Chapter 20

Lecture
Carboxylic Acids
羧酸

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 Introduction
• The functional group of carboxylic acids consists of a C═O with
—OH bonded to the same carbon.
羧酸的官能團由與相同碳鍵合的C = O和-OH組成。
• The carboxyl group is usually written —COOH.
羧基通常寫成 -COOH。
• Aliphatic acids have an alkyl group bonded to —COOH.
脂肪酸具有與-COOH鍵合的烷基。
• Aromatic acids have an aryl group.
芳族酸具有芳基。
• Fatty acids are long-chain aliphatic acids.
脂肪酸是長鏈脂肪酸。

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 20-2 Nomenclature of Carboxylic Acids
羧酸的命名
Common Names

• Many aliphatic acids have historical names.

許多脂肪酸都有歷史名稱。
• Positions of substituents on the chain are labeled with Greek
letters starting at the carbon attached to the carboxylic carbon.
鏈上取代基的位置⽤與羧基碳連接的碳原⼦開始的希臘字⺟
標記。
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 IUPAC Names

• Remove the final -e from the alkane name, and add the ending
-oic acid.
從烷烴名稱中除去最後的-e，並加入結束的-oic酸。
• The carbon of the carboxyl group is number 1.
羧基的碳為1。
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 Unsaturated Acids

• Remove the final -e from the alkene name, and add the ending
-oic acid.
從烯烴名稱中除去最後的-e，並加入結束的-oic酸。
• Start numbering at the carboxyl group and the location of the
double bond is given.
在羧基上開始編號並給出雙鍵的位置。
• Stereochemistry is specified (E or Z).
規定立體化學（E或Z）。

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 Aromatic Acids

• Aromatic acids are named as derivatives of benzoic acid.

• 芳香酸被命名為苯甲酸的衍⽣物。
• Ortho-, meta-, and para- prefixes are used to specify the location
of a second substituent.
• 鄰位，間位和對位前綴⽤於指定第⼆個取代基的位置。
• Numbers are used to specify locations when more than two
substituents are present
• 當存在多於兩個取代基時，數字⽤於指定位置。

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 Dicarboxylic Acids
• Aliphatic diacids are usually called by their common names using
Greek letters beginning with the carbon next to the carboxyl
group.
脂族⼆酸通常使⽤希臘字⺟通過其通⽤名稱來命名，所述希
臘字⺟以鄰近羧基的碳開始。

• For the IUPAC name, number the chain from the end closest to a
substituent.
對於IUPAC名稱，從距離取代基最近的鏈上編號。

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© 2017 Pearson Education, Ltd. Problem 1, 2, 25, 26
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 20-3 Structure and Physical Properties of Carboxylic Acids
羧酸的結構和物理性質

• The sp2 hybrid carbonyl carbon atom is planar, with nearly trigonal
bond angles.
sp2雜化羰基碳原⼦是平⾯的，具有近三⾓形的鍵⾓。
• The O—H bond also lies in this plane, eclipsed with the C═O
bond.
O-H鍵也位於此平⾯上，與C = O鍵重疊。
• The sp3 oxygen has a C—O—H angle of 106°.
sp3氧氣的C-O-H⾓度為106°。
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 Resonance Structures of Formic Acid

• One of the unshared electron pairs on the hydroxyl oxygen atom is

delocalized into the electrophilic pi system of the carbonyl group, O
—H eclipsed with C═O, to get an overlap of the orbital with an
orbital of a lone pair on oxygen.
羥基氧原⼦上的非共享電⼦對之⼀被離域為羰基的親電⼦π系
統，O = H與C = O重疊，以使 軌道與孤電⼦對的軌道在氧上
重疊。

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 Boiling Points

• Carboxylic acids boil at considerably higher temperatures than do

alcohols, ketones, or aldehydes of similar molecular weights.
羧酸在比相似分⼦量的醇，酮或醛⾼得多的溫度下沸騰。
• The high boiling points of carboxylic acids result from formation of
a stable, hydrogen-bonded dimer.
羧酸的⾼沸點由穩定的氫鍵⼆聚體形成。

