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):第十三章.羧酸衍生|授课类型理论课 t( Carboxylic acid derivatives 授课时间第4周第5558节 教学目标或要求:了解羧酸衍生物的分类,命名和光谱性质。了解酰卤和酸酐的化学 反应性质及其乙酰乙酸乙酯和丙二酸二乙酯在有机合成上的应用。重点掌握羧酸衍生 物的化学反应性质及其有关有机合成制备方法 教学内容(包括基本内容、重点、难点) 酸酸衍生物 本章的重点是羧酸衍生物中羰基上的亲核取代反应和亲核取代反应历程(特别是酯的水解反应 历程)、羧酸衍生物在有机合成中的应用和几个重要的有机人名反应等。难点是对不同结构的羧酸 衍生物中羰基上的亲核取代反应历程的理解 Nomenclature of Carboxylic Acid Derivatives The following page contains a detailed description of the IUPAC rules for the naming of common carboxy lic acid derivatives; a summary of these rules is given in the figure be low. amde -carboxylic acid -carboxamide NH2 -oyl halide carbonyl halide -oate -carboxylate anhydride -nitrile mile Simple carboxy lic acids are named as derivatives of the parent alkane using the suffix -oic acid Select the longest continuous carbon chain, containing the carboxy lic acid group, and derive the
有机化学(双语教学) 课程教案 授课题目（教学章节或主题）：第十三章．羧酸衍生 物 （Carboxylic acid derivatives） 授课类型 理论课 授课时间 第 4 周第 55-58 节 教学目标或要求：了解羧酸衍生物的分类，命名和光谱性质。了解酰卤和酸酐的化学 反应性质及其乙酰乙酸乙酯和丙二酸二乙酯在有机合成上的应用。重点掌握羧酸衍生 物的化学反应性质及其有关有机合成制备方法。 教学内容（包括基本内容、重点、难点）： 酸酸衍生物 本章的重点是羧酸衍生物中羰基上的亲核取代反应和亲核取代反应历程（特别是酯的水解反应 历程）、羧酸衍生物在有机合成中的应用和几个重要的有机人名反应等。难点是对不同结构的羧酸 衍生物中羰基上的亲核取代反应历程的理解。 Nomenclature of Carboxylic Acid Derivatives The following page contains a detailed description of the IUPAC rules for the naming of common carboxylic acid derivatives; a summary of these rules is given in the figure below. 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 ber the carbon chain, begin the end nearest to the carboxy lic acid group 3. Number the substituents and write the name, listing substituents alphabetically Carboxy lic acid substituents attached to rings are named using the suffix -carboxylic acid Several simple examples are shown below 1 2-ethydpentanoic acid 3-bromo-2-ethyilbutanoic acid OoH COOH 2-cycloherenecarboryhic 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 ethyl 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-ethy l butanoic 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 arent ring is a cyclohexene letting the carboxy lic acid be carbon #l, 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 Simple acid halides are named by identifying the acyl group using the suffix -oyI followed by the halogen. elect the longest continuous carbon chain, containing the acyl group, and derive the parent name by placing the-e ending with -oyl, then append the halogen. 2. Num ber the carbon chain, beginning at the end nearest to the acyl group
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: 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. Simple acid halides are named by identifying the acyl group, using the suffix -oyl followed by the halogen. 1. Select the longest continuous carbon chain, containing the acyl group, and derive the parent name by replacing the -e ending with -oyl, then append the halogen. 2. Number the carbon chain, beginning at the end nearest to the acyl group
3. Number the substituents and write the name, listing substituents alpha betically. 4. Acid halide substituents attached to rings are named using the suffix -carbonyl Several simple examples are shown below: Z-ethyipe chloride 3-bromo-2-ethyibutanoyl CH 2-cycloherenecarbomyl chloride 5-bromo-2-methyit fluoride In the first example, the parent chain is a pentane and the acy l group is assigned as carbon #1. On the pentane parent, there is an ethy l group in position #2 hence the name, 2-ethy lpentanoyl chloride 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 butanoyl bromide). Attached to the chain at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name 3-bromo-2-ethy l butanoyl bromide In the third example, the acyl group is attached to a cycloalkene ring and will therefore be named as a carbonyl chloride"substituent (rule #4). The parent ring is a cyclohexene; letting the acyl group be carbon #l, the name is 2-cyclohexenecarbonyl chloride 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 benzoyl fluoride Simple acid anhydrides are named by replacing the ending acid with anhydride Select the longest continuous carbon chain, conta ining the carboxy lic acid group, and derive the parent name by replacing the -e ending with -oic anhydride 2. Num ber the carbon chain, beginning at the end nearest to the acyl grou
3. Number the substituents and write the name, listing substituents alphabetically. 4. Acid halide substituents attached to rings are named using the suffix -carbonyl. Several simple examples are shown below: In the first example, the parent chain is a pentane and the acyl group is assigned as carbon #1. On the pentane parent, there is an ethyl group in position #2; hence the name, 2-ethylpentanoyl chloride. 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 butanoyl bromide). Attached to the chain at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name 3-bromo-2-ethylbutanoyl bromide. In the third example, the acyl group is attached to a cycloalkene ring and will therefore be named as a "carbonyl chloride" substituent (rule #4). The parent ring is a cyclohexene ; letting the acyl group be carbon #1, the name is 2-cyclohexenecarbonyl chloride. 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-methylbenzoyl fluoride. Simple acid anhydrides are named by replacing the ending "acid" with "anhydride". 1. Select the longest continuous carbon chain, containing the carboxylic acid group, and derive the parent name by replacing the -e ending with -oic anhydride. 2. Number the carbon chain, beginning at the end nearest to the acyl group
