Chapter 13 Carboxylic Acids, Esters, Amines, and Amides
13.1 Carboxylic Acids
Copyright © 2005 by Pearson Education, Inc. Publishing as Benjamin Cummings
1 Carboxylic Acids
A carboxylic acid contains a carboxyl group, which • is a carbonyl group (C=O) attached to a hydroxyl group (—OH). • is found on carbon 1 in carboxylic acids.
O
CH3 — C—OH hydroxyl group or CH3COOH carbonyl group
2 Models of Carboxylic Acids
The three-dimensional models show the geometry of atoms in carboxylic acid molecules.
3 IUPAC Names
The IUPAC names of carboxylic acids: • Replace the -e in the alkane name with -oic acid.
CH4 methane HCOOH methanoic acid CH —CH ethane CH —COOH ethanoic acid 3 3 3 • Number substituents from the carboxyl carbon 1.
CH3 O | ║ CH3—CH—CH2—C—OH 4 3 2 1 3-methylbutanoic acid
4 Names and Sources of Some Carboxylic Acids
5 Common Carboxylic Acids
Methanoic acid (formic acid) O ║ H─C─OH
ethanoic acid (acetic acid) O ║
CH3─C─OH
6 Aromatic Carboxylic Acids
O Benzoic acid • is the aromatic C OH carboxylic acid. benzoic acid
O O
• locates substituents C OH C OH by numbering the ring from carbon 1 in the carboxyl group. Cl NH2 3-chlorobenzoic acid 4-aminobenzoic acid
7 Learning Check
Give the IUPAC names of each compound.
A. CH3─CH2─COOH propanoic acid
CH3 | B. CH3─CH─CH2─COOH 3-methylbutanoic acid C. O
C OH 3-bromobenzoic acid
Br
8 Chapter 13 Carboxylic Acids, Esters, Amines and Amides
13.2 Properties of Carboxylic Acids
Copyright © 2005 by Pearson Education, Inc. Publishing as Benjamin Cummings
9 Polarity of Carboxylic Acids
Carboxylic acids
• are strongly polar.
• have two polar groups: hydroxyl (−OH) and carbonyl (C=O).
10 Polarity of Carboxylic Acids
Carboxylic acids • form dimers in which hydrogen bonds form between two carboxyl groups.
O H—O || | CH3—C C—CH3 | || O—H O A dimer of acetic acid
• have higher boiling points than alcohols, ketones, and aldehydes of similar mass.
11 Comparison of Boiling Points
Compound Molar Mass Boiling Point O ║
CH3−CH2−C−H 58 49 C
CH3−CH2−CH2−OH 60 97 C
O ║
CH3−C−OH 60 118 C
12 Solubility in Water
Carboxylic acids: Water molecules • form hydrogen bonds with many water molecules.
• with 1-4 carbon atoms are very soluble in water.
13 Boiling Points and Solubility
14 Acidity of Carboxylic Acids
Carboxylic acids • are weak acids. • ionize in water to produce carboxylate ions and hydronium ions. O O ║ ║ – + CH3−C−OH + H2O CH3−C−O + H3O
15 Neutralization of Carboxylic Acids
Carboxylic acid salts • are a product of the neutralization of a carboxylic acid with a strong base. – + CH3—COOH + NaOH CH3—COO Na + H2O acetic acid sodium acetate (carboxylic acid salt) • are used as preservatives and flavor enhancers.
16 Learning Check
Write the equation for the reaction of propanoic acid with:
A. water – + CH3—CH2—COOH + H2O CH3—CH2—COO + H3O
B. KOH – + CH3—CH2—COOH + KOH CH3—CH2—COO K + H2O
17 Chapter 13 Carboxylic Acids, Esters, Amines, and Amides
13.3 Esters
Copyright © 2005 by Pearson Education, Inc. Publishing as Benjamin Cummings
18 Esters
In an ester, the H in the carboxyl group is replaced with an alkyl group.
O
CH3 — C—O —CH3 ester group
19 Esterification
Esterification is the reaction of a carboxylic acid and alcohol in the presence of an acid catalyst to produce an ester. O H+
CH3—C—OH + H—O—CH2—CH3
O
CH3—C—O—CH2—CH3 + H2O ethyl acetate (an ester)
20 Learning Check
Write the equation for the reaction of propanoic acid and methanol in the presence of an acid catalyst. O H+
CH3—CH2—C—OH + H—O—CH3 propanoic acid methanol
O CH3—CH2—C—O—CH3 + H2O
21 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.
