Acid Chlorides

An activated form of the carboxylic acid.

Chloride is a good leaving group, so
undergoes acyl substitution easily.
To synthesize acid chlorides use thionyl
chloride or oxalyl chloride with the acid:

O O
O O C Cl
C OH
+ C C + HCl + CO + CO2
Cl Cl

=>
Esters from Acid Chlorides
Acid chlorides react with alcohols to give
esters in good yield.
Mechanism is nucleophilic addition of the
alcohol to the carbonyl as chloride ion
leaves, then deprotonation:
O O
CCl COCH3
+ CH3OH + HCl
=>
Diazomethane
CH2N2 reacts with carboxylic acids to
produce methyl esters quantitatively.
Very toxic, explosive. Dissolve in ether.

O O

C OH C OCH
+ CH2N 2 3 + N2

=>
Amines
Amines are organic compounds in which
one or more H in ammonia, NH3, is
replaced with alkyl or aromatic groups:

H H H

H N H R N H R N R
ammonia
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

H3C N H H3C N H H3C N CH3

Primary amine Secondary amine tertiary amine

Common Names of Amines

Simple amines are named as

alkylamines.

The alkyl groups bonded to the N atom

are listed in alphabetical order in front
of amine.
 CH 3
H
H 3C CH 2 NH 2 H 3C N CH 3 H 3C N CH 3

ethylamine dimethylamine
trimethylamine
(primary amine) (secondary amine)
(tertiary amine)

CH 3

H 3C N CH 2 CH 3

ethyldimethylamine
(tertiary amine)
IUPAC Names of Amines
In the IUPAC system, amines are named
as alkanamines.
The e in the alkane name of the longest
chain is changed to amine.
NH2

H3C CH2 NH2 H3C CH CH3

ethanamine 2-propanamine
 NH2 NH2

H3C CH2 CH CH2 CH3 H3C C CH3

3-pentamine CH3

2-methyl-2-propanamine

CH3

H3C CH2 C CH2 CH2 CH2 NH2

CH3
4,4-dimethylhexan-1-amine
 CH 3

H 3C CH 2 C CH 2 CH 2 CH 2 NH 2

CH 3

4,4-dimethylhexan-1-amine

NH 2

cyclohexylamine
Naming of Secondary and Tertiary
Amines

Each alkyl groups bonded to the N atom

is named as N-alkyl groups in front of
the amine name for the longest chain.
 HN CH 3
H
H 3C CH 2 CH 2 N CH 3
H 3C CH CH 2 CH 3
N-methyl-1-propanamine
N-methyl-2-butanamine

H
H 3C CH 2 CH 2 N CH 2 CH 3

N-ethyl-1-propanamine

CH 3

H 3C N CH 2 CH 2 CH 2 CH 3

N,N-dimethylbutan-1-amine
 H3C CH3
N

H3C CH2 CH2 C CH2 CH3

N
H3C CH3

N,N,N',N'-tetramethylhexane-3,3-diamine

H3C CH3
N

CH3 CH2 C CH2 CH2 CH3

H

N,N-dimethylhexan-3-amine
or
3-(N,N-dimethylamino)hexane
 O
HN CH 3
H 3C CH 2 CH C H

N
H 3C CH 3

N-methylcyclohexylamine 2-(dimethylamino)butanal
Aromatic Amines
The amine of benzene is named aniline:
CH3
NH2
N
CH3

aniline N,N-dimethylaniline

NH2

Cl

3-chloroaniline
Boiling Points of Amines,
Alcohols, and Alkanes

The boiling points of amines are higher

than alkanes, but lower than alcohols
of similar mass:
Hydrogen Bonding for
Amines

The polar N-H bond provides hydrogen

bonding in 1and 2 amines, but not 3.

However, the N-H bonds in amines are

not as polar as the O-H bonds in
alcohols.
Hydrogen bonds in amines
Solubility in Water
Amines with 1-5 carbon atoms are
soluble in water.

The N atom in amines forms hydrogen

bonds with the polar O-H bond in water.
Hydrogen bonds in aqueous solutions of
amines
Learning Check
Consider the following compounds:
1) CH3CH2CH2NH2
2) CH3CH2NHCH3
3) CH3CH2CH2CH3
A. Which compound has the highest
boiling point?
B. Which compound is soluble in
water?
Solution
A. Which compound has the highest
boiling point?
1) CH3CH2CH2NH2

B. Which compound is soluble in water?

1) CH3CH2CH2NH2
2) CH3CH2NHCH3
Amines React as Bases
Amines are basic, weak bases, like
ammonia in water:
NH3 + H2O NH4 OH
ammonium
hydroxide

H3C NH2 + H2O H3C NH3 OH

methylammonium
hydroxide
Neutralization forms Amine
Salts
An amine salt will forms when an amine
is
neutralized by acid.

For this reason amines consider basic as

ammonia.
Is named by replacing the
amine part of the name with
ammonium followed by the
name of the negative ion.

H3C NH2 + HCl H3C NH3 Cl

methylamine methylammonium
chloride
Properties of Amine Salts
Amine salts are:

- Solids at room temperature.

- Soluble in water and body fluids.
- The form used for drugs.
Heterocyclic Amines
In a heterocyclic amine, a five- or six-
atom ring contains one or more nitrogen
atoms:
 N

N N N
H H H
Pyrrolidine Pyrrole Imidazole

N
N N

N N N
N N
H
H
Piperidine Pyridine Pyrimidine Purine

CH 2 CH 3

N-ethylpyrrolidine
Alkaloids
Alkaloids are:
Physiologically active nitrogen-
containing compounds.
Produced by plants.
Used as stimulants, anesthetics, and
antidepressants.
Caffeine
Is a stimulant of
the central
nervous system.
Is found in coffee
beans, tea,
chocolate, and soft
drinks.
Contains an
imidazole and
pyrimidine rings.
Nicotine
Increases the adrenaline, is a
hormone made by the adrenal gland,
level in the blood.
Causes addiction to tobacco.
Contains a pyrrolidine ring.

N
CH3
 Alkaloids such as morphine and
codeine are produced by the poppy.
For centuries, morphine and codeine
have been used as painkillers.
Heroin is a modification of morphine.
To maker it easier to administer
alkaloidal drugs in the dissolved state,
they are often prepared as their water-
soluble amine salts. Morphine, for
example, a potent sedative and
painkiller, is often given as morphine
sulfate, the salt of morphine and sulfuric
acid. Codeine, sometimes used in cough
medicines, is often present as codeine
phosphate.