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 Melting Points
• Aliphatic acids with more than eight carbons are solids at room
temperature.
多於八個碳的脂肪酸在室溫下是固體。
• Double bonds (especially cis) lower the melting point. The
following acids all have 18 carbons:
– Stearic acid (saturated): 72 °C
– Oleic acid (one cis double bond): 16 °C
– Linoleic acid (two cis double bonds): –5 °C
雙鍵（特別是順式）降低了熔點。 以下酸都有18個碳：
– 硬脂酸（飽和）：72℃
– 油酸（⼀個順式雙鍵）：16℃
– 亞油酸（兩個順式雙鍵）：-5℃

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 Solubility
• Water solubility decreases with the length of the carbon chain.
⽔溶性隨著碳鏈的長度⽽降低。
• Acids with more than 10 carbon atoms are nearly insoluble in water.
具有10個以上碳原⼦的酸幾乎不溶於⽔。
• They are very soluble in alcohols.
它們非常溶於醇。
• They are also soluble in relatively nonpolar solvents like chloroform
because the hydrogen bonds of the dimer are not disrupted by the
nonpolar solvent.
它們也溶於相對非極性溶劑如氯仿中，因為⼆聚體
的氫鍵不被非極性溶劑破壞。

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 20-4 Acidity of Carboxylic Acids
羧酸的酸度

• A carboxylic acid may dissociate in water to give a proton and a

carboxylate ion.
羧酸可以在⽔中離解以產⽣質⼦和羧酸根離⼦。
• The equilibrium constant Ka for this reaction is called the acid-
dissociation constant.
該反應的平衡常數Ka被稱為酸解離常數。
• The acid will be mostly dissociated if the pH of the solution is higher
than the pKa of the acid.
如果溶液的pH⾼於酸的pKa，酸將⼤部分解離。
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 Energy Diagram of Carboxylic Acids and Alcohols

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 Acetate Ion Structure

• Each oxygen atom bears half of the negative charge.

每個氧原⼦帶有⼀半的負電荷。
• The delocalization of the negative charge over the two oxygens
makes the acetate ion more stable than an alkoxide ion.
兩個氧原⼦上的負電荷的離域使得⼄酸根離⼦比醇鹽離⼦更
穩定。
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 Substituent Effects on Acidity

• The magnitude of a substituent effect depends on its distance

from the carboxyl group.
取代基效應的⼤⼩取決於其與羧基的距離。

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 Aromatic Carboxylic Acids

• Electron-withdrawing groups enhance the acid strength, and

electron-donating groups decrease the acid strength.
吸電⼦基團提⾼酸強度，給電⼦基團降低酸強度。
• Effects are strongest for substituents in the ortho and para positions.
對鄰位和對位取代基的影響最強。

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 Problem 3, 29, 32,
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33, 34, 42
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 20-5 Salts of Carboxylic Acids 羧酸鹽
Deprotonation of Carboxylic Acids

• The hydroxide ion completely deprotonates the acid to

form the carboxylate salt.
氫氧根離⼦完全去質⼦酸形成羧酸鹽。

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 Protonation of Carboxylic Acids

• Adding a strong acid, like HCl, regenerates the carboxylic

acid.
加入⼀種強酸如HCl，使羧酸再⽣。

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 Naming Carboxylic Acid Salts
• First name the cation.
⾸先命名陽離⼦。
• Then name the anion by replacing the
-ic acid with -ate.
然後通過⽤-ate代替α-酸來命名陰離⼦。

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 Properties of Acid Salts
• Usually solids with no odor
通常固體沒有氣味
• Carboxylate salts of Na+, K+, Li+, and NH4+ are soluble in
water.
Na +，K +，Li +和NH 4 +的羧酸鹽可溶於⽔。
• Soap is the soluble sodium salt of a long-chain fatty acid.
肥皂是長鏈脂肪酸的可溶性鈉鹽。
• Salts can be formed by the reaction of an acid with NaHCO3,
releasing CO2.
鹽可以通過酸與NaHCO3的反應形成，釋放CO2。

