Chapter 16 Carboxylic Acids and Esters

16.1 Carboxylic Acids

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Carboxylic Acids
A carboxylic acid Contains a carboxyl group, which is a carbonyl group (C=O) attached to a hydroxyl group (OH). Has the carboxyl group on carbon 1. carbonyl group O CH3 COH hydroxyl group or CH3COOH carboxyl group

Models of Carboxylic Acids

The three-dimensional models show the geometry of atoms in carboxylic acid molecules.

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

IUPAC Names
The IUPAC names of carboxylic acids

Replace the -e in the alkane name with -oic acid.

CH4 methane HCOOH methanoic acid CH3CH3 ethane CH3COOH ethanoic acid

Number substituents from the carboxyl carbon 1. CH3 O | CH3CHCH2COH

4 3 2 1

3-methylbutanoic acid
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Common Names
The common names of simple carboxylic acids Are formic acid (1C), acetic acid (2C), propionic acid (3C), and butyric acid (4C). HCOOH formic acid CH3COOH acetic acid Locate substituents using , , for the carbon atoms adjacent to the carboxyl carbon. CH3 | CH3CHCH2COOH 3-methylbutanoic acid (-methylbutryic acid)
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Alpha Hydroxy Acids

Alpha hydroxy acids (AHAs) Occur naturally in fruit, milk, and sugarcane. Are used in skin care products.

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Names and Sources of Some Carboxylic Acids

TABLE 16.1

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Common Carboxylic Acids

Methanoic acid (formic acid) O HCOH
ethanoic acid (acetic acid) O CH3COH
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Aromatic Carboxylic Acids

Benzoic acid Is the aromatic carboxylic acid.
Locates substituents by assigning 1 to the carbon attached to the carboxyl group. Has common names that assign prefixes ortho, meta, and para for 2 substituents. ortho 1, 2 location

meta
para

1, 3 location
1, 4 location
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Aromatic Carboxylic Acids

O

O
C OH

O C OH

C OH

Cl NH2
benzoic acid 3-chlorobenzoic acid m-chlorobenzoic acid 4-aminobenzoic acid p-aminobenzoic acid

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Learning Check
Give the IUPAC and common names: A. CH3COOH
CH3 | CH3CHCOOH
COOH Br

B.

C.

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Solution
A. B. CH3COOH CH3 | CH3CHCOOH
COOH Br

ethanoic acid (acetic acid) 2-methylpropanoic acid (-methylpropionic acid) 2-bromobenzoic acid (o-bromobenzoic acid)

C.

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Preparation of Carboxylic Acids

Carboxylic acids can be prepared by oxidizing primary alcohols or aldehydes. The oxidation of ethanol produces ethanoic acid (acetic acid). OH O | [O] || CH3CH2 CH3CH O [O] || CH3COH

ethanol (ethyl alcohol)

ethanal (acetaldehyde)

ethanoic acid (acetic acid)

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Learning Check
What alcohol could be used to prepare the following: 1. butanoic acid

2. propanoic acid

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Solution
What alcohol could be used to prepare the following: [O] [O] 1. butanol butanal butanoic acid

[O]
2. 1-propanol propanal

[O]
propanoic acid

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Chapter 16 Carboxylic Acids and Esters

16.2 Properties of Carboxylic Acids

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

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Polarity of Carboxylic Acids

Carboxylic acids Are strongly polar. Have two polar groups: hydroxyl (OH) and carbonyl (C=O). O + - + CH3CO H

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Boiling Points of Carboxylic Acids

The boiling points of carboxylic acids Are higher than alcohols, ketones, and aldehydes of similar mass. Are high because they form dimers in which hydrogen bonds form between the polar groups in the two carboxyl groups. O HO || | CH3C CCH3 | || OH O
A dimer of acetic acid
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Comparison of Boiling Points

Compound O CH3CH2CH CH3CH2CH2OH O CH3COH Molar Mass Boiling Point

58 60

49C 97C

60

118C
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Solubility in Water
Carboxylic acids Form hydrogen bonds with many water molecules. With 1-4 carbon atoms are very soluble in water.
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Water molecules

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Boiling Points and Solubility

TABLE 16.2

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Acidity of Carboxylic Acids

Carboxylic acids Are weak acids. Ionize in water to produce carboxylate ions and hydronium ions. O O CH3COH + H2O CH3CO + H3O+

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

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Neutralization of Carboxylic Acids

Carboxylic acid salts Are a product of the neutralization of a carboxylic acid with a strong base. CH3COOH + NaOH CH3COO Na+ + H2O acetic acid sodium acetate (carboxylic acid salt) Are used as preservatives and flavor enhancers.

