遜成環反應 (The Robinson Annulation Reaction) ................................. 134
12.5.2 施托克烯胺反應 (Stork Enamine Reaction) ................................................. 134
12.5.3 曼尼赫反應 (The Mannich Reaction) ......................................................... 135
12.5.4  α,β- 不飽和酮的烷基化 .............................................................................. 135
12.6 重點整理 ........................................................................................................... 135
12.7 習題 ................................................................................................................. 136

第十三章 羧酸和羧酸的衍生物 ................................................................................... 139
13.1 羧酸的命名 ........................................................................................................ 139
13.1.1 單一個羧酸 .............................................................................................. 139
13.1.2 兩個 (雙) 羧酸 .......................................................................................... 139
13.2 羧酸的物理性質 ................................................................................................. 140
13.2.1 羧酸的酸度 .............................................................................................. 140
13.3 羧酸的製備........................................................................................................ 141
13.3.1 炔類的臭氧化 ........................................................................................... 141
13.3.2 一級醇的氧化 ........................................................................................... 142
13.3.3 烷基苯的氧化 ........................................................................................... 142
13.3.4 腈的水解 ................................................................................................. 142
13.3.5 格里納試劑的羰基化 .................................................................................. 142
13.4 羧酸的反應 ........................................................................................................ 142
13.5 羧酸衍生物的命名與製備 ..................................................................................... 143
13.5.1 醯鹵；鹵化醯基 (Acid Halides) .................................................................. 143
13.5.2 酯 .......................................................................................................... 143
13.5.3 酸酐 ....................................................................................................... 144
13.5.4 醯胺 ....................................................................................................... 145
13.5.5 腈 .......................................................................................................... 147
13.6 羧酸衍生物的反應性 ........................................................................................... 148
13.6.1 醯鹵 ....................................................................................................... 148
13.6.2 酯 .......................................................................................................... 148
13.6.3 酸酐 ....................................................................................................... 149
13.6.4 醯胺 ....................................................................................................... 149
13.6.5 腈 .......................................................................................................... 149
13.7 羧酸衍生物的重排反應 ........................................................................................ 150
13.8 重點整理 ...........................................................................................................
150 13.9 習題 ................................................................................................................. 151

第十四章 芳香族化合物 ........................................................................................... 153
14.1 芳香族衍生物的命名 ........................................................................................... 153
14.1.1 單取代芳香族衍生物的命名......................................................................... 153
14.1.2 雙取代芳香族衍生物的命名......................................................................... 154
14.1.3 多取代苯環衍生物 ..................................................................................... 154
14.2 苯環的結構........................................................................................................ 155
14.3 苯環的穩定性 .................................................................................................... 155
14.4 其它芳香族化合物 .............................................................................................. 156
14.4.1 輪烯 (Annulene) ..................................................................................... 157
14.4.2 芳香族的離子 ........................................................................................... 157
14.5 芳香族化合物的反應 ........................................................................................... 158
14.5.1 苄位的氧化 .............................................................................................. 158
14.5.2 苄位的游離基反應 ..................................................................................... 158
14.5.3 苄位的取代反應 ........................................................................................ 159
14.5.4 苄位的消除反應 ........................................................................................ 159
14.6 親電子性芳香族取代反應 ..................................................................................... 159
14.6.1 鹵化 (Halogenation) ................................................................................ 160
14.6.2 硝基化 (Nitration) ................................................................................... 160
14.6.3 硫酸化 (Sulfonation) ................................................................................ 160
14.6.4 夫里德耳 - 夸夫特烷化作用 (Friedel-Crafts Alkylation) .................................. 161
14.6.5 夫里德耳 - 夸夫特醯基化作用 (Friedel-Crafts Acylation) ................................ 161
14.7 親電子芳香族取代反應速率和位置選擇性 ................................................................ 162
14.7.1 活化基團 (Activating Groups, Activators) ................................................... 162
14.7.2 去活化基團 (Deactivating Groups, Deactivators) ......................................... 163
14.7.3 鹵素 ....................................................................................................... 163
14.8 合成方法的運用 ................................................................................................. 164
14.8.1 定向效應 (Directing Effects) ..................................................................... 164
14.8.2 立體效應 (Steric Effects) ........................................................................... 165
14.8.3 保護基 (Protecting Groups) 的運用 ............................................................ 165
14.9 親核性芳香族取代反應 (Nucleophilic Aromatic Substitution Reactions) ..........166
14.10 芳香族取代和消除反應 ....................................................................................... 166
14.11 苯環的還原 ...................................................................................................... 167
14.11.1 伯奇還原反應 (Birch Reduction) .............................................................. 167
14.12 芳香族雜環的酸度 ............................................................................................. 167
14.13 重點整理 ......................................................................................................... 169
14.14 習題 ............................................................................................................... 169

第十五章 共軛系統與周環反應 ................................................................................... 173
15.1 共軛雙鍵 ........................................................................................................... 173
15.2 共軛雙鍵的加成 ................................................................................................. 173
15.2.1 共軛雙鍵的合成 ........................................................................................ 173
15.2.2 熱力學與動力學 ........................................................................................ 174
15.3 分子軌域理論 (Molecular Orbital Theory) ............................................................ 174
15.3.1 1,3-Butadiene 的分子軌域理論 .................................................................. 174
15.3.2 1,3,5-Hexatriene 的分子軌域理論 .............................................................. 175
15.4 周環反應 (Pericyclic Reactions) .......................................................................... 175
15.4.1 環化加成反應 (Cycloaddition Reactions) .................................................... 175
15.4.2 電子環化反應 (Electrocyclic Reactions) ..................................................... 178
15.4.3 σ 遷移反應 (Sigmatropic Reactions) .......................................................... 180
15.5 重點整理 ........................................................................................................... 182
15.6 習題 ................................................................................................................. 183