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 Extraction of Carboxylic Acids

• A carboxylic acid is more soluble in the organic phase, but its salt is more soluble
in the aqueous phase.
羧酸更易溶於有機相，但其鹽在⽔相中更易溶解。
• Acid–base extractions can move the acid from the ether phase into the aqueous
phase and back into the ether phase, leaving impurities behind.
酸鹼提取可以將酸從⼄醚相轉移到⽔相中，並回到⼄醚相中，留下雜質。

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 20-6 Commercial Sources of Carboxylic Acids
羧酸的商業來源
Basic Hydrolysis of Fats and Oils

• The basic hydrolysis of fats and oils produces soap (this

reaction is known as saponification).
脂肪和油的鹼性⽔解產⽣肥皂（該反應被稱為皂
化）。
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 Some Important Acids
• Acetic acid is in vinegar and other foods, and is used
industrially as a solvent, catalyst, and reagent for synthesis.
醋酸在醋等食品中，在⼯業上作為溶劑，催化劑，合成
⽤試劑使⽤。
• Fatty acids are from fats and oils.
脂肪酸來⾃脂肪和油。
• Benzoic acid is found in drugs and preservatives.
苯甲酸被發現在藥物和防腐劑。
• Adipic acid is used to make nylon 66.
⼰⼆酸⽤於製造尼龍66。
• Phthalic acid is used to make polyesters.
鄰苯⼆甲酸被⽤來製造聚酯。
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 20-8 Synthesis of Carboxylic Acids
羧酸的合成

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 Synthesis Review
• Oxidation of primary alcohols and aldehydes with chromic acid
• ⽤鉻酸氧化伯醇和醛
• Cleavage of an alkene with hot KMnO4 produces a carboxylic
acid if there is a vinylic hydrogen present.
• 如果存在⼄烯基氫，則⽤熱KMnO 4裂解烯烴產⽣羧酸。
• Ozonolysis of an alkyne
• 炔的臭氧分解
• Alkyl benzenes are oxidized to benzoic acid by hot KMnO4 or
hot chromic acid.
• 通過熱KMnO4或熱鉻酸將烷基苯氧化成苯甲酸。

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 Oxidation of Primary Alcohol to Carboxylic Acids

• Primary alcohols and aldehydes are commonly oxidized to acids

by chromic acid (H2CrO4 formed from Na2Cr2O7 and H2SO4).
伯醇和醛通常被鉻酸（由Na2Cr2O7和H2CrO4形成的H2SO4)
氧化成酸。
• Potassium permanganate is occasionally used, but the yields are
often lower.
偶爾使⽤⾼錳酸鉀，但收率往往較低。

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 Cleavage of Alkenes Using KMnO4

• Warm, concentrated permanganate solutions oxidize the glycols,

cleaving the central C═C bond.
溫熱的濃縮⾼錳酸鹽溶液氧化⼆醇，切割中央C = C鍵。
• Depending on the substitution of the original double bond, ketones
or acids may result.
取決於原雙鍵的取代，可能導致酮或酸。

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 Alkyne Cleavage Using Ozone or KMnO4

• With alkynes, either ozonolysis or a vigorous

permanganate oxidation cleaves the triple bond to give
carboxylic acids.
⽤炔烴，無論是臭氧分解還是劇烈的⾼錳酸鹽
氧化都能裂解三鍵產⽣羧酸。

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 Side-Chain Oxidation of Alkylbenzenes

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 Carboxylation of Grignard Reagents

• Grignard reagents react with CO2 to produce, after protonation, a

carboxylic acid.
格⽒試劑與CO 2反應⽣成質⼦化後的羧酸。
• This reaction is sometimes called “CO2 insertion,” and it increases
the number of carbons in the molecule by one.
這種反應有時被稱為“CO2插入”，它使分⼦中的碳數增加⼀
個。
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 Hydrolysis of Nitriles

• Basic or acidic hydrolysis of a nitrile (—CN) produces a carboxylic acid.

