有机化学Chap12(2012-1)资料.ppt

Preparation of Aromatic Amine Fe/HCl can reduce nitro group but can not reduce carbon-carbon double bond. Ni, Pd, Pt 1. Sequence of the basicity of amines Amine Quaternary ammonium hydrate is a very strong base, its basicity is similar to inorganic base, such as NaOH. We have known that the more substituted a carbocation, the more stable it is. Similarly, the more substituted an ammonium ion, the more stable it is. More stable ammonium ion means its corresponding amine is a good competitor for H+. The steric interference make tertiary amine difficult to combine proton, so its basicity is weaker than secondary and primary amine. For aromatic amine, the p-p conjugation make benzene ring withdraw electron from amino group, so the basicity is weaker. 2. Acylation amide × crystal × -I effect weak acid benzene sulfonamide ※ ※ ※ 3.Hinsberg Reaction（兴斯堡反应 ） 4. React with nitrous acid HNO2 1 Primary amines ※ ※ 2 Secondary amines nitrosoamines yellow oil 亚硝胺 亚硝胺是四大食品污染物之一。迄今为止，已发现的亚硝胺有300多种，其中90%左右可以诱发动物不同器官的肿瘤。〔1〕大量的实验证明某些食品中存在一定量的亚硝胺，其中有的是食品中天然形成，有的是生产过程需要添加的，人体可经消化道、呼吸道等途径接触这些致癌物。〔2〕也可通过胎盘使子代接触，引起子代的肿瘤，甚至在一次大剂量接触后，经一定潜伏期诱发出肿瘤。 亚硝酸盐广泛存在于自然界环境中，尤其是在食物中。因此，亚 　　硝酸盐每天都会随着粮食、蔬菜、鱼肉、蛋奶进入人体。例如蔬菜中 　　亚硝酸盐的平均含量大约为4毫克/千克，肉类约为3毫克/千克，蛋类 　　约为5毫克/千克。某些食品中含量更高，如豆粉的平均含量可达10毫 　　克/千克，咸菜中的平均含量也在7毫克/千克以上。 　　亚硝酸盐不都是人体“过客” 　　亚硝酸盐是亚硝胺类化合物的前体物质。在自然界中，亚硝酸盐 　　极易与胺化合，生成亚硝胺。在人体胃的酸性环境中，亚硝酸盐也可 　　以转化为亚硝胺 3 Tertiary amines Aliphatic tertiary amines do not react with nitrous acid to give an isolable product. yellow solid ※ ※ white precipitation 5. Special Reaction of Aniline Diazo and Azo Compounds Ⅰ. Diazotization Reaction benzene diazonium chloride 0~5℃ Ⅱ. Reaction of Diazo Salt 1. Substitution H3PO2: hypophosphorous acid 次磷酸 2. Coupled Reaction 偶联反应 Amides 1. Acidity and Basicity Almost amides are neutral. A classic exceptional example is phthalimide, which is very weak acid. 2. Hydrolysis 3. React with Nitrous Acid 4. Biuret Reaction 缩二脲反应 Biuret can dissolve in alkali solution. If a