Chapter 13B Amines and Amides

13.4 Amines

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

Amines
Amines Are derivatives of ammonia NH3. Contain N attached to one or more alkyl or aromatic groups. CH3 CH3NH CH3 CH3NCH3
NH2

CH3NH2

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. A tertiary (3) amine has three carbon groups. H CH3 CH3 | | | CH3NH CH3NH CH3NCH3 1 2 3

Models of Amines
The three-dimensional models show the shapes of amine molecules with one or more alkyl groups bonded to the nitrogen atom.

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

Naming Amines: Common

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. CH3CH2NH2 CH3NHCH3 CH3 | CH3NCH2CH3 ethylamine dimethylamine

ethyldimethylamine

Naming Amines: IUPAC

In the IUPAC system, Amines are named as alkanamines. The e in the alkane name of the longest chain is changed to amine. The chain is numbered to locate the amine group and substituents. NH2 | CH3CH2NH2 CH3CHCH3 Ethanamine 2-Propanamine
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Naming Amines: IUPAC

2o or 3o amines
Number longest alkane chain

Alkyl grps bonded to N are named as N-alkyl grp

CH3CH2CH2NHCH3
3 2 1

HNCH3 | CH3CHCH2CH3
1 2 3 4

N-Methyl-1-propanamine

N-Methyl-2-butanamine

Learning Check
Give the common and IUPAC names, and classify as primary, secondary, or tertiary: A. CH3CH2CH2NH2

CH3 | B. CH3CH2NCH3

Solution
Give the common and IUPAC names, and classify as primary, secondary, or tertiary: A. CH3CH2CH2NH2 n-propylamine, 1-propanamine, 1 CH3 | B. CH3CH2NCH3 ethyldimethylamine, N,N-dimethylethanamine, 3
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Learning Check
Write a structural formula for A. 2-pentanamine

B.

N-methyl-1-butanamine

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Solution
A. 2-pentanamine NH2 | CH3CHCH2CH2CH3
N-methyl-1-butanamine CH3CH2CH2CH2NHCH3

B.

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Aromatic Amines
The amine of benzene is aniline. Alkyl groups on the N use the prefix N- and the alkyl name.

NH2

NH2

NH CH3

Cl
Aniline 3-chloroaniline N-methylaniline
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Learning Check
Give a name for each: A. CH3NHCH2CH3 CH3 | CH3CH2NCH2CH2CH2CH3
NH2

B.
C.

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Solution
A. CH3NHCH2CH3 ethylmethylamine; N-methylethanamine

CH3 | B. CH3CH2NCH2CH2CH2CH3 N-ethyl-N-methyl-1-butanamine C.

NH2

aniline

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Properties of Amines

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Boiling Points:
Alcohols > Amines >Alkanes
of similar mass.

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Hydrogen Bonding for Amines

The polar N-H bond Provides hydrogen bonding in 1and 2 amines, but not 3. In amines is not as polar as the O-H bonds in alcohols.

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Solubility in Water
Amines are soluble in water If they have 1-5 carbon atoms. Because the N atom in smaller amines forms hydrogen bonds with the polar O-H bond in water.

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Learning Check
Consider the following compounds: 1. CH3CH2CH2NH2 2. CH3CH2NHCH3 3. CH3CH2CH2CH3
A. Which compound has the highest boiling point?

B. Which compound(s) is(are) soluble in water?

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Solution
Consider the following compounds: 1. CH3CH2CH2NH2 2. CH3CH2NHCH3 3. CH3CH2CH2CH3 A. Which compound has the highest boiling point? 1. CH3CH2CH2NH2

B. Which compound(s) is(are) soluble in water? 1. CH3CH2CH2NH2 2. CH3CH2NHCH3

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Amines React as Bases

Amines are Bronsted-Lowry bases that attract a H+ from H2O to the N atom. Weak bases in water. NH3 + H2O NH4+ + OH
ammonium hydroxide

CH3NH2 + H2O

CH3NH3+ + OH
methylammonium hydroxide
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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. CH3NH2 + HCl
methylamine

CH3NH3+Cl
methylammonium chloride

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Properties of Amine Salts

Amine salts are Solids at room temperature. Soluble in water and body fluids. The form used for drugs.

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Cocaine
Cocaine Is sold illegally as an amine salt. Is reacted with NaOH to produce the free amine form known as crack.

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Learning Check
Write the equation for ethylamine when it reacts with each of the following: 1. + H2O

2. + HCl

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Solution
Write the equation for ethylamine when it reacts with each of the following: 1. CH3CH2NH2 + H2O 2. CH3CH2NH2 + HCl CH3CH2NH3+ OH CH3CH2NH3+ Cl

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Heterocyclic Amines and Alkaloids

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Heterocyclic Amines
A heterocyclic amine Is a cyclic organic compound. Has a five- or six-atom ring. Contains one or more nitrogen atoms.