腈（-CN）的鹼性或酸性⽔解產⽣羧酸。
• The overall reaction, starting from the alkyl halide, adds an extra carbon to the
molecule.
Problem 11, 35, 44
整個反應從烷基⿄開始，向分⼦中加入額外的碳。

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 20-9 Reactions of Carboxylic Acids and Derivatives;
Nucleophilic Acyl Substitution
羧酸和衍⽣物的反應; 親核酰基取代
• The group bonded to the acyl carbon determines the class of compound:
– —OH, carboxylic acid
– —Cl, acid chloride
– —OR′, ester
– —NH2, amide
鍵合到酰基碳上的基團決定了化合物的類別：
-OH，羧酸
-Cl，酰氯
-OR'，酯
-NH 2，酰胺
• These interconvert via nucleophilic acyl substitution.
這些通過親核酰基取代相互轉化。

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 Nucleophilic Acyl Substitution

• Carboxylic acids react by nucleophilic acyl substitution, where

one nucleophile replaces another on the acyl (C═O) carbon atom.
羧酸通過親核酰基取代反應，其中⼀個親核試劑取代酰基
（C = O）碳原⼦上的另⼀個。

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 Basic Hydrolysis of an Ester

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20-10 Condensation of Acids with Alcohols: The Fischer Esterification
酸與醇的縮合：費歇爾酯化

• Reaction of a carboxylic acid with an alcohol under acidic conditions produces an

ester.
在酸性條件下羧酸與醇的反應產⽣酯。
• Reaction is an equilibrium; the yield of ester is not high.
反應是平衡的; 酯的收率不⾼。
• To drive the equilibrium toward the formation of products, use a large excess of
alcohol.
為了推動產品形成的平衡，使⽤⼤量的酒精。
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 Mechanism of the Fischer Esterification

• Step 1:
– The carbonyl oxygen is protonated to activate the carbon toward
nucleophilic attack.
– The alcohol attacks the carbonyl carbon.
– Deprotonation of the intermediate produces the ester hydrate.
步驟1：
– 羰基氧被質⼦化以激活碳向親核攻擊。
– 酒精攻擊羰基碳。
– 中間體的去質⼦化產⽣酯⽔合物。

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 Mechanism of the Fischer Esterification

• Step 2:
– Protonation of one of the hydroxide groups creates a good
leaving group.
– Water leaves.
– Deprotonation of the intermediate produces the ester.
第2步：
– ⼀個氫氧根基團的質⼦化產⽣了⼀個良好的離去基團。
– ⽔離開。
– 中間體的去質⼦化產⽣酯。
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 Solved Problem 1
Ethyl orthoformate hydrolyzes easily in dilute acid to give formic acid and three equivalents of
ethanol. Propose a mechanism for the hydrolysis of ethyl orthoformate.

Solution
Ethyl orthoformate resembles an acetal with an extra alkoxy group, so this mechanism should
resemble the hydrolysis of an acetal (Section 18-18). There are three equivalent basic sites:
the three oxygen atoms. Protonation of one of these sites allows ethanol to leave, giving a
resonance-stabilized cation. Attack by water gives an intermediate that resembles a
hemiacetal with an extra alkoxy group.

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 Solution (Continued)
Protonation and loss of a second ethoxyl group give an intermediate that is simply a
protonated ester.

Hydrolysis of ethyl formate follows the reverse path of the Fischer esterification. This part of
the mechanism is left to you as an exercise.
Problem 13, 14, 15, 16,
37, 38, 41

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 20-11 Esterification Using Diazomethane
⽤重氮甲烷酯化

• Carboxylic acids are converted to their methyl esters very simply

by adding an ether solution of diazomethane.
通過加入重氮甲烷的⼄醚溶液，可以非常簡單地將羧酸轉化
成它們的甲酯。
• The reaction usually produces quantitative yields of ester.
反應通常產⽣酯的定量收率。
• Diazomethane is a very toxic, explosive, yellow gas.
重氮甲烷是⼀種非常有毒，易爆，黃⾊的氣體。
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 Mechanism of Diazomethane Esterification
Step 1: Proton transfer, forming a carboxylate ion and a methyldiazonium ion.
步驟1：質⼦轉移，形成羧酸根離⼦和甲基重氮離⼦。

Step 2: Nucleophilic attack on the methyl group displaces nitrogen.