第十六章 胺類化合物 .............................................................................................. 185
16.1 胺類的命名 ........................................................................................................ 185
16.1.1 一級胺的命名 ........................................................................................... 185
16.1.2 二級胺的命名 ........................................................................................... 186
16.1.3 三級胺的命名 ........................................................................................... 186
16.1.4 四級胺鹽的命名 ........................................................................................ 186
16.2 胺類的物理性質 ................................................................................................. 186
16.2.1 胺類的幾何形狀 ........................................................................................ 186
16.2.2 胺類的溶解度和沸點 .................................................................................. 187
16.2.3 胺類的鹼度 .............................................................................................. 187
16.2.4 非定域化的效應 ........................................................................................ 189
16.3 胺類的製備 ........................................................................................................ 190
16.3.1 氨的烷基化 .............................................................................................. 190
16.3.2 疊氮化合物 (Azide，-N3) 的還原 ................................................................. 191
16.3.3 加柏利合成 (Gabriel Synthesis) ................................................................. 191
16.3.4 還原胺化反應 (Reductive Amination) ......................................................... 191
16.3.5 還原腈 .................................................................................................... 192
16.3.6 由羧酸轉變成醯胺後再還原......................................................................... 192
16.3.7 還原硝基 (NO2) ........................................................................................ 192
16.4 胺類的反應 ........................................................................................................ 192
16.4.1 醯化反應 ................................................................................................. 193
16.4.2 霍夫曼消除作用 (Hofmann Elimination) .................................................... 194
16.4.3 亞硝化 (Nitrosation) ................................................................................ 194
16.4.4 與一級胺反應的重氮化 ............................................................................... 195
16.4.5 桑德邁爾反應 (Sandmeyer Reactions) ........................................................ 195
16.4.6 重氮偶合反應 (Azo Coupling) .................................................................... 195
16.4.7 與二級胺反應 ........................................................................................... 196
16.5 吡啶 (Pyridine)、吡咯 (Pyrrole) 與咪唑 (Imidazole) .............................................. 196
16.6 磺胺類藥物 (Sulfonamides) ................................................................................ 197
16.7 重點整理 ........................................................................................................... 197
16.8 習題 ................................................................................................................. 198

第十七章 有機金屬 ................................................................................................. 201
17.1 有機金屬化合物 ................................................................................................. 201
17.2 有機金屬化合物的命名 ........................................................................................ 201
17.3 有機鋰試劑 (Organolithium Reagents)................................................................. 202
17.4 有機鎂試劑 (Organomagnesium Reagents) .......................................................... 202
17.5 有機銅試劑 (Organocopper Reagents) ................................................................. 203
17.5.1 偶合反應 (Corey-Posner/Whitesides-House) .............................................. 203
17.5.2 立體專一性 .............................................................................................. 204
17.6 有機錫試劑 (Organotin Reagents) ....................................................................... 204
17.6.1 有機錫化合物的製備 .................................................................................. 204
17.6.2 立體專一性 .............................................................................................. 204
17.7 有機硼試劑 (Organoboron Reagents) ................................................................... 205
17.7.1 立體專一性 .............................................................................................. 206
17.7.2 有機硼試劑與有機錫試劑的優點與缺點 ......................................................... 206
17.8 有機鋅試劑 (Organozinc Reagents) ..................................................................... 206
17.8.1 環丙烷化反應 (Cyclopropanation Reaction)................................................ 206             西蒙斯 - 史密斯反應 (Simmons-Smith Reaction) .......................................... 206
17.8.2 立體專一性 .............................................................................................. 207
17.9 根岸偶聯反應 (Negishi Reaction) ........................................................................ 207
17.9.1 有機鋅試劑的製備 ..................................................................................... 207
17.9.2 立體專一性 .............................................................................................. 208
17.10 赫克反應 (The Heck Reaction) .......................................................................... 208
17.10.1 立體專一性 ............................................................................................ 208
17.11 有機矽試劑 (檜山偶聯反應，Hiyama Coupling) .................................................... 209
17.11.1 立體專一性 ............................................................................................ 209
17.12 薗頭偶合反應 (Sonogashira Coupling) ............................................................... 209
17.13 歧化反應 (Metathesis) ...................................................................................... 210
17.14 重點整理 ......................................................................................................... 210
17.15 習題 ............................................................................................................... 211

第十八章 游離基反應 .............................................................................................. 213
18.1 何謂游離基 ........................................................................................................ 213
18.1.1 游離基的結構 ........................................................................................... 213
18.1.2 游離基的穩定性 ........................................................................................ 213
18.1.3 游離基的共振結構 ..................................................................................... 213
18.2 甲烷的氯化........................................................................................................ 214
18.2.1 游離基起始劑 ........................................................................................... 214
18.2.2 游離基抑制劑 ........................................................................................... 214
18.3 鹵化的選擇性 .................................................................................................... 215
18.4 鹵化的立體選擇性 .............................................................................................. 216
18.4.1 掌性中心的產生 ........................................................................................ 216
18.4.2 掌性的消失 .............................................................................................. 216
18.5 烯丙位的溴化..................................................................................................... 216
18.6 游離基溴化氫的加成 - 反馬克尼可夫的產物 ............................................................. 217
18.7 重點整理 ........................................................................................................... 218
18.8 習題 ................................................................................................................. 219