22 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. methyl ethanoate (acetate) O
CH3— O—C —CH3
IUPAC: methyl ethanoate common: methyl acetate
23 Esters in Plants
Esters give flowers and fruits their pleasant fragrances and flavors.
Copyright © 2005 by Pearson Education, Inc. Publishing as Benjamin Cummings
24 Learning Check
Give the IUPAC and common names of the following compound, which is responsible for the flavor and odor of pears. from 1-propanol O
CH3—C—O—CH2—CH2—CH3
Propyl ethanoate (IUPAC) Propyl acetate (common)
25 Learning Check
Draw the structure of the following compounds.
A. 3-bromobutanoic acid
Br | CH3—CH—CH2—COOH
B. ethyl propionoate O
CH3—CH2 —C—O—CH2—CH3
26 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+ H—C—O—CH2—CH3 + H2O
O H—C—OH + H—O—CH2—CH3
27 Base Hydrolysis (Saponification)
Base hydrolysis or saponification, • is the reaction of an ester with a strong base. • produces the salt of the carboxylic acid and an alcohol. O || CH3—C—O—CH2—CH3 + NaOH O – + CH3—C—O Na + HO—CH2—CH3 salt of carboxylic acid alcohol
28 Base Hydrolysis of Fatty Acids Produces Soaps
29 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.
30 Learning Check
Write the organic products when methyl acetate reacts with
A. water and an acid catalyst. O CH3—C—OH + HO—CH3
B. KOH. O – + CH3—C—O K + HO—CH3
31 Chapter 13 Carboxylic Acids, Ester, Amines, and Amides 13.4 Amines
32 Amines
Amines
• are derivatives of ammonia, NH3. • contain N attached to one or more alkyl or aromatic groups.
CH CH 3 3 N H 2
CH3—NH2 CH3—NH CH3—N—CH3
33 Classification of Amines
Amines are classified as primary, secondary, or tertiary. • In a primary (1°) amine, one carbon group is bonded to the nitrogen atom. • A secondary (2°) amine has two carbon groups bonded to the nitrogen atom. • A tertiary (3°) amine has three carbon groups bonded to the nitrogen atom.
H CH3 CH3 | | | CH3—N—H CH3—N—H CH3—N—CH3 1° 2° 3°
34 Models of Amines
The three-dimensional models show the shapes of amine molecules with one or more alkyl groups bonded to the nitrogen atom.
35 Naming Amines
Simple amines • are named as alkylamines. • List the names of the alkyl groups bonded to the N atom in alphabetical order in front of amine.
CH3—CH2—NH2 ethylamine
CH3—NH—CH3 dimethylamine CH3 |
CH3—N—CH2—CH3 ethyldimethylamine
36 Learning Check
Give the common name and classify as primary, secondary, or tertiary.
A. CH3—CH2—CH2—NH2 propylamine, 1°
CH3 |
B. CH3—CH2—N—CH3 ethyldimethylamine, 3°
37 Aromatic Amines
• The amine of benzene is named aniline. • Alkyl groups on the N use the prefix N- with alkyl name.
aniline 3-chloroaniline N-methylaniline
38 Learning Check
Give the common name of each compound.
A. CH3—NH—CH2—CH3 ethylmethylamine
CH3 |
B. CH3—CH2—N—CH2—CH3 diethylmethylamine
C. NH2 aniline
39 Hydrogen Bonding for Amines
The N−H bond • provides hydrogen bonding in 1°and 2° amines, but not in 3° amines. • is not as polar as the O-H bonds in alcohols.
40 Solubility in Water
Amines • with 1-5 carbon atoms are soluble in water. • form hydrogen bonds with the polar O-H bond in water.
41 Learning Check
Consider the following compounds:
1) CH3—CH2—CH2—NH2
2) CH3—CH2—NH—CH3
3) CH3—CH2—CH2—CH3
A. Which compound has the highest boiling point?
1) CH3—CH2—CH2—NH2
B. Which compound is soluble in water?
1) CH3—CH2—CH2—NH2 2) CH3—CH2—NH—CH3
42 Amines React as Bases
Like ammonia, amines are weak bases in water.
+ – NH3 + H2O NH4 + OH ammonium hydroxide
+ – CH3—NH2 + H2O CH3—NH3 + OH methylammonium hydroxide
43 Neutralization forms Amine Salts
An amine salt • forms when an amine is neutralized by acid. • is named by replacing the amine part of the name with ammonium followed by the name of the negative ion. + – CH3—NH2 + HCl CH3—NH3 Cl methylamine methylammonium chloride
44 Properties of Amine Salts
Amine salts are • solids at room temperature. • soluble in water and body fluids. • the form used for drugs.
