有机化学教学课件：第11章 酚和醌

1、酚 和 醌苯酚 2-萘酚 3-硝基苯酚 5-甲基-1-萘酚 4-羟基苯磺酸 sp2杂化 1酚的制备异丙苯法反应同时生成了两个重要的化工原料苯酚和丙酮O2H3O+异丙苯(Cumene)氢过氧化异丙苯(Cumene hydroperoxide)苯酚(Phenol)丙酮(Acetone)2异丙苯生成酚的机理H3O+H3O+H2O3酚的制备卤代芳烃的取代反应经历了消除加成机理，有中间体苯炔生成4氯苯的取代反应不可能通过SN1或SN2的机理进行5氯苯被氨基取代的机理：消除加成反应反应经历了苯炔中间体6苯炔中间体的结构同位素标记证明了苯炔的存在7酚的制备卤代芳烃的取代反应经历了加成消除机理8加成消除反应机

2、理9酚的制备苯磺酸的碱熔10酚的物理性质沸点11酚的物理性质溶解度12酚的分子内氢键b.p.= 295Cb.p.= 217C分子内氢键13酚的物理性质红外光谱苯酚的红外光谱OH: 35203100 cm1 CO: 1230 cm114酚的化学性质酸性pKa=17.1pKa= 10.015酚的化学性质酸性pKa= 10.21pKa= 10.14pKa= 10.0pKa= 0.25pKa= 8.39pKa= 7.1516酚的化学性质酸碱平衡pKa=10.0pKa=10.25pKa=10.0pKa=6.38平衡向右移动平衡向左移动pKa= 4.0pKa=6.38平衡向右移动17酚的化学性质醚的生成1

3、8酚的化学性质酯的生成H0 = 19 kJ/mole H0 = +6 kJ/mole 19芳环上的取代反应卤化(定量白色沉淀)(一取代反应)20芳环上的取代反应硝化21芳环上的取代反应磺化22苦味酸间接制备法2,4,6-三硝基苯酚(苦味酸)2,4,6-Trinitrophenol(Picric acid)23芳环上的取代反应烷基化和酰基化24芳环上的取代反应烷基化和酰基化25芳环上的取代反应缩合反应26酚醛高聚物酚醛树脂27酚与FeCl3的显色反应蓝紫色深绿色暗绿色任何稳定的烯醇式结构都能够和FeCl3发生显色反应28醌(Quinone)苯醌邻苯醌(o-Benzoquinone)(对苯)醌(p

4、-Benzoquinone)4-甲基-1,2-苯醌(4-Methyl-1,2-benzoquinone)29苯醌的制备苯酚和苯胺的氧化MnO2310CH2SO4MnSO4K2Cr2O7H2SO4, 30C氢醌(Hydroquinone)1,4-苯醌(1,4-Benzoquinone)30苯醌的反应加成2,3,5,6-四溴环己二酮Br2Br2HCl1,4-亲核加成互变异构31苯醌的反应生成肟H2NOHH2NOHHNO2互变异构32醌的反应还原2-Methyl-1,4-naphthoquinoneNa2S2O4Ether2-Methyl-1,4-dihydroxynaphthaleneNaBH43

5、3苯醌和对苯二酚的氧化还原转换The ready reversibility of this reaction is essential to the role that quinones play in cellular respiration, the process by which an organism uses molecular oxygen to convert its food to carbon dioxide, water, and energy. Electrons are not transferred directly from the substrate mole

6、cule to oxygen but instead are transferred by way of an electron transport chain involving a succession of oxidationreduction reactions.34Ubiquitous Quinone (Ubiquinone)()nUbiquinone(coenzyme Q) n = 6 10The length of its side chain varies among different organisms; the most common form in vertebrate

7、s has n 10, and ubiquinones in which n 6 to 9 are found in yeasts and plants.发现于所有的细胞中35氢醌氢的生成醌氢醌(Quinhydrone)氢醌(对苯)醌等物质的量的对苯二酚（氢醌）和对苯醌生成分子间配合物醌氢醌。该物质为暗绿色结晶，熔点为171C，在水溶液中大部分解离为对苯二酚和对苯醌。在对苯二酚的水溶液中加入FeCl3，溶液先呈绿色，再变棕色，最后有暗绿色的醌氢醌析出。36醌萘醌和蒽醌1,4-萘醌(1,4-Naphthoquinone)1,2-萘醌(1,2-Naphthoquinone)9,10-蒽醌(9,10

8、-Anthraquinone)9,10-菲醌(9,10-phenanthraquinone)37茜素(Alizarin)Quinones are colored; p-benzoquinone, for example, is yellow. Many occur naturally and have been used as dyes. Alizarin is a red pigment extracted from the roots of the madder(茜草) plant. Its preparation from anthracene, a coal tar derivative, in 1868 was a significant step in the development of the synthetic dyestuff industry.Alizarin38维生素KVitamin KH2()3Vitamin K()3Vitamin K is required for proper clotting of blood. Vitamin K deficiencies are rare because the vitamin is synthesized by intestinal bacteria. Vi