第十九章 合成聚合物 .............................................................................................. 221
19.1 聚合物的命名..................................................................................................... 221
19.2 聚合物反應型態的分類 ........................................................................................ 221
19.2.1 同元聚合物 (Homopolymer) ..................................................................... 221
19.2.2 共聚合物 (Copolymer).............................................................................. 222
19.2.3 縮合聚合物 (Condensation Polymer) ......................................................... 222
19.3 聚合物的分類 .................................................................................................... 223
19.3.1 鏈增長聚合物 (Chain-growth Polymers) ..................................................... 223
19.3.2 逐步增長聚合物 (Step-growth Polymers) .................................................... 223
19.4 聚合物結構的分類 .............................................................................................. 223
19.4.1 線型 (Linear) .......................................................................................... 223 19.4.2
支鏈 (Branched) ...................................................................................... 223
19.4.3 交聯 (Cross-Linked) ................................................................................ 223
19.5 聚合物的性質..................................................................................................... 224
19.5.1 熱塑性橡膠 (Thermoplastic Polymers)....................................................... 224
19.5.2 熱固性橡膠 (Thermosetting Polymers) ...................................................... 224
19.5.3 彈性體 (Elastomer) .................................................................................. 224
19.6 游離基聚合 ........................................................................................................ 225
19.7 陰離子聚合 (Anionic Polymerization) .................................................................. 226
19.8 陽離子聚合 (Cationic Polymerization) ................................................................. 227
19.9 聚醯胺 (Polyamides) .......................................................................................... 227
19.10 聚酯 (Polyesters) ............................................................................................. 227
19.11 聚氨酯 (Polyurethanes, PU) .............................................................................. 228
19.12 聚碳酸酯 (Polycarbonate, PC) ........................................................................... 228
19.13 聚合物的立體化學 - 齊格勒 - 納他催化劑 ............................................................... 229
19.14 合成橡膠 ......................................................................................................... 229
19.15 可回收的聚合物 ................................................................................................ 229
19.16 生物可分解的聚合物 .......................................................................................... 230
19.17 重點整理 ......................................................................................................... 230
19.18 習題 ............................................................................................................... 231

第二十章 碳水化合物 .............................................................................................. 233
20.1 單醣的分類........................................................................................................ 233
20.1.1 D- 醣和 L- 醣 ........................................................................................... 233
20.1.2 醛醣 (Aldoses) ........................................................................................ 234
20.1.3 酮醣 (Ketoses) ......................................................................................... 235
20.2 單醣的環形結構 ................................................................................................. 236
20.2.1 哌喃醣 (Pyranoses) .................................................................................. 236
20.2.2 呋喃糖 (Furanoses) .................................................................................. 237
20.3 單醣的反應........................................................................................................ 237
20.3.1 酯化和醚化 .............................................................................................. 237
20.3.2 醣苷的形成 .............................................................................................. 238
20.3.3 差向異構作用 (Epimerization) ................................................................... 239
20.3.4 單醣的氧化 .............................................................................................. 239
20.3.5 單醣的還原 .............................................................................................. 240
20.3.6 單醣鏈的加長 (The Kiliani-Fischer Synthesis) ............................................ 240
20.3.7 單醣鏈的縮短 (The Wohl Degradation 和 Ruff Degradation) ........................ 241
20.4 雙醣 ................................................................................................................. 241
20.4.1 麥芽糖 (Maltose) ..................................................................................... 241
20.4.2 纖維雙醣 (Cellobiose) .............................................................................. 242
20.4.3 乳糖 (Lactose) ......................................................................................... 242
20.4.4 蔗糖 (Sucrose) ........................................................................................ 242
20.5 多醣 ................................................................................................................. 243
20.5.1 澱粉 (Starch) ........................................................................................... 243
20.5.2 纖維素 (Cellulose) ................................................................................... 243
20.6 胺醣 (Amino Sugars) ......................................................................................... 244
20.6.1 N- 醣苷 ................................................................................................... 244
20.7 重點整理 ........................................................................................................... 245
20.8 習題 ................................................................................................................. 246
中英文字詞解釋 ..................................................................................................... 249
習題簡答 .............................................................................................................. 259

第一章 結構與鍵結 ................................................................................................. 1
1.1 混成的原子軌域 (Hybridized Atomic Orbitals) ........................................................ 1
1.2 預測分子的幾何形狀 ............................................................................................. 1
1.2.1 四面體 (Tetrahedral) ................................................................................. 2
1.2.2 三角錐狀 (Trigonal Pyramidal) ................................................................... 2
1.2.3 彎曲狀 (Bent) ............................................................................................ 2
1.2.4 三角平面 (Trigonal Planar)......................................................................... 3
1.2.5 直線 (Linear) ............................................................................................ 3
1.3 極性共價鍵 ......................................................................................................... 3
1.3.1 偶極矩和分子的極性 (Dipole Moment and Molecular Polarity) ....................... 3
1.4 分子之間的作用力與分子的物理性質 ........................................................................ 5
1.4.1 氫鍵 (Hydrogen Bonding) .......................................................................... 5
1.4.2 偶極 - 偶極作用力 (Dipole-Dipole Interactions) ............................................ 5
1.4.3 偶極 - 誘導偶極作用力 (Dipole-Induced Dipole Interactions) ......................... 5
1.4.4 倫敦分散力 (Fleeting Dipole-Dipole Interactions, London Dispersion Forces) 6
1.5 重點整理 ............................................................................................................ 7
1.6 習題 .................................................................................................................. 8

第二章 分子的表示方式 ........................................................................................... 9
2.1 有機分子的表示方式 ............................................................................................. 9
2.2 鍵 - 線結構式 (Bond-Line Structure) ..................................................................... 9
2.3 形式電荷 (Formal Charge) ................................................................................... 10
2.3.1 決定孤對電子的數目 ................................................................................... 10
2.4 鍵 - 線結構式的三維表示方式 ................................................................................. 11
2.5 共振和彎曲的箭頭 ................................................................................................ 11
2.6 評斷相對共振結構的重要性 .................................................................................... 12
2.7 共振混合 (Resonance Hybrid) .............................................................................. 13
2.8 非定域化的 (Delocalized) 與定域化的 (Localized) 孤對電子 ....................................... 13
2.8.1 非定域化的孤對電子 ................................................................................... 13
2.8.2 定域化的孤對電子 ...................................................................................... 14
2.9 重點整理 ............................................................................................................ 15
2.10 習題 ................................................................................................................. 15