3. Number the substituents and write the name, listing substituents alpha betically Several simple examples are shown below: benzoic anhydride phthalic anhydride In the first example, the parent chains are both pentane hence the name pentanoic anhydride (also as bis pentanoic anhydride) In the second example, there are two parent chains; ethanoic acid and butanoic acid; hence the name butanoic ethanoic anhydride(acetic can be used in place of ethanoic) In the third example, the name is based on benzoic acid as the parent, and the name is simply benzoic anhydride. In the last example, the name is based on phthalic acid and the name is simply phthalic anhydride Simple amides are named by replacing the ending -oic acid with -amide 1. Select the longest continuous carbon cha in, conta ining the acyl group, and derive the parent name by placing the -e ending with - amide 2. Num ber the carbon chain, beginning at the end nearest to the acyl group 3. Num ber the substituents and write the name, listing substituents alphabetically 4. Acid halide substituents attached to rings are named using the suffix - carboxamide 5. If the nitrogen atom is further substituted, the substituents are preceded by N-to indicate that they are attached to the nitrogen Several simple examples are shown below
3. Number the substituents and write the name, listing substituents alpha betically. Several simple examples are shown below: In the first example, the parent chains are both pentane; hence the name, pentanoic anhydride (also as bis-pentanoic anhydride). In the second example, there are two parent chains; ethanoic acid and butanoic acid; hence the name butanoic ethanoic anhydride (acetic can be used in place of ethanoic). In the third example, the name is based on benzoic acid as the parent, and the name is simply benzoic anhydride. In the last example, the name is based on phthalic acid and the name is simply phthalic anhydride. Simple amides are named by replacing the ending -oic acid with -amide . 1. Select the longest continuous carbon chain, containing the acyl group, and derive the parent name by replacing the -e ending with -amide. 2. Number the carbon chain, beginning at the end nearest to the acyl group. 3. Number the substituents and write the name, listing substituents alphabetically. 4. Acid halide substituents attached to rings are named using the suffix -carboxamide. 5. If the nitrogen atom is further substituted, the substituents are preceded by N- to indicate that they are attached to the nitrogen. Several simple examples are shown below:
NH2 Z-ethyipentanamide 3-brom0-2-et CH3 o N-methyl5-bromo-2- In the first example, the parent chain is a pentane and the acy l group is assigned as carbon #1. On the pentane parent, there is an ethy l group in position #2 hence the name, 2-ethy pentanamide 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 butane). Attached to the chain at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name 3-bromo-2-ethy butanamide In the third example, the acyl group is attached to a cycloalkene ring and will therefore be named as carboxamide"substituent (rule #4). The parent ring is a cyclohexene; letting the acyl group be carbon #1, the name is 2-cyclohexenecarboxamid In the last example, the name is based on benzoic acid as the parent and the nitrogen has a methyl substituent. In this case, we simply number the substituents to give the lowest number sequence at the first point of difference and arrange alphabetically: N-methy 1-5-bromo-2-methy lbenzamide Simple carboxylate esters are named as derivatives of the carboxylic acid, by changing the suffix -oic acid to -oate, and naming the alcohol portion first. Select the longest continuous carbon chain, conta ining the acyl group, and derive the parent name by replacing the-e ending with -oate, then a ppend the the alcohol to the front of the name 2. Num ber the carbon chain, beginning at the end nearest to the acyl group. 3. Number the substituents and write the name, listing substituents alpha betically 4. Acid halide substituents attached to rings are named using the suffix -carboxylate Several simple examples are shown below
