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):第十二章.羧酸授课类型|理论课 Carboxylic Acid 授课时间第3周第61-64节 教学目标或要求:了解羧酸的分类,命名及同分异构现象。了解羧酸的化学反应性质 及其制备方法。重点掌握羧酸的化学反应性质及其有关制备。 教学内容(包括基本内容、重点、难点) 羧酸 本章的重点是羧酸的重要反应及其应用和酯化反应历程。重要反应有羧酸衍生物的 生成,脱羧反应和α-氢取代反应等。酯化反应历程包括两种脱水方式,即酰氧键断裂 和烷氧键断裂。难点是对结构与性质的关系的认识和理解。 Nomenclature of Carboxylic Acids Simple carboxy lic acids are named as derivatives of the parent alkane, using the suffix -oic acid elect the longest continuous carbon chain, conta ining the carboxylic acid group, and derive the parent name by replacing the -e ending with -oic acid 2. Num ber the carbon chain, beginning at the end nearest to the carboxylic acid grou 3. Number the substituents and write the name, listing substituents alpha betically 4. Carboxy lic acid substituents attached to rings are named using the suffix -carboxylic acid Several simple examples are shown below:
有机化学(双语教学) 课程教案 授课题目（教学章节或主题）：第十二章．羧酸 (Carboxylic Acid) 授课类型 理论课 授课时间 第 3 周第 61-64 节 教学目标或要求：了解羧酸的分类，命名及同分异构现象。了解羧酸的化学反应性质 及其制备方法。重点掌握羧酸的化学反应性质及其有关制备。 教学内容（包括基本内容、重点、难点）： 羧酸 本章的重点是羧酸的重要反应及其应用和酯化反应历程。重要反应有羧酸衍生物的 生成，脱羧反应和α-氢取代反应等。酯化反应历程包括两种脱水方式，即酰氧键断裂 和烷氧键断裂。难点是对结构与性质的关系的认识和理解。 Nomenclature of Carboxylic Acids Simple carboxylic acids are named as derivatives of the parent alkane, using the suffix -oic acid 1. Select the longest continuous carbon chain, containing the carboxylic acid group, and derive the parent name by replacing the -e ending with -oic acid. 2. Number the carbon chain, beginning at the end nearest to the carboxylic acid group. 3. Number the substituents and write the name, listing substituents alphabetically. 4. Carboxylic acid substituents attached to rings are named using the suffix -carboxylic acid. Several simple examples are shown below:
2-ethyipentanoic acii 3-bromo-2-ethyibutanoic acid Rcycloherenecarboryhic acid 5-bromo-2-methyibenzoic aicd In the first example, the parent chain is a pentane and the carboxylic acid group is assigned as carbon #1. On the pentane parent, there is an ethy l group in position #2 hence the name, 2-ethy pentanoic acid In the second example, there are two potential four-carbon chains; in this case the chain with the most substituents is selected as parent,(a butanoic acid Attached to the butanoic acid at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name 3-bromo-2-ethylbutanoic acid In the third example, the carboxylic acid is attached to a cycloalkene ring and will therefore be named as a"carboxylic acid" substituent (rule #4).The parent ring is a cyclohexene; letting the carboxylic acid be carbon #1, the name is 2-cyclohexenecarboxylic acid In the last example, the name is based on benzoic acid as the parent. In this case, we simply number the substituents to give the lowest number sequence at the first point of difference and arrange alphabetically 5-bromo-2-methy benzoic acid Reactions which Yield Carboxylic Acids Oxidation of Aromatic Side-Chains with Neutral Permaganate
In the first example, the parent chain is a pentane and the carboxylic acid group is assigned as carbon #1. On the pentane parent, there is an ethyl group in position #2; hence the name, 2-ethylpentanoic acid. In the second example, there are two potential four-carbon chains; in this case, the chain with the most substituents is selected as parent, (a butanoic acid). Attached to the butanoic acid at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name 3-bromo-2-ethylbutanoic acid. In the third example, the carboxylic acid is attached to a cycloalkene ring and will therefore be named as a "carboxylic acid" substituent (rule #4). The parent ring is a cyclohexene ; letting the carboxylic acid be carbon #1, the name is 2-cyclohexenecarboxylic acid. In the last example, the name is based on benzoic acid as the parent. In this case, we simply number the substituents to give the lowest number sequence at the first point of difference and arrange alphabetically; 5-bromo-2-methylbenzoic acid. Reactions which Yield Carboxylic Acids Oxidation of Aromatic Side-Chains with Neutral Permaganate
Mno4 /H2O, heat Mno4/H2O,heat Mno4 /H2O, heat benzylic carbon must have at least one hydrogen. Warm, neutral permaganate anion will oxidize aromatic side-chains which contain at least one benzylic hydrogen to the corresponding carboxylic acid. CrO, H 个jm CH3 COOH/H2O Primary alcohols can be oxidized smoothly to the corresponding carboxylic acid with either CrO,/H,, or sodium dichromate KMno, H3o HO Acidic MnO. will oxidize an alkene bearing at least one alkyl or aryl substituent to the corresponding carboxylic acid. Terminal alkenes are converted to co 2 under these conditions H,o312504 or Na2Cr2O7 Aldehydes are smoothly oxidized to the corresponding carboxylic acid with either CrO,/H, SO, or sodium dichromate