第三章 碳氫化合物和有機化合物的分類 ....................................................................... 17
3.1 烷類 / 環烷類 (Alkanes/Cycloalkanes) ................................................................... 17
3.1.1 命名 ......................................................................................................... 17
3.2 烯類 (Alkenes) .................................................................................................... 21
3.2.1 布萊特規則 (Bredt’s Rule) ........................................................................... 22
3.2.2 命名......................................................................................................... 23
3.3 炔類 (Alkynes) .................................................................................................... 24
3.3.1 命名 ......................................................................................................... 25
3.3.2 乙炔的酸度和末端炔 ................................................................................... 26
3.4 官能基 (Functional Groups) ................................................................................. 27
3.5 重點整理 ............................................................................................................ 28
3.6 習題 .................................................................................................................. 28

第四章 酸和鹼 ....................................................................................................... 29
4.1 酸和鹼的定義 ...................................................................................................... 29
4.1.1 共軛酸和共軛鹼 ......................................................................................... 29
4.1.2 酸鹼的質子理論 ......................................................................................... 29
4.1.3 運用 pKa 數值比較鹼度 (Basicity) ................................................................. 30
4.1.4 運用 pKa 數值預測平衡的位置 ....................................................................... 31
4.1.5 酸鹼的電子理論 ......................................................................................... 32
4.2 布朗斯特酸的定量概念 .......................................................................................... 32
4.2.1 共軛鹼的穩定度 ......................................................................................... 32
4.2.2 影響負電荷的穩定度 ................................................................................... 33
4.3 平衡位置與試劑的選擇 .......................................................................................... 34
4.4 溶劑效應 ............................................................................................................ 35
4.5 重點整理 ............................................................................................................ 35
4.6 習題 .................................................................................................................. 36

第五章 構型 .......................................................................................................... 37
5.1 紐曼投影式 (Newman Projection) ......................................................................... 37
5.1.1 乙烷 ......................................................................................................... 37
5.1.2 丙烷 ......................................................................................................... 38
5.1.3 丁烷 ......................................................................................................... 38
5.2 環烷 .................................................................................................................. 39
5.3 環丙烷構型 ......................................................................................................... 39
5.4 環丁烷構型 ......................................................................................................... 39
5.5 環戊烷構型 ......................................................................................................... 40
5.6 環己烷構型 ......................................................................................................... 40
5.6.1 單取代環己烷構型 ...................................................................................... 40
5.6.2 雙取代環己烷構型 ...................................................................................... 41
5.7 重點整理 ............................................................................................................ 43
5.8 習題 .................................................................................................................. 43

第六章 立體異構性 ................................................................................................. 45
6.1 異構性 (Isomerism) ............................................................................................ 45
6.1.1 構型異構物 ............................................................................................... 46
6.2 立體異構性 (Stereoisomerism) ............................................................................. 46
6.2.1 掌性 (Chirality) ......................................................................................... 46
6.2.2 分子的掌性 ............................................................................................... 47
6.2.3 鏡像異構物 (Enantiomers) ......................................................................... 47
6.2.4 非鏡像異構物 (Diastereoisomers) ............................................................... 47
6.2.5 內消旋化合物 (Meso Compounds) ............................................................... 48
6.3 運用 Cahn-Ingold-Prelog 系統標示組態 (Configuration) .......................................... 48
6.3.1 命名 ......................................................................................................... 49
6.4 含有掌性中心的掌性分子 ....................................................................................... 49
6.4.1 費雪投影式 (Fischer Projection) ................................................................. 49
6.5 光學活性 (Optical Activity) ................................................................................... 51
6.5.1 比旋光度 (Specific Rotation)....................................................................... 51
6.5.2 鏡像異構物超越量 (Enantiomeric Excess, ee) ............................................... 52
6.6 不具掌性中心的掌性化合物 .................................................................................... 52
6.6.1 阻轉異構體 (Atropisomers) ........................................................................ 52
6.6.2 丙二烯 (Allenes) ........................................................................................ 53
6.6.3 含氮和含硫化合物 ...................................................................................... 53
6.7 鏡像異構物的解析 (Resolution of Enantiomers) ..................................................... 54
6.7.1 掌性解析試劑 ............................................................................................ 54
6.8 重點整理 ............................................................................................................ 55
6.9 習題 .................................................................................................................. 55

第七章 取代反應 .................................................................................................... 59
7.1 鹵烷 .................................................................................................................. 59
7.1.1 命名 ......................................................................................................... 59
7.1.2 鹵烷的物理性質 ......................................................................................... 59
7.1.3 鹵烷的製備 ............................................................................................... 60
7.2 SN2 反應 ............................................................................................................. 61
7.2.1 離去基...................................................................................................... 61
7.2.2 動力學...................................................................................................... 61
7.2.3 受質結構影響 SN2 的反應速率 ....................................................................... 62
7.2.4 親核劑的強度影響 SN2 的反應速率 ................................................................. 62
7.2.5 SN2 反應的立體專一性 ................................................................................. 63
7.2.6 溶劑影響 SN2 的反應速率 ............................................................................. 64
7.2.7 親核劑 vs 鹼 .............................................................................................. 65
7.3 SN1 反應 ............................................................................................................. 65
7.3.1 動力學...................................................................................................... 66
7.3.2 重排反應 .................................................................................................. 66
7.3.3 受質的影響 ............................................................................................... 67
7.3.4 SN1 反應的立體化學 .................................................................................... 67
7.3.5 溶劑的影響 ............................................................................................... 68
7.4 SN1 與 SN2 的離去基 ............................................................................................. 68
7.5 重點整理 ............................................................................................................ 69
7.6 習題 .................................................................................................................. 69 第八章 消除反應 .................................................................................................... 71
8.1 消除反應 ............................................................................................................ 71
8.2 烯類的穩定度 ...................................................................................................... 71
8.2.1 環烯的穩定度 ............................................................................................ 71
8.3 E2 反應機制 ........................................................................................................ 72
8.3.1 脫鹵氫反應 (Dehydrohalogenation) ............................................................ 72
8.3.2 動力學 ..................................................................................................... 72
8.3.3 結構影響 E2 反應的速率 .............................................................................. 72
8.3.4 E2 反應的位置選擇性 .................................................................................. 73
8.3.5 E2 反應的立體選擇性 .................................................................................. 73
8.3.6 E2 反應的立體專一性 .................................................................................. 73
8.4 E1 反應機制 ........................................................................................................ 74
8.4.1 動力學 ...................................................................................................... 74
8.4.2 重排反應 .................................................................................................. 75
8.5 E1 反應的速率 ..................................................................................................... 75
8.6 E1 反應的位置選擇性 ............................................................................................ 75
8.7 E1 反應的立體選擇性 ............................................................................................ 76
8.8 判別取代反應還是消除反應 .................................................................................... 76
8.9 重點整理 ............................................................................................................ 77
8.10 習題 ................................................................................................................. 78