步驟2：對甲基的親核攻擊取代氮。

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20-12 Condensation of Acids with Amines: Direct Synthesis of Amides
酸與胺的縮合：直接合成酰胺

• The initial reaction of a carboxylic acid with an amine gives an ammonium carboxylate
salt.
羧酸與胺的初始反應產⽣羧酸銨鹽。 Problem 18
• Heating this salt to well above 100 °C drives off steam and forms an amide.
將這種鹽加熱⾄遠⾼於100℃，蒸汽形成酰胺。

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 20-13 Reduction of Carboxylic Acids 羧酸的還原
LiAlH4 or BH3 Reduction of Carboxylic Acids

• LiAlH4 reduces carboxylic acids to primary alcohols.

LiAlH4將羧酸還原成伯醇。
• The intermediate aldehyde reacts faster with the reducing agent
than the carboxylic acid.
中間體醛與還原劑反應比羧酸更快。
• Borane can also reduce the carboxylic acid to the alcohol.
硼烷還可以將羧酸還原成醇。

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 Reduction of Acid Chlorides to Aldehydes

• Lithium aluminum tri(tert-butoxy)hydride is a weaker reducing agent than

lithium aluminum hydride.
三（叔丁氧基）氫化鋰鋁是比氫化鋁鋰弱的還原劑。
• It reduces acid chlorides because they are strongly activated toward
nucleophilic addition of a hydride ion.
它減少了酰基氯，因為它們被強烈地活化為氫化物離⼦的親核加成。
• Under these conditions, the aldehyde reduces more slowly, and it is easily
isolated.
在這些條件下，醛減少得更慢，並且容易分離。
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 20-14 Alkylation of Carboxylic Acids to Form Ketones
羧酸烷基化形成酮
Conversion of Carboxylic Acids to Ketones

• A general method of making ketones involves the reaction of a

carboxylic acid with two equivalents of an organolithium
reagent.
製備酮的⼀般⽅法涉及羧酸與兩當量有機鋰試劑的反應。

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 Mechanism of Ketone Formation

• The first equivalent of organolithium acts as a base, deprotonating

the carboxylic acid.
有機鋰的第⼀個等價物作為鹼，使羧酸去質⼦化。
• The second equivalent adds to the carbonyl.
第⼆個等價物增加了羰基。
• Hydrolysis forms the hydrate of the ketone, which converts to the
ketone.
⽔解形成酮的⽔合物，其轉化為酮。
Problem 19, 20, 21
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 20-15 Synthesis and Use of Acid Chlorides
酰氯的合成與應⽤

• The best reagents for converting carboxylic acids to acid chlorides

are thionyl chloride (SOCl2) and oxalyl chloride (COCl2).
將羧酸轉化為酰氯的最佳試劑是亞硫酰氯（SOCl2）和草酰
氯（COCl2）。
• They form gaseous by-products that do not contaminate the
product.
它們形成不會污染產品的氣體副產物。

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 Mechanism of Acid Chloride Formation

Step 1:

Step 2:

Step 3:

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 Effective Esterification of a Carboxylic Acid

• Esterification of an acyl chloride is more efficient than

the Fischer esterification.
酰基氯的酯化比費歇爾酯化更有效。

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 Amide Synthesis

• Ammonia and amines react with acid chlorides to give amides

氨和胺與酰氯反應⽣成酰胺
• NaOH, pyridine, or a second equivalent of amine is used to
neutralize the HCl produced in order to prevent protonation of the
amine.
⽤氫氧化鈉，吡啶或第⼆當量的胺中和產⽣的鹽酸以防⽌胺
的質⼦化。 Problem 24, 36, 39
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