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

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Learning Check
Write the equation for the reaction of propanoic acid with A. water

B. KOH

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Solution
Write the equation for the reaction of propanoic acid with A. water
CH3CH2COOH + H2O CH3CH2COO + H3O+

B. KOH
CH3CH2COOH + KOH CH3CH2COO K+ + H2O

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Chapter 16 Carboxylic Acids and Esters

16.3 Esters 16.4 Naming Esters

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Esters
In an ester, The H in the carboxyl group is replaced with an alkyl group.

O CH3 COCH3 ester group

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Esterification
Esterification is The reaction of a carboxylic acid and alcohol in the presence of an acid catalyst to produce an ester. O H+ CH3COH + HOCH2CH3 O CH3COCH2CH3 + H2O
ethyl acetate (an ester)
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Learning Check
Write the equation for the reaction of propanoic acid and methanol in the presence of an acid catalyst.

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Solution
Write the equation for the reaction of propanoic acid and methanol in the presence of an acid catalyst. O H+ CH3CH2COH + HOCH3 propanoic acid methanol O CH3CH2COCH3 + H2O

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Naming Esters
The name of an ester contains the names of The alkyl group from the alcohol. The carbon chain from the acid with ate ending. from alcohol from acid O methyl CH3 OC CH3 ethanoate (acetate) IUPAC: methyl ethanoate common: methyl acetate
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Ester Products
Aspirin Is used to relieve pain and reduce inflammation. Is an ester of salicylic acid and acetic acid. Oil of wintergreen Is used to soothe sore muscles. Is an ester of salicylic acid and methanol.
O C OH O O C CH3

O C O CH3 OH
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Esters in Plants
Esters give flowers and fruits their pleasant fragrances and flavors.
TABLE 16.4

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Learning Check
Give the IUPAC and common names of the following compound, which is responsible for the flavor and odor of pears.

O CH3COCH2CH2CH3

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Solution
Give the IUPAC and common names of the following compound, which is responsible for the flavor and odor of pears. from 1-propanol O CH3COCH2CH2CH3 Propyl ethanoate (IUPAC) Propyl acetate (common)

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Learning Check
Name the following esters: O A. CH3CH2CH2COCH3 O CH3CH2 COCH2CH3

B.

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Solution
A. Methyl butanoate (methyl butyrate) B. Ethyl propanoate (methyl propionate)

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Learning Check
Write the structure of the following esters: A. Ethyl pentanoate

B. Propyl butyrate

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Solution
A. Ethyl pentanoate O CH3CH2CH2CH2COCH2CH3 B. Propyl butyrate O CH3CH2CH2COCH2CH2CH3

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Chapter 16 Carboxylic Acids and Esters

16.5 Properties of Esters

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Acid Hydrolysis of Esters

In acid hydrolysis An ester reacts with water to produce a carboxylic acid and an alcohol. An acid catalyst is required. O H+ HCOCH2CH3 + H2O
O HCOH

+ HOCH2CH3
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Base Hydrolysis (Saponification)

Base hydrolysis (also called saponification) Is the reaction of an ester with a strong base. Produces the salt of the carboxylic acid and an alcohol. O || CH3COCH2CH3 + NaOH O CH3CO Na+ + HOCH2CH3
salt of carboxylic acid alcohol

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Soaps
The base hydrolysis of long chain fatty acids produces acid salts called soaps.

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Cleaning Action of Soap

A soap Contains a nonpolar end that dissolves in nonpolar fats and oils, and a polar end that dissolves in water. Forms groups of soap molecules called micelles that dissolve in water and are washed away.
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Learning Check
Write the organic products when methyl acetate reacts with A. Water and an acid catalyst

B. KOH

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Solution
Write the organic products when methyl acetate reacts with: A. Water and an acid catalyst O CH3COH + HOCH3 B. KOH O CH3CO K+ + HOCH3

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