第九章 加成反應 .................................................................................................... 81
9.1 加成反應的類型 ................................................................................................... 81
9.2 烯類的加成 - 熱力學的觀點 .................................................................................... 81
9.3 氫鹵化 - 位置選擇性 - 馬可尼可夫加成 (Markovnikov Addition).................................. 82
9.4 氫鹵化的重排反應 ................................................................................................ 83
9.4.1 氫負離子重排 (Hydride shift) 與甲基負離子重排 (Methyl shift) ........................ 83
9.5 酸催化水合反應 ................................................................................................... 83
9.6 氧汞化 - 去汞化 (Oxymercuration-Demercuration) ................................................. 83
9.7 氫化反應 (Hydrogenation) ................................................................................... 84
9.8 硼氫化 - 氧化作用 (Hydroboration-Oxidation) ........................................................ 84
9.9 鹵化 (Halogenation) 反應 .................................................................................... 85
9.10 鹵醇 (Halohydrin) 反應 ...................................................................................... 85
9.11 環氧化 (Epoxidation) ......................................................................................... 86
9.12 順式雙醇化作用 (syn Dihydroxylation) .................................................................. 86
9.13 炔類的加成反應 ................................................................................................. 87
9.14 炔類的氫鹵化反應 .............................................................................................. 87
9.15 炔類的水合反應 ................................................................................................. 88
9.16 炔類的硼氫化 - 氧化反應 ...................................................................................... 89
9.17 炔類的鹵化反應 ................................................................................................. 89
9.18 重點整理 ........................................................................................................... 90
9.19 習題 ................................................................................................................. 91
第十章 醇、酚、醚、環氧、硫和硫醇 .......................................................................... 93
10.1 醇的命名 ........................................................................................................... 93
10.1.1 醇的物理性質 ........................................................................................... 94
10.1.2 醇的製備 ................................................................................................. 94
10.1.3 有機金屬與醛的加成反應 ............................................................................ 95
10.1.4 有機金屬與酮和酯的加成反應 ..................................................................... 95
10.1.5 醛、酮、酯和酸的還原 ............................................................................... 95
10.2 醇的氧化 ........................................................................................................... 96
10.3 醇的反應 ........................................................................................................... 97
10.3.1 SN2 反應 ................................................................................................. 97
10.3.2 SN1 反應 ................................................................................................. 98
10.3.3 E2 反應 .................................................................................................. 98
10.3.4 E1 反應 .................................................................................................. 99
10.3.5 酯化反應 ................................................................................................. 99
10.4 酚的命名 ........................................................................................................... 99
10.4.1 酚的氧化 ................................................................................................. 100
10.5 醚的命名 ........................................................................................................... 100
10.5.1 醚的製備 ................................................................................................. 101
10.5.2 酸催化烯類與醇類的反應 ............................................................................ 101
10.5.3 烷氧汞化 - 去汞化 (Alkoxymercuration-Demercuration) .............................. 101
10.5.4 醚的反應 ................................................................................................. 102
10.5.5 醚的運用 ................................................................................................. 103
10.6 環氧的命名 ........................................................................................................ 104
10.6.1 環氧的製備 .............................................................................................. 105
10.6.2 環氧的反應 .............................................................................................. 105
10.7 硫和硫醇 ........................................................................................................... 106
10.7.1 硫化合物的命名 ........................................................................................ 106
10.7.2 硫衍生物的命名 ........................................................................................ 106
10.7.3 硫醚的合成 .............................................................................................. 107
10.7.4 硫化合物的反應 ........................................................................................ 107
10.8 重點整理 ...........................................................................................................108
10.9 習題 .................................................................................................................108

第十一章 醛類和酮類 .............................................................................................. 111
11.1 醛類的命名 ........................................................................................................ 111
11.2 醛類的製備........................................................................................................ 112
11.2.1 氧化 ....................................................................................................... 112
11.2.2 臭氧氧化切斷 ........................................................................................... 112
11.2.3 硼氫化 - 氧化 ........................................................................................... 112
11.2.4 鄰二醇的氧化切斷 ..................................................................................... 112
11.2.5 氰的還原 ................................................................................................. 113
11.2.6 醯氯的還原 .............................................................................................. 113
11.3 酮類的命名........................................................................................................ 113
11.4 酮類的製備 ........................................................................................................ 114
11.4.1 二級醇的氧化 ........................................................................................... 114
11.4.2 臭氧氧化切斷 ........................................................................................... 114
11.4.3 酸催化水解末端的炔類 ............................................................................... 114
11.4.4 夫里德耳 - 夸夫特醯化作用 (Friedel-Crafts Acylation) ................................... 114
11.5 醛類和酮類中與羰基的反應 .................................................................................. 114
11.5.1 與水的反應 - 水合物的形成 (Hydrate Formation) .......................................... 114
11.5.2 半縮醛 (Hemiacetal) 的形成 ...................................................................... 115
11.5.3 縮醛的形成 .............................................................................................. 115
11.5.4 與胺類的反應 ........................................................................................... 116
11.5.5 沃夫 - 奇希諾還原 (Wolff-Kishner Reduction).............................................. 117
11.5.6 與硫醇的反應 ........................................................................................... 117
11.5.7 與有機金屬的反應 ..................................................................................... 118
11.5.8 與氰化氫 (HCN) 的反應 - 氰醇 (Cyanohydrin) 的合成 .................................... 119
11.5.9 威悌反應 (Wittig Reaction) ....................................................................... 120
11.5.10 與氫負離子的反應 ................................................................................... 121
11.5.11 拜耳 - 維立格氧化反應 (Baeyer-Villiger Oxidation) ..................................... 121
11.5.12 克萊門森還原作用 (Clemmensen Reduction) ............................................ 121
11.6 重點整理 ........................................................................................................... 122
11.7習題 ................................................................................................................. 123