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Examples of Heterocyclic Amines

N N H Pyrrolidine N H Pyrrole N H Imidazole N N H Piperidine N Pyridine N Pyrimidine N N Purine N N H

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Learning Check
Identify the following heterocyclic amines:
1. 2. 3.

N H

N H

N H

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Solution
Identify the following heterocyclic amines:
1. 2. 3.

N H
1. piperidine

N H
2. pyrrole

N H
3. imidazole

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Alkaloids
Alkaloids are Physiologically active nitrogen-containing compounds. Produced by plants. Used as stimulants, anesthetics, and antidepressants. Often habit forming.

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Caffeine
Caffeine Is a stimulant of the central nervous system. Is found in coffee beans, tea, chocolate, and soft drinks. Contains an imidazole ring.

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Nicotine
Nicotine Increases the adrenaline level in the blood. Causes addiction to tobacco. Contains a pyrrolidine ring.

N CH3
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Alkaloids Related to Morphine

Alkaloids Such as morphine and codeine are produced by the poppy. Have been used for centuries as painkillers. Such as heroin and codeine are modifications of morphine.

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Morphine and Codeine

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Pharmacology
An area of research in pharmacology Is to design drugs such as procaine, lidocaine, and demerol that retain some of the characteristics of alkaloids. Is to modify the structures of cocaine and morphine to produce anesthesia, but without the addictive side effects.

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Pharmacology

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Learning Check
Identify the heterocyclic amine in serotonin.

HO
serotonin

CH2 CH2 NH2

N H

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Solution
Identify the heterocyclic amine in serotonin.

CH2 HO N H

CH2
pyrrole

NH2

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Amides

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Preparation of Amides
Amides are prepared By reacting a carboxylic acid with ammonia or an amine (1 or 2). Using heat. O Heat CH3COH + NH3

O CH3CNH2 + H2O

O O Heat CH3COH + CH3NH2 CH3CNHCH3 + H2O

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Amides
In amides, an amino group(NH2) replaces the OH group of carboxylic acids. O O || || CH3COH CH3CNH2

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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) HCNH2 Formamide (common) O CH3CH2CNH2

Propanamide (IUPAC) Propionamide (common)

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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 CNCH3 N-methylethanamide (IUPAC) N-methylacetamide (common) O H CH3CH2 CNCH2CH3 N-ethylpropanamide (IUPAC) N-ethylpropionamide (common)
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Aromatic Amides
The amide of benzene is named benzamide.

O C NH2

O C NH CH3

Benzamide

N-methylbenzamide
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Learning Check
Give the IUPAC and common names for the following: O CH3CH2CH2CNH2 O H CH3CNCH2CH3

A.

B.

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Solution
O CH3CH2CH2CNH2 butanamide; butryamide

A.

B.

OH CH3CNCH2CH3 N-ethylethanamide; N-ethylacetamide

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Learning Check
Draw the structures of
A. B. pentanamide N-methylbutyramide

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Solution
A.

pentanamide O CH3CH2CH2CH2CNH2

B.

N-methylbutyramide O CH3CH2CH2CNHCH3

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Classification of Amides
Amides are classified according to the number of carbon atoms bonded to the nitrogen atom. O H || | CH3CNH Primary (1) amide O H || | CH3CNCH3

Secondary (2) amide

O CH3 || | CH3 CNCH3

Tertiary (3) amide

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Learning Check
Give the common and IUPAC names for the following amides and classify as primary, secondary, or tertiary: O || CH3CH2CH2CNH2

A.

B.

O CH3 || | CH3CNCH2CH3
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Solution
O || A. CH3CH2CH2CNH2 butryamide (common); butanamide (IUPAC) primary(1) amide
O CH3 || | CH3CNCH2CH3 N-ethyl-N-methylacetamide (common); N-ethyl-N-methylethanamide (IUPAC) tertiary (3) amide

B.

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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.

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Some Amides in Health and Medicine

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

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.

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Hydrogen Bonding of Amides

O || CH3CNH | H O || CH3CNH | H

Hydrogen bonding occurs between primary amides.

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Hydrolysis of Amides

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Hydrolysis of Amides
Amides undergo
acid hydrolysis base hydrolysis

carboxylic acid ammonium salt

salt of carboxylic acid and an amine or ammonia

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Hydrolysis Reactions
acid hydrolysis O || CH3CNH2

O || CH3COH + NH4+Cl
HCl + H2O NaOH O || CH3CO Na+ + NH3

base hydrolysis
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Learning Check
Write the equation for the hydrolysis of N-ethylpropanamide with NaOH.

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Solution
Write the products of the hydrolysis of N-ethylpropanamide with NaOH.
O CH3CH2CNCH2CH3 + NaOH N-ethylpropanamide

O CH3CH2CO Na+ + CH3CH2NH2

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