Warm, neutral permaganate anion will oxidize aromatic side-chains which contain at least one benzylic hydrogen to the corresponding carboxylic acid. Primary alcohols can be oxidized smoothly to the corresponding carboxylic acid with either CrO3/H2SO4 or sodium dichromate. Acidic MnO4 - will oxidize an alkene bearing at least one alkyl or aryl substituent to the corresponding carboxylic acid. Terminal alkenes are converted to CO2 under these conditions. Aldehydes are smoothly oxidized to the corresponding carboxylic acid with either CrO3/H2SO4 or sodium dichromate
Ag,o metallic silver is deposited in a thin Mirror coating Aldehydes(but not ketones)are oxidized by Ag,0 in aqueous ammonia to give the carboxylic acid and metallic silver This is used as a qualitative test for aldehydes since the silver metal is deposited in a thin film, forming a silver mirror"(the Tollens test) Mno hexanedioic acid Acidic MnO. will oxidize a ketone to the corresponding carboxylic acid, in this case, splitting the ring. The reaction is slower than the oxidation of alkenes, allowing disubstituted alkene carbons to be oxidized to the ketone, without significant over-oxidation H3o Nitriles can be hydrolyzed to the corresponding carboxylic acids. Typically vigorous conditions are required (heat and concentrated acid) -MgBr- co2 LOH O=c=o Grignard reagents react with CO, to yield carboxylic acids. This is an important me thod for the preparation of carboxy lic acids and yields are generally good
Aldehydes (but not ketones) are oxidized by Ag2O in aqueous ammonia to give the carboxylic acid and metallic silver. This is used as a qualitative test for aldehydes since the silver metal is deposited in a thin film, forming a "silver mirror" (the Tollens test). Acidic MnO4 - will oxidize a ketone to the corresponding carboxylic acid, in this case, splitting the ring. The reaction is slower than the oxidation of alkenes, allowing disubstituted alkene carbons to be oxidized to the ketone, without significant over-oxidation. Nitriles can be hydrolyzed to the corresponding carboxylic acids. Typically, vigorous conditions are required (heat and concentrated acid). Grignard reagents react with CO2 to yield carboxylic acids. This is an important method for the preparation of carboxylic acids and yields are generally good
Reactions of Carboxylic Acids 1. BHA, THF 2. H3O H Carboxylic acids can be reduced to primary alcohols with liAlH, or with bh, followed by work-up with aqueous acid. In the reduction with LiAlH, an intermediate aldehyde is formed, which is rapidly reduced to give the primary alcohol oH CCL Heavy metal salts of carboxylic acids undergo decarboxylation on heating in organic solvents. In the presence of Bra, the radical intermediate is trapped as an alkyl bromide (the Hunsdiecker reaction)
Reactions of Carboxylic Acids Carboxylic acids can be reduced to primary alcohols with LiAlH4 or with BH3 followed by work-up with aqueous acid. In the reduction with LiAlH4, an intermediate aldehyde is formed, which is rapidly reduced to give the primary alcohol. Heavy metal salts of carboxylic acids undergo decarboxylation on heating in organic solvents. In the presence of Br2, the radical intermediate is trapped as an alkyl bromide (the Hunsdiecker reaction)
SoCl2 CH2COOH Carboxy lic acids can be converted into acid halides by reaction with Socla phosgene, or PBr, OR COOH ROH,H CH2COOH -OR Nc/cHg Carboxy lic acids can be converted into esters by reaction with the corresponding lcohol in the presence of an acid catalyst (Fischer esterification), b alkylation of the carboxy late anion with an alkyl halide in an S,2 reaction, or by reaction with diazome thane(methyl esters only 教学手段与方法:课堂讲授 思考题、讨论题、作业:第807面 Additiona| Problems;1819-1840)
Carboxylic acids can be converted into acid halides by reaction with SOCl2, phosgene, or PBr3. Carboxylic acids can be converted into esters by reaction with the corresponding alcohol in the presence of an acid catalyst (Fischer esterification), by alkylation of the carboxylate anion with an alkyl halide in an SN2 reaction, or by reaction with diazomethane (methyl esters only). 教学手段与方法：课堂讲授 思考题、讨论题、作业：第 807 面.Additional Problems;18.19-18.40)
参考资料(含参考书、文献等) 1. Solomons, Organic Chemistry, fifth adition 2. Oxford; Organic Chemistry 3.北京大学,有机化学 4.南京大学,有机化学,(上,下) 5.邢其毅,有机化学,(上,下) 注:1、每项页面大小可自行添减;2一次课为一个教案;3、“重点"、“难点"、“教学手段 与方法”部分要尽量具体;4、授课类型指:理论课、讨论课、实验或实习课、练习或习题 课等
参考资料（含参考书、文献等）： 1. Solomons, Organic Chemistry, fifth adition 2. Oxford; Organic Chemistry 3. 北京大学， 有机化学 4．南京大学， 有机化学，（上，下） 5．邢其毅，有机化学， （上，下） 注：1、每项页面大小可自行添减；2 一次课为一个教案；3、“重点”、“难点”、“教学手段 与方法”部分要尽量具体；4、授课类型指：理论课、讨论课、实验或实习课、练习或习题 课等