第十二章、醛與酮的 α 位置碳的化學 .......................................................................... 125
12.1 烯醇和烯醇鹽 α 位置的鹵化 .................................................................................. 125
12.1.1 在酸性條件 .............................................................................................. 126
12.1.2 赫耳 - 華哈德 - 季林斯基反應 (Hell-Volhard-Zelinsky Reaction) ..................... 127
12.1.3 鹼性條件 ................................................................................................. 127
12.1.4 O- 烷基化或 C- 烷基化 (O-Alkylation and C-Alkylation) ................................ 127
12.1.5 鹵化 ....................................................................................................... 128
12.1.6 鹵仿反應 (Haloform Reaction) .................................................................. 128
12.2 醛醇反應與醛醇縮合 (Aldol Reactions and Aldol Condensations) ........................... 128
12.2.1 醛醇 ( 加成 ) 反應 ..................................................................................... 128
12.2.2 醛醇縮合 (Aldol Condensations) ............................................................... 129
12.2.3 交聯醛醇反應 (Crossed Aldol Reactions) .................................................... 129
12.2.4 克萊森 - 施密特縮合反應 (Claisen-Schmidt Condensations) .......................... 130
12.2.5 分子內的醛醇反應 (Intramolecular Aldol Reactions) ................................... 130
12.3 酯的縮合 ........................................................................................................... 130
12.3.1 克萊森縮合 (Claisen Condensations) ......................................................... 130
12.3.2 交聯克萊森縮合 (Crossed Claisen Condensations) ...................................... 131
12.3.3 狄克曼縮合反應 (Dieckmann Condensations) ............................................. 131
12.4 烯醇鹽 α 位置的烷基化 ........................................................................................ 132
12.4.1 乙醯乙酸酯合成 (Acetoacetic Ester Synthesis) ............................................ 132
12.4.2 丙二酸酯合成法 (Malonic Ester Synthesis) ................................................. 133
12.4.3 克腦文蓋爾縮合反應 (Knoevenagel Reaction) .............................................. 133
12.5 共軛加成反應 .................................................................................................... 133
12.5.1 魯賓遜成環反應 (The Robinson Annulation Reaction) ................................. 134
12.5.2 施托克烯胺反應 (Stork Enamine Reaction) ................................................. 134
12.5.3 曼尼赫反應 (The Mannich Reaction) ......................................................... 135
12.5.4  α,β- 不飽和酮的烷基化 .............................................................................. 135
12.6 重點整理 ........................................................................................................... 135
12.7 習題 ................................................................................................................. 136

第十三章 羧酸和羧酸的衍生物 ................................................................................... 139
13.1 羧酸的命名 ........................................................................................................ 139
13.1.1 單一個羧酸 .............................................................................................. 139
13.1.2 兩個 (雙) 羧酸 .......................................................................................... 139
13.2 羧酸的物理性質 ................................................................................................. 140
13.2.1 羧酸的酸度 .............................................................................................. 140
13.3 羧酸的製備........................................................................................................ 141
13.3.1 炔類的臭氧化 ........................................................................................... 141
13.3.2 一級醇的氧化 ........................................................................................... 142
13.3.3 烷基苯的氧化 ........................................................................................... 142
13.3.4 腈的水解 ................................................................................................. 142
13.3.5 格里納試劑的羰基化 .................................................................................. 142
13.4 羧酸的反應 ........................................................................................................ 142
13.5 羧酸衍生物的命名與製備 ..................................................................................... 143
13.5.1 醯鹵；鹵化醯基 (Acid Halides) .................................................................. 143
13.5.2 酯 .......................................................................................................... 143
13.5.3 酸酐 ....................................................................................................... 144
13.5.4 醯胺 ....................................................................................................... 145
13.5.5 腈 .......................................................................................................... 147
13.6 羧酸衍生物的反應性 ........................................................................................... 148
13.6.1 醯鹵 ....................................................................................................... 148
13.6.2 酯 .......................................................................................................... 148
13.6.3 酸酐 ....................................................................................................... 149
13.6.4 醯胺 ....................................................................................................... 149
13.6.5 腈 .......................................................................................................... 149
13.7 羧酸衍生物的重排反應 ........................................................................................ 150
13.8 重點整理 ...........................................................................................................
150 13.9 習題 ................................................................................................................. 151

第十四章 芳香族化合物 ........................................................................................... 153
14.1 芳香族衍生物的命名 ........................................................................................... 153
14.1.1 單取代芳香族衍生物的命名......................................................................... 153
14.1.2 雙取代芳香族衍生物的命名......................................................................... 154
14.1.3 多取代苯環衍生物 ..................................................................................... 154
14.2 苯環的結構........................................................................................................ 155
14.3 苯環的穩定性 .................................................................................................... 155
14.4 其它芳香族化合物 .............................................................................................. 156
14.4.1 輪烯 (Annulene) ..................................................................................... 157
14.4.2 芳香族的離子 ........................................................................................... 157
14.5 芳香族化合物的反應 ........................................................................................... 158
14.5.1 苄位的氧化 .............................................................................................. 158
14.5.2 苄位的游離基反應 ..................................................................................... 158
14.5.3 苄位的取代反應 ........................................................................................ 159
14.5.4 苄位的消除反應 ........................................................................................ 159
14.6 親電子性芳香族取代反應 ..................................................................................... 159
14.6.1 鹵化 (Halogenation) ................................................................................ 160
14.6.2 硝基化 (Nitration) ................................................................................... 160
14.6.3 硫酸化 (Sulfonation) ................................................................................ 160
14.6.4 夫里德耳 - 夸夫特烷化作用 (Friedel-Crafts Alkylation) .................................. 161
14.6.5 夫里德耳 - 夸夫特醯基化作用 (Friedel-Crafts Acylation) ................................ 161
14.7 親電子芳香族取代反應速率和位置選擇性 ................................................................ 162
14.7.1 活化基團 (Activating Groups, Activators) ................................................... 162
14.7.2 去活化基團 (Deactivating Groups, Deactivators) ......................................... 163
14.7.3 鹵素 ....................................................................................................... 163
14.8 合成方法的運用 ................................................................................................. 164
14.8.1 定向效應 (Directing Effects) ..................................................................... 164
14.8.2 立體效應 (Steric Effects) ........................................................................... 165
14.8.3 保護基 (Protecting Groups) 的運用 ............................................................ 165
14.9 親核性芳香族取代反應 (Nucleophilic Aromatic Substitution Reactions) ..........166
14.10 芳香族取代和消除反應 ....................................................................................... 166
14.11 苯環的還原 ...................................................................................................... 167
14.11.1 伯奇還原反應 (Birch Reduction) .............................................................. 167
14.12 芳香族雜環的酸度 ............................................................................................. 167
14.13 重點整理 ......................................................................................................... 169
14.14 習題 ............................................................................................................... 169

第十五章 共軛系統與周環反應 ................................................................................... 173
15.1 共軛雙鍵 ........................................................................................................... 173
15.2 共軛雙鍵的加成 ................................................................................................. 173
15.2.1 共軛雙鍵的合成 ........................................................................................ 173
15.2.2 熱力學與動力學 ........................................................................................ 174
15.3 分子軌域理論 (Molecular Orbital Theory) ............................................................ 174
15.3.1 1,3-Butadiene 的分子軌域理論 .................................................................. 174
15.3.2 1,3,5-Hexatriene 的分子軌域理論 .............................................................. 175
15.4 周環反應 (Pericyclic Reactions) .......................................................................... 175
15.4.1 環化加成反應 (Cycloaddition Reactions) .................................................... 175
15.4.2 電子環化反應 (Electrocyclic Reactions) ..................................................... 178
15.4.3 σ 遷移反應 (Sigmatropic Reactions) .......................................................... 180
15.5 重點整理 ........................................................................................................... 182
15.6 習題 ................................................................................................................. 183

第十六章 胺類化合物 .............................................................................................. 185
16.1 胺類的命名 ........................................................................................................ 185
16.1.1 一級胺的命名 ........................................................................................... 185
16.1.2 二級胺的命名 ........................................................................................... 186
16.1.3 三級胺的命名 ........................................................................................... 186
16.1.4 四級胺鹽的命名 ........................................................................................ 186
16.2 胺類的物理性質 ................................................................................................. 186
16.2.1 胺類的幾何形狀 ........................................................................................ 186
16.2.2 胺類的溶解度和沸點 .................................................................................. 187
16.2.3 胺類的鹼度 .............................................................................................. 187
16.2.4 非定域化的效應 ........................................................................................ 189
16.3 胺類的製備 ........................................................................................................ 190
16.3.1 氨的烷基化 .............................................................................................. 190
16.3.2 疊氮化合物 (Azide，-N3) 的還原 ................................................................. 191
16.3.3 加柏利合成 (Gabriel Synthesis) ................................................................. 191
16.3.4 還原胺化反應 (Reductive Amination) ......................................................... 191
16.3.5 還原腈 .................................................................................................... 192
16.3.6 由羧酸轉變成醯胺後再還原......................................................................... 192
16.3.7 還原硝基 (NO2) ........................................................................................ 192
16.4 胺類的反應 ........................................................................................................ 192
16.4.1 醯化反應 ................................................................................................. 193
16.4.2 霍夫曼消除作用 (Hofmann Elimination) .................................................... 194
16.4.3 亞硝化 (Nitrosation) ................................................................................ 194
16.4.4 與一級胺反應的重氮化 ............................................................................... 195
16.4.5 桑德邁爾反應 (Sandmeyer Reactions) ........................................................ 195
16.4.6 重氮偶合反應 (Azo Coupling) .................................................................... 195
16.4.7 與二級胺反應 ........................................................................................... 196
16.5 吡啶 (Pyridine)、吡咯 (Pyrrole) 與咪唑 (Imidazole) .............................................. 196
16.6 磺胺類藥物 (Sulfonamides) ................................................................................ 197
16.7 重點整理 ........................................................................................................... 197
16.8 習題 ................................................................................................................. 198

第十七章 有機金屬 ................................................................................................. 201
17.1 有機金屬化合物 ................................................................................................. 201
17.2 有機金屬化合物的命名 ........................................................................................ 201
17.3 有機鋰試劑 (Organolithium Reagents)................................................................. 202
17.4 有機鎂試劑 (Organomagnesium Reagents) .......................................................... 202
17.5 有機銅試劑 (Organocopper Reagents) ................................................................. 203
17.5.1 偶合反應 (Corey-Posner/Whitesides-House) .............................................. 203
17.5.2 立體專一性 .............................................................................................. 204
17.6 有機錫試劑 (Organotin Reagents) ....................................................................... 204
17.6.1 有機錫化合物的製備 .................................................................................. 204
17.6.2 立體專一性 .............................................................................................. 204
17.7 有機硼試劑 (Organoboron Reagents) ................................................................... 205
17.7.1 立體專一性 .............................................................................................. 206
17.7.2 有機硼試劑與有機錫試劑的優點與缺點 ......................................................... 206
17.8 有機鋅試劑 (Organozinc Reagents) ..................................................................... 206
17.8.1 環丙烷化反應 (Cyclopropanation Reaction)................................................ 206             西蒙斯 - 史密斯反應 (Simmons-Smith Reaction) .......................................... 206
17.8.2 立體專一性 .............................................................................................. 207
17.9 根岸偶聯反應 (Negishi Reaction) ........................................................................ 207
17.9.1 有機鋅試劑的製備 ..................................................................................... 207
17.9.2 立體專一性 .............................................................................................. 208
17.10 赫克反應 (The Heck Reaction) .......................................................................... 208
17.10.1 立體專一性 ............................................................................................ 208
17.11 有機矽試劑 (檜山偶聯反應，Hiyama Coupling) .................................................... 209
17.11.1 立體專一性 ............................................................................................ 209
17.12 薗頭偶合反應 (Sonogashira Coupling) ............................................................... 209
17.13 歧化反應 (Metathesis) ...................................................................................... 210
17.14 重點整理 ......................................................................................................... 210
17.15 習題 ............................................................................................................... 211