45 Alkaloids
Alkaloids are • physiologically active nitrogen-containing compounds. • obtained from plants. • used as anesthetics, antidepressants, and in stimulants such as caffeine. • often addictive.
46 Cocaine
Cocaine is • sold illegally as the amine salt. • reacted with NaOH to produce the free amine form known as “crack.”
47 Caffeine
Caffeine • is a stimulant of the central nervous system. • is found in coffee beans, tea, chocolate, and soft drinks.
48 Nicotine
Nicotine • increases the adrenaline level in the blood. • causes addiction to tobacco.
N
C H 3
Morphine and codeine are • alkaloids. • obtained from the oriental poppy plant. • used as painkillers. • modified to make heroin.
50 Learning Check
Write the structural formula for
A methylpropylamine CH3–CH2–CH2–NH–CH3
B. 2-chloroaniline NH 2 Cl
51 Chapter 13 Carboxylic Acids, Esters, Amines, and Amides
13.5 Amides
Copyright © 2005 by Pearson Education, Inc. Publishing as Benjamin Cummings
52 Amides
In amides,
• an amino group(–NH2) replaces the –OH group of carboxylic acids. O O || || CH3—C—OH CH3—C—NH2
Copyright © 2005 by Pearson Education, Inc. Publishing as Benjamin Cummings
53 Aromatic Amide
The aromatic amine is benzamide.
O
C
NH2
benzamide
54 Preparation of Amides
Amides are produced • by reacting a carboxylic acid with ammonia or an amine (1 or 2 ). • using heat.
O O Heat CH3—C—OH + NH3 CH3—C—NH2 + H2O
O O Heat CH3—C—OH + CH3—NH2 CH3—C—NH—CH3 + H2O
55 Naming Amides
Amides are named as alkanamides. • IUPAC replaces –oic acid ending with –amide. • Common names replace -ic acid ending with –amide. O Methanamide (IUPAC)
H—C—NH2 Formamide (common)
O Propanamide (IUPAC)
CH3—CH2—C—NH2 Propionamide (common)
56 Naming Amides with N Groups
An alkyl group bonded to the N atom is named as N-alkyl in front of the amide name. O H │
CH3 —C—N—CH3 N-methylethanamide (IUPAC) N-methylacetamide (common) O H │
CH3—CH2 —C—N—CH2—CH3 N-ethylpropanamide (IUPAC) N-ethylpropionamide (common)
57 Learning Check
Give the IUPAC and common names for the following:
O
A. CH3–CH2–CH2–C–NH2 butanamide; butryamide
O H │
B. CH3–C–N–CH2–CH3
N-ethylethanamide; N-ethylacetamide
58 Learning Check
Draw the structures of:
A. pentanamide O
CH3–CH2–CH2–CH2–C–NH2
B. N-methylbutyramide O
CH3–CH2–CH2–C–NH–CH3
59 Some Amides in Health and Medicine
• Urea is the end product of protein metabolism. • Saccharin is an artificial sweetener. • Some amides such as phenobarbital, Nembutal and Seconal are barbiturates. • Acetaminophen is used to reduce fever and pain.
60 Some Amides in Health and Medicine
61 Physical Properties of Amides
Amides
• that are primary (−NH2) or secondary (−NH−) form hydrogen bonds. • that are primary have higher melting points than secondary. • that are tertiary (no H on N) do not form hydrogen bonds and have lower melting points. • all form hydrogen bonds with water. • with 1-5 carbon atoms are soluble in water.
62 Hydrogen Bonding of Amides
O || CH3—C—N—H | H Hydrogen bonding occurs between primary amides. O || CH3—C—N—H | H
63 Hydrolysis of Amides
Amides undergo
• Acid hydrolysis to produce a carboxylic acid and an ammonium salt.
• Base hydrolysis to produce the salt of a carboxylic acid and an amine or ammonia.
64 Hydrolysis Reactions
acid hydrolysis O || + – O CH3—C—OH + NH4 Cl || HCl + H2O CH3—C—NH2
NaOH O || – + CH3—C—O Na + NH3
base hydrolysis
65 Learning Check
Write the products of the hydrolysis of N-ethylpropanamide with NaOH.
O – + CH3—CH2—C—O Na + CH3—CH2—NH2
66