In the first example, the parent chain is a pentane and the acyl group is assigned as carbon #1. On the pentane parent, there is an ethyl group in position #2; hence the name, 2-ethylpentanamide. 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 butane). Attached to the chain at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name 3-bromo-2-ethylbutanamide. In the third example, the acyl group is attached to a cycloalkene ring and will therefore be named as a "carboxamide" substituent (rule #4). The parent ring is a cyclohexene ; letting the acyl group be carbon #1, the name is 2-cyclohexenecarboxamide. In the last example, the name is based on benzoic acid as the parent and the nitrogen has a methyl substituent. In this case, we simply number the substituents to give the lowest number sequence at the first point of difference and arrange alphabetically; N-methyl-5-bromo-2-methylbenzamide. Simple carboxylate esters are named as derivatives of the carboxylic acid, by changing the suffix -oic acid to -oate, and naming the alcohol portion first. 1. Select the longest continuous carbon chain, containing the acyl group, and derive the parent name by replacing the -e ending with -oate, then append the the alcohol to the front of the name. 2. Number the carbon chain, beginning at the end nearest to the acyl group. 3. Number the substituents and write the name, listing substituents alphabetically. 4. Acid halide substituents attached to rings are named using the suffix -carboxylate. Several simple examples are shown below:
methyl 2-ethytpentanoate ethyl 3-bromo-2-ethylbutanoate C CH yclopenty12-cycloherenecarborylate methyl 5-bromo-2 In the first example, the alcohol is methanol the parent chain is a pentane and the acyl group is assigned as carbon #l. On the pentane parent, there is an ethyl group in position #2: hence the name, methyl 2-ethylpentanoate In the second example, the alcohol is ethanol and there are two potential four-carbon chains: in this case, the chain with the most substituents is selected as parent, (a butanoyl bromide). Attached to the chain at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name ethy l 3-bromo-2-ethy butanoate In the third example, the alcohol is cyclopentanol and the acyl group is attached to a cycloalkene ring and will therefore be named as a"carboxy late substituent (rule#4). The parent ring is a cyclohexene: letting the acyl group be carbon #l, the name is cyclopenty l 2-cyclohexenecarboxylate In the last example, the alcohol is methanol and 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: methy l 5-bromo-2-methy benzoate Simple nitriles are named as derivatives of the parent alkane, using the suffix nitrile to -oate, and naming the alcohol portion first. elect the longest continuous carbon chain, containing the nitrile, and derive the parent name by appending-nitrile 2. Num ber the carbon chain, beginning at the end nearest to the nitrile group 3. Number the substituents and write the name, list ing substituents alphabetically 4. Acid halide substituents attached to rings are named using the suffix-carbonitrile Several simple examples are shown below:
In the first example, the alcohol is methanol the parent chain is a pentane and the acyl group is assigned as carbon #1. On the pentane parent, there is an ethyl group in position #2; hence the name, methyl 2-ethylpentanoate. In the second example, the alcohol is ethanol and there are two potential four-carbon chains; in this case, the chain with the most substituents is selected as parent, (a butanoyl bromide). Attached to the chain at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name ethyl 3-bromo-2-ethylbutanoate. In the third example, the alcohol is cyclopentanol and the acyl group is attached to a cycloalkene ring and will therefore be named as a "carboxylate" substituent (rule #4). The parent ring is a cyclohexene ; letting the acyl group be carbon #1, the name is cyclopentyl 2-cyclohexenecarboxylate. In the last example, the alcohol is methanol and 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; methyl 5-bromo-2-methylbenzoate. Simple nitriles are named as derivatives of the parent alkane, using the suffix -nitrile to -oate, and naming the alcohol portion first. 1. Select the longest continuous carbon chain, containing the nitrile, and derive the parent name by appending -nitrile. 2. Number the carbon chain, beginning at the end nearest to the nitrile group. 3. Number the substituents and write the name, listing substituents alphabetically. 4. Acid halide substituents attached to rings are named using the suffix -carbonitrile. Several simple examples are shown below:
2-ethylpentanenitrile 3-bromo-2-ethydbutanenitmile CH3 Z-cycloherenecarbonitn Br 5bromo-2 methydberzomitmle In the first example, the parent chain is a pentane and the nitrile group is assigned as carbon #1. On the pentane parent, there is an ethy l group in position #2: hence the name, 2-ethy pentanenitrile 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 butanenitrile Attached to the chain at carbon #2 is an ethy l group and at carbon #3, a bromine; hence the name 3-bromo-2-ethy butanenitrile. In the third example the nitrile group is attached to a cycloalkene ring and will therefore be named as carbonitrile"substituent (rule #4). The parent ring is a cyclohexene; letting the acyl group be carbon #l, the name is 2-cyclohexenecarbonitrile In the last example the name is based on benzonitrile 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 KB5-BROMO-2-METHYLBENZONITRILE B> The Partitioning of Tetrahedral Intermediates The attack of a nucleophile on an acy l derivative results in the formation of a transient tetrahedral intermediate. This intermediate partitions, that is breaks down, by a series of parallel pathways to generate a series of products which is governed by the exact nature of the intermediate and the individual microscopic rate constants for each potential pathway. For tetrahedral intermediates formed from simply acyl derivatives, it is possible to apply a simple set of rules to determine which group around the tetrahedral center