第十八章 游離基反應 .............................................................................................. 213
18.1 何謂游離基 ........................................................................................................ 213
18.1.1 游離基的結構 ........................................................................................... 213
18.1.2 游離基的穩定性 ........................................................................................ 213
18.1.3 游離基的共振結構 ..................................................................................... 213
18.2 甲烷的氯化........................................................................................................ 214
18.2.1 游離基起始劑 ........................................................................................... 214
18.2.2 游離基抑制劑 ........................................................................................... 214
18.3 鹵化的選擇性 .................................................................................................... 215
18.4 鹵化的立體選擇性 .............................................................................................. 216
18.4.1 掌性中心的產生 ........................................................................................ 216
18.4.2 掌性的消失 .............................................................................................. 216
18.5 烯丙位的溴化..................................................................................................... 216
18.6 游離基溴化氫的加成 - 反馬克尼可夫的產物 ............................................................. 217
18.7 重點整理 ........................................................................................................... 218
18.8 習題 ................................................................................................................. 219

第十九章 合成聚合物 .............................................................................................. 221
19.1 聚合物的命名..................................................................................................... 221
19.2 聚合物反應型態的分類 ........................................................................................ 221
19.2.1 同元聚合物 (Homopolymer) ..................................................................... 221
19.2.2 共聚合物 (Copolymer).............................................................................. 222
19.2.3 縮合聚合物 (Condensation Polymer) ......................................................... 222
19.3 聚合物的分類 .................................................................................................... 223
19.3.1 鏈增長聚合物 (Chain-growth Polymers) ..................................................... 223
19.3.2 逐步增長聚合物 (Step-growth Polymers) .................................................... 223
19.4 聚合物結構的分類 .............................................................................................. 223
19.4.1 線型 (Linear) .......................................................................................... 223 19.4.2
支鏈 (Branched) ...................................................................................... 223
19.4.3 交聯 (Cross-Linked) ................................................................................ 223
19.5 聚合物的性質..................................................................................................... 224
19.5.1 熱塑性橡膠 (Thermoplastic Polymers)....................................................... 224
19.5.2 熱固性橡膠 (Thermosetting Polymers) ...................................................... 224
19.5.3 彈性體 (Elastomer) .................................................................................. 224
19.6 游離基聚合 ........................................................................................................ 225
19.7 陰離子聚合 (Anionic Polymerization) .................................................................. 226
19.8 陽離子聚合 (Cationic Polymerization) ................................................................. 227
19.9 聚醯胺 (Polyamides) .......................................................................................... 227
19.10 聚酯 (Polyesters) ............................................................................................. 227
19.11 聚氨酯 (Polyurethanes, PU) .............................................................................. 228
19.12 聚碳酸酯 (Polycarbonate, PC) ........................................................................... 228
19.13 聚合物的立體化學 - 齊格勒 - 納他催化劑 ............................................................... 229
19.14 合成橡膠 ......................................................................................................... 229
19.15 可回收的聚合物 ................................................................................................ 229
19.16 生物可分解的聚合物 .......................................................................................... 230
19.17 重點整理 ......................................................................................................... 230
19.18 習題 ............................................................................................................... 231

第二十章 碳水化合物 .............................................................................................. 233
20.1 單醣的分類........................................................................................................ 233
20.1.1 D- 醣和 L- 醣 ........................................................................................... 233
20.1.2 醛醣 (Aldoses) ........................................................................................ 234
20.1.3 酮醣 (Ketoses) ......................................................................................... 235
20.2 單醣的環形結構 ................................................................................................. 236
20.2.1 哌喃醣 (Pyranoses) .................................................................................. 236
20.2.2 呋喃糖 (Furanoses) .................................................................................. 237
20.3 單醣的反應........................................................................................................ 237
20.3.1 酯化和醚化 .............................................................................................. 237
20.3.2 醣苷的形成 .............................................................................................. 238
20.3.3 差向異構作用 (Epimerization) ................................................................... 239
20.3.4 單醣的氧化 .............................................................................................. 239
20.3.5 單醣的還原 .............................................................................................. 240
20.3.6 單醣鏈的加長 (The Kiliani-Fischer Synthesis) ............................................ 240
20.3.7 單醣鏈的縮短 (The Wohl Degradation 和 Ruff Degradation) ........................ 241
20.4 雙醣 ................................................................................................................. 241
20.4.1 麥芽糖 (Maltose) ..................................................................................... 241
20.4.2 纖維雙醣 (Cellobiose) .............................................................................. 242
20.4.3 乳糖 (Lactose) ......................................................................................... 242
20.4.4 蔗糖 (Sucrose) ........................................................................................ 242
20.5 多醣 ................................................................................................................. 243
20.5.1 澱粉 (Starch) ........................................................................................... 243
20.5.2 纖維素 (Cellulose) ................................................................................... 243
20.6 胺醣 (Amino Sugars) ......................................................................................... 244
20.6.1 N- 醣苷 ................................................................................................... 244
20.7 重點整理 ........................................................................................................... 245
20.8 習題 ................................................................................................................. 246
中英文字詞解釋 ..................................................................................................... 249
習題簡答 .............................................................................................................. 259