理解有機化學

　　有機化學的反應即是親核劑尋找親電子劑的反應，本書會提及部分的反應機制讓學生有初步的了解，但不會鉅細靡遺，本書淺顯易懂，希望能夠對莘莘學子對於有心理解有機化學能有所助益。

　　本書包含二十章節，書寫本書的目的是想把有機化學之美介紹給一般有機會學習有機化學的學子們。有機化學給人們的印象是需要"死記”，然而它是一個非常有邏輯的學科，只要掌握一些基本的命名規則，對於往後"看懂"分子才能夠奠定基礎。另外學習有機化學時需要掌握立體效應、電子效應以及親核劑尋找親電子劑的原則。

　　藥物化學、材料化學和生物化學等皆與有機化學息息相關，希望藉由這本書，在各位接觸有機化學時不再畏懼並且愛上它。-作者施增廉
 

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