附件2 粒大浮 教 案 2003~~2004学年第Ⅱ学期 院(系、所、部)化学与环境学院有机化学研究所 教研室有机化学 课程名称有机化学(双语教学) 授课对象化学教育 授课教师杨定乔 职称职务教授 教材名称 Organic Chemistry 2004年03月01日
附件 2 教 案 2003~~ 2004 学年 第 II 学期 院（系、所、部）化学与环境学院有机化学研究所 教 研 室 有机化学 课 程 名 称 有机化学（双语教学） 授 课 对 象 化学教育 授 课 教 师 杨定乔 职 称 职 务 教授 教 材 名 称 Organic Chemistry 2004 年 03 月 01 日
有机化学(双语教学)课程教案 授课题目(教学章节或主题):第十四章.含氮有机|授课类型|理论课 化合物( Amine) 授课时间第7周第6974节 教学目标或要求:了解硝基化合物的分类,命名。了解胺的分类,命名,重氮和偶尔 氮化合物及分子重排。重点掌握胺的化学性质及重氮和偶氮化合物。 教学内容(包括基本内容、重点、难点) 含氮化合物 本章的重点是各种含氮化合物的重要反应及其在有机合成中的应用、芳环上的亲核取 代反应历程、Cope消去和 Hofmann消去反应的机理和立体化学、活泼中间体碳烯和类 碳烯的生成及其应用、烯胺的生成及其在有机合成中的应用等。 Nomenclature of Aliphatic Amines Simple amines are named as derivatives of the parent alkane, using the suffix-amine, or by using-amino to name a numbered substituent, using the following rules by replacing the-e ending with -amine, or by nam ing the nitrogen as an amino substrat a rent name elect the longest continuous carbon chain, containing the amino group, and derive the 2. Number the carbon chain, beginning at the end nearest to the amino group or, to give the lowest number at the first point of difference 3. Num ber the substituents and write the name, listing substituents alpha betically. Thus for the following example, you would number from the end closest to the nitrogen, generating the names, 3-methylpentanamine(or 1-amino-3-methy lpentane) and 5-methy 1-2-he 2-amino-5-methy1-2-hexane), respectively NH2 5 In this example, however, you number to give the lowest number at the first point of difference generating the name, 5-amino-2, 3-dimethy lhexane(not
有机化学(双语教学) 课程教案 授课题目（教学章节或主题）：第十四章．含氮有机 化合物 (Amine) 授课类型 理论课 授课时间 第 7 周第 69-74 节 教学目标或要求：了解硝基化合物的分类，命名。了解胺的分类，命名，重氮和偶尔 氮化合物及分子重排。重点掌握胺的化学性质及重氮和偶氮化合物。 教学内容（包括基本内容、重点、难点）： 含氮化合物 本章的重点是各种含氮化合物的重要反应及其在有机合成中的应用、芳环上的亲核取 代反应历程、Cope 消去和 Hofmann 消去反应的机理和立体化学、活泼中间体碳烯和类 碳烯的生成及其应用、烯胺的生成及其在有机合成中的应用等。 Nomenclature of Aliphatic Amines Simple amines are named as derivatives of the parent alkane, using the suffix -amine, or by using -amino to name a numbered substituent, using the following rules: 1. Select the longest continuous carbon chain, containing the amino group, and derive the parent name by replacing the -e ending with -amine, or by naming the nitrogen as an amino substituent. 2. Number the carbon chain, beginning at the end nearest to the amino group, or, to give the lowest number at the first point of difference. 3. Number the substituents and write the name, listing substituents alphabetically. Thus for the following example, you would number from the end closest to the nitrogen, generating the names, 3-methylpentanamine (or 1-amino-3-methylpentane) and 5-methyl-2-hexanamine (or 2-amino-5-methyl-2-hexane), respectively. In this example, however, you number to give the lowest number at the first point of difference, generating the name, 5-amino-2,3-dimethylhexane (not
2-amino-4, 5-dimethy lhexane) NH2 Some examples ar-13-diammocycloherane Nh 1-amino-4-pheny pentane ar4-phenytpentanamin H2N CH3 4amino-1 1-dimethyicycloherane Multiple substituents on the nitrogen are named using simple multipliers CH H2C一 HsC-N-CH3 amine Tetramethylammonium 2NH NN-dimethylpropylamme Benzylamine (phenyimethyanamime) quarternary based on the number of substituents on the nitrogen. o Amines are further categorized as primary, secondary, tertiary ar
2-amino-4,5-dimethylhexane). Some examples: Multiple substituents on the nitrogen are named using simple multipliers: Amines are further categorized as "primary, secondary, tertiary and quarternary" based on the number of substituents on the nitrogen:
CHa N-h HoC- H3C—CH3 Secondary Amme Tertiary Amine Quatermary Ammonium H Secondary Amme Primary Amine Reactions of Aliphatic Amines Simple amines and ammonia are strong nucleophiles and will undergo an S,2 reaction with alkyl halides ( or alkyl groups with good leaving groups")to give further substitution on the nitrogen, as described previously. They will also react with activated carbony l compounds to undergo acyl transfer reactions; thus amides are readily formed by the reaction of amines with acid halides, acid anhydrides or carboxylate esters CH2 CH2NH2 The reaction of an amine with a sulfony l halide forms the sulfonamide. A common reagent utilized in this reaction is p-toluenesulfonyl chloride, producing the corresponding p-toluenesulfonamide
Reactions of Aliphatic Amines Simple amines and ammonia are strong nucleophiles and will undergo an SN2 reaction with alkyl halides (or alkyl groups with "good leaving groups") to give further substitution on the nitrogen, as described previously. They will also react with activated carbonyl compounds to undergo acyl transfer reactions; thus amides are readily formed by the reaction of amines with acid halides, acid anhydrides or carboxylate esters. The reaction of an amine with a sulfonyl halide forms the sulfonamide. A common reagent utilized in this reaction is p-toluenesulfonyl chloride, producing the corresponding p-toluenesulfonamide
+ cha- H.CHN-SO sulfonamide The base solubility of sulfonamides forms the basis of the Hinsberg test, for distinguishing primary, secondary and tertiary amines; primary p-toluenesulfonamides undergo ionization in strong base to give the base-soluble anion, secondary p-toluenesul fonamides lack the acidic hydrogen and do not form a soluble anion; tertiary amines would yield highly unstable cationic quarternary sulfonamides, and generally do not react at all. Thus the formation of a base-soluble sulfonamide indicates the presence of a primary CH2CH2N CISO2 CH2CH2N-SO2 primary sulfonamide, base soluble H,CHN-S .a secondary sulfonamide, not base soluble Reaction of primary amines with an excess of iodome thane converts the primary amine into the quarternary ammonium salt. The cationic nitrogen which is now formed is a good leaving group and will undergo E2 elimination on reaction with Ag.0 to give the alkene, in a reaction known as the Hofmann Elimination
The base solubility of sulfonamides forms the basis of the Hinsberg test, for distinguishing primary, secondary and tertiary amines; primary p-toluenesulfonamides undergo ionization in strong base to give the base-soluble anion, secondary p-toluenesulfonamides lack the acidic hydrogen and do not form a soluble anion; tertiary amines would yield highly unstable cationic quarternary sulfonamides, and generally do not react at all. Thus, the formation of a base-soluble sulfonamide indicates the presence of a primary amine. Reaction of primary amines with an excess of iodomethane converts the primary amine into the quarternary ammonium salt. The cationic nitrogen which is now formed is a good leaving group, and will undergo E2 elimination on reaction with Ag2O to give the alkene, in a reaction known as the Hofmann Elimination