In the first example, the parent chain is a pentane and the nitrile group is assigned as carbon #1. On the pentane parent, there is an ethyl group in position #2; hence the name, 2-ethylpentanenitrile. 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 butanenitrile). Attached to the chain at carbon #2 is an ethyl group and at carbon #3, a bromine; hence the name 3-bromo-2-ethylbutanenitrile. In the third example the nitrile group is attached to a cycloalkene ring and will therefore be named as a "carbonitrile" substituent (rule #4). The parent ring is a cyclohexene ; letting the acyl group be carbon #1, the name is 2-cyclohexenecarbonitrile. In the last example the name is based on benzonitrile 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; . The Partitioning of Tetrahedral Intermediates The attack of a nucleophile on an acyl derivative results in the formation of a transient tetrahedral intermediate. This intermediate partitions, that is, breaks down, by a series of parallel pathways to generate a series of products which is governed by the exact nature of the intermediate and the individual microscopic rate constants for each potential pathway. For tetrahedral intermediates formed from simply acyl derivatives, it is possible to apply a simple set of rules to determine which group around the tetrahedral center is
the best leaving group", and hence, what will be the predominate product of a given reaction In general, for tetrahedral intermediates involving anionic leaving groups you can assume that the best leaving group will be that group which has the strongest conjugate acid R fr anionic leaving groups, m general, the group which has the strongest conjugate acid (forms the most stable anion) wube the best leaving group ifR1-OHis a stronger acid than R,OH, R1-o vill be the preferred leaving group For example, consider the intermediate shown below. The potential leaving groups are methoxide and phenoxide. The conjugate acids of methoxide and phenolate anions are methanol, pk=16, and phenol, pk=9 (approximate pk values The strongest acid is phenol, and the major product formed will be ethy l acetate. -strongest acid e best leaving group H CH3-OH =94 Another example: the tetrahedral intermediate shown below has two potential leaving groups, chloride and phenoxide. The strongest con jugate acid is HCl hence chloride anion is most likely to leave and the ma jor product will be pheny l acetate
the "best leaving group", and hence, what will be the predominate product of a given reaction. In general, for tetrahedral intermediates involving anionic leaving groups, you can assume that the best leaving group will be that group which has the strongest conjugate acid. For example, consider the intermediate shown below. The potential leaving groups are methoxide and phenoxide. The conjugate acids of methoxide and phenolate anions are methanol, pKa=16, and phenol, pKa=9 (approximate pKavalues). The strongest acid is phenol, and the major product formed will be ethyl acetate. Another example; the tetrahedral intermediate shown below has two potential leaving groups, chloride and phenoxide. The strongest conjugate acid is HCl, hence chloride anion is most likely to leave and the major product will be phenyl acetate
most stable anion est leaving group 十 Again, the process is simply to examine the potential leaving groups, determine which has the strongest conjugate acid (the lower pk), reform the carbonyl allowing that group to leave and draw the final product. Reactions of Carboxylic Acid Derivatives es H2O NH Lia Acid halides are the most reactive acy l derivatives, and can be readily converted into carboxylic acids, esters and amides, by simple reaction with the appropriate nucleophile. The reaction involves an addition-elimination mechanism. as shown below
Again, the process is simply to examine the potential leaving groups, determine which has the strongest conjugate acid (the lower pKa), reform the carbonyl, allowing that group to leave and draw the final product. Reactions of Carboxylic Acid Derivatives Acid Halides Acid halides are the most reactive acyl derivatives, and can be readily converted into carboxylic acids, esters and amides, by simple reaction with the appropriate nucleophile. The reaction involves an addition-elimination mechanism, as shown below: