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诱导效应 X > －OCOR > －OR > 共轭效应 X < －OCOR < －OR < NH2 NH2
离去能力 X > －OCOR > －OR > NH2
O R CH C H
α-氢的酸性
O CH3 C O Cl CH3 C ~17 O OCH3 CH3 C ~30 NH2 CH3 CH3 ~50 H O CH3 C ~20 CH3
C CH3
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O CH3 C CH3
700~800℃ CH2 C O
CH3CO2H CH3CO2H O CH3 C O
700~800℃ OH CH2 C O O C CH3 O
乙烯酮
C CH3
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酯的命名：RCO2R’
O R C OH
O R C OR'
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羧酸的氢被烃基取代

酯 ×酸×(烃基名)酯 -ic acid → alkyl -ate
O C OCH3 O O C OC(CH3)3
CH3C OCH2CH3 乙酸乙酯 Ethyl acetate 苯甲酸甲酯 环己烷羧酸叔丁酯 Methyl benzoate tert-Buthyl cyclohexanecarboxylate
第十一章 羧酸衍生物 Carboxylic Acid Derivatives
Organic Chemistry Xiamen University

Carboxylic acids are just one member of a class of acyl derivatives, RCOY, where the acyl group is bonded to an electronegatives substituent -Y that can act as a leaving group in substitution reactions. Numerous acyl derivatives are possible, but we’ll be concerned only with four of the more common ones, in addition to carboxylic acids themselves: acid halides, acid anhydrides, esters, and amides.
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腈的命名：RCN

腈 ×腈(含CN碳原子) Alkanenitrile -ic acid or –oic acid→-onitrile -carboxylic acid →-carbonitrile
CH3 CH3 CN CN
CH3CN
乙腈 苯甲腈 2,2-二甲基环己烷甲腈 Acetonitrile Benzonitrile 2,2-Dimethylcyclohexancarbonitrile
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11.2 羧酸衍生物的结构和反应性
Structure and Reactivity of Carboxylic Acid Derivatives
PCl3 PCl5
CH3CH2COCl + H3PO3 CH3(CH2)6COCl + POCl3
CH3(CH2)6CO2H
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酸酐的制备
P 2 O5 (CH3CO)2O O C O
2
2 CH3CO2H O
C OH + (CH3CO)2O O HCO2Na + CH3COCl HC O O
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酰胺的命名：RCONH2

酰胺 ×酸 →×酰胺 N-烃基×酰胺 -ic acid → -amide -carboxylic acid → -carboxamide
O O C O HC N(CH3)2 N,N-二甲基甲酰胺
DMF
酰胺 Amide
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11.1 羧酸衍生物的命名 Nomenclature of Carboxylic Acid Derivatives
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Acid halides: RCOX
R O R O R O H O Y R C C R Y R C C H Y H C C H Y H C C H
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11.3 羧酸衍生物的制备
Preparation of Carboxylic Acid Derivatives
O
OH
H+ CH3CO2C2H5 + H2O 或OH+ H2O H+ 或OH-
CH3CONH2
O
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羧酸衍生物
O R C OH R O C
R
C
Y O O O C R
X
R
C
X = F, Cl, Br, I
羧酸 Carboxylic acid O R C 酯 Ester OR'
酰卤 Acyl halide O R C NH2
酸酐 Acid anhydride R C N 腈 Nitrle
酯的制备
O C OH
+ C2H5OH
H2SO4
O C OC2 H5
+ H 2O
CH3 CH2 CH2 CH3COCl 或 (CH3CO)2O
O C ONa
+ CH3I
CH3 CH2 CH2 O C OC2 H5
O C OCH3
+ C2H5OH
CH3
Organic Chemistry Xiamen University
Organic Chemistry Xiamen University
酸酐的命名: RCO2COR’

酸酐 ×酸 →×(酸)酐 acid→anhydride
O O O
x酸×酸酐
O O O
O
CH3C O C CH3
HC O C CH3
乙酸酐 Acetic anhydride
甲(酸)乙(酸)酐 Acetic formic anhydride
丁二酸酐 Butanedioic anhydride
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Esters: RCO2R’

Systematic names for esters are derived by first giving the name of the alkyl group attached to oxygen and then identifying the carboxylic acid. In so doing, the –ic acid ending is replaced by –ate.
11.4 羧酸衍生物的水解、醇解、 氨解反应
Hydrolysis, Alcoholysis and Amonolysis Reactions of Carboxylic Acid Derivatives
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1. 水解反应
CH3COCl (CH3CO)2O + H2O + H2O CH3CO2H + HCl 2CH3CO2H CH3CO2H + C 2H5OH CH3CO2H + NH3
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Amides: RCONH2

Amides with an unsubstituted –NH2 group are named by replacing the –oic acid or –ic acid ending with –amide or by replacing the –carboxylic acid ending with –carboxamide.
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Acid anhydrides: RCO2COR’

Symmetrical anhydrides of straightchain monocarboxylic acids, and cyclic anhydrides of dicarboxylic acids, are named by replacing the word acid with anhydride
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Y Nu
pKa
~16 O CH3 C ~26
O R C
O R C
Y
Nu
O
O R C Nu Y
O OR' R C
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离去基团
O
NH2 R C
OCOR' R C
X
反应性增强
酰胺的制备
O C OH 200 C O C NH2