Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.1

Introduction Amines are organic derivatives of ammonia, NH3 Classification of Amines Primary amines
H N R H

Secondary amines Tertiary amines

H

N R

R'

R''

N R

R'

Chapter 19 : Amines

19.1 : Introduction 19. : omenclature

19. : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.1

Classify the following amines:
i. C
ii. C

C
C

C

1° °
C

Aliphatic amines

iii. C

C C

C

°

iv.

C

° 1°

v.

Aromatic amines

vi. C

C

°
C

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

IUPAC Nomenclature In primary amines, the suffix µamine¶ replaces the µe¶ in the name of the parent alkane
i. C 3 C 2 C 1 N

propane amine e

Secondary and tertiary amines are named as N-substituted derivatives of primary amines
ii


2 1

N-methylethane mine a e

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

Examples: Structure IUPAC Name Methanamine Methanamine 2-propanamine propanamine Cyclopentanamine Cyclopentanamine N-methylpentanamine methylpentanamine

C

N

2

CH 3 CH(NH 2 )CH 3
NH2

CH 3CH 2CHCH 2CH 3 NHCH 3
CH3 CH3CH2 N CH2CH3

N-ethyl-N-methyl ethylethanamine ethanamine

hapter 19 : Amines

19.1 : Introduction 19. : omenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : hemical properties

19.

IUPA omenclature When multiple functional groups are present and the ±NH2 group does not take priority, it is named as an ³amino´ substituent Examples:
2
4 3 2

1

OO
1

-aminoethanoic acid

O
,4-diaminophenol

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

IUPAC Nomenclature Aromatic amines are named as derivatives of aniline

N-ethyl-N-methylaniline ethyl-

Chapter 19 : Amines

19.1 : Introduction 19. : Nomenclature

19. : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.

Common Name Most primary amines are named as alkylamines Structure IUPAC Name methylamine methylamine

C
C
C
C

N
C N
C
N C

ethylamine ethylamine
N

C

propylamine propylamine dimethylamine dimethylamine

C

N C

C

methylethylamine methylethylamine

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19. : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19. Boiling point Solubility Basicity

(i) Boiling Point Both primary and secondary amines can form intermolecular hydrogen bonds.
H CH N HCH CH H CH NN CH H hydrogen bonds CH

CH

CH N H CH

CHN N H CH
CH

no hydrogen bond

hydrogen bonds

1° amines

° amines 2° amines

Tertiary amines cannot form hydrogen bonds to each other.

Examples: The table below compares the boiling points of isomeric amines. Amines Class Relative molecular mass Boliling points/oC

CH3CH2CH2NH2 NHCH3CH2-NH-CH3 CH3 | CH3-N-CH3

1° 2° 3°

59 59 59

49 37 4

Boiling Point : CH3CH2CH2NH2 > CH3CH2NH(CH3) > (CH3)3N

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

(i) Boiling Point Amines have higher boiling points than alkanes or haloalkanes of similar relative molecular mass due to intermolecular hydrogen bonding Example Amines have lower boiling points than alcohols or carboxylic acids of comparable molecular weight because
H- bond in RNH2 is weaker than the H- bond in ROH and RCOOH (Nitrogen is less electronegative than the Oxygen)

Examples: The table below compares the boiling points of organic compounds of comparable relative molecular mass.
Amines Type Relative molecular mass Boliling points/oC

CH3CH2CH2CH3 butane CH3CH2Cl chloroethane CH3CH2CH2NH2 1-propanamine

Alkane Haloalkane Amine

58 64.5 59

-0.5 12.5 48.6

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

(i) Boiling Point Amines have higher boiling points than alkanes or haloalkanes of similar relative molecular mass due to intermolecular hydrogen bonding Example Amines have lower boiling points than alcohols or carboxylic acids of comparable molecular weight because
H- bond in RNH2 is weaker than the H- bond in ROH and RCOOH (Nitrogen is less electronegative than the Oxygen) Example

Examples: The table below compares the boiling points of organic compounds of comparable relative molecular mass.
Amines Type Relative molecular mass Boiling points/oC

CH3CH2CH2CH3 butane CH3CH2Cl chloroethane CH3CH2 2NH2 CH3CH2CH2NH2 1-propanamine CH3CH2CH2 H 1-propanol CH3C H ethanoic acid

Alkane Haloalkane Amine Alcohol Carboxylic acid

58 64.5 59 60 60

-0.5 12.5 48.6 97.2 118

Boiling Point : Carboxylic acid > Alcohol > Amine > Haloalkane > Alkane

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

(ii) Solubility All amines including tertiary amines, are capable of forming hydrogen bonds with water molecules. Thus simple amines (amines of fewer than 5 carbons) are generally water soluble and dissolve to form basic aqueous solutions

Comparison the solubility between 1°,2° and 3°amine

The solubility :
1
O H N H O H H H O H H H
o

3° < 2 ° < 1 °
3o
O H H

Increasing o 2 solubility
O H R N R H O H H H

R

R

N R

R

: hydrogen bonds 2 hydrogen bonds per a 2° amine molecule 1 hydrogen bond per a 3° amine molecule

3 hydrogen bonds per a 1° amine molecule

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

Basicity  An amine is a nucleophile (a Lewis base base) because its lone pair of non-bonding electrons on nitrogen

H H N H
Ammonia

H

+ H

H

H

N

+

H+

H

-

H
Ammonium ion

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

Basicity ± (i) Inductive effect  An alkyl group is electron donating group, and it stabilises the alkylammonium ion by dispersing its positive charge
H N H H

+ H

H

N

+

H+

H

-

H

1° Amine Stabilised by the alkyl group

alkylammonium ion @Stronger base

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

H N H

H

+ H

H

N

+

H+

H

-

1° Amine

H alkylammonium ion
+

N H

+ H

H

N

H

+

H

2° Amine

H alkylammonium ion

Strength as a base : Methyl, 1°, 2°

Increasing

Chapter 19 : Amines

19.1 : Introduction 19. : omenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

Basicity ± (ii) esonance effect  Aromatic amines (e.g., aniline) are weaker bases than the corresponding aliphatic and cyclic amines
Example:

Cyclohexylamine pKb = 3.36

Aniline pKb = 9.42

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Boiling point Solubility Basicity

Basicity ± (ii) esonance effect Aromatic amines are less basic The lone pair electrons of nitrogen atom are delocalised and overlapped with the aromatic ring electrons system make it less available for bonding to H+
H H H H

arylamines are stabilised due to the 4 resonance structures

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 eduction of nitro compound eduction of nitriles eduction of amides Hoffmann¶s degradation of amides

eduction of nitro compounds 
Aromatic amines can be prepared by reduction of nitro compounds using Zn/H+ or SnCl2/H+

Zn/H+ or
N
2

SnCl2/H+

NH2 Aniline anline

nitrobenzene

hapter 9 : mines
9.3 : hysi al roperties

9. : Intro u tion 9. : reparation

9. :

omen lature

9.5 : hemi al properties

9. e u tion of nitro ompoun e u tion of nitriles e u tion of ami es offmann¶s egra ation of ami es

Reduction of nitriles 
Nitriles are reduced to primary amines by H2 / catalyst, LiAlH4 / H+ or NaBH4 / H+.

atalyst ( t

i

)

Example :
. i l .

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Reduction of nitro compound Reduction of nitriles Reduction of amides Hoffmann¶s degradation of amides

Reduction of amides 
Reduction of an amide using LiAlH4 / H+ or NaBH4 / H+ can yield a primary, secondary, or tertiary amine depending on the type of amide used
1. LiAlH 4 R C NH 2 2. H + H R C NH 2 + H 2 H

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Reduction of nitro compound Reduction of nitriles Reduction of amides Hoffmann¶s degradation of amides

Example :
i. CH3 C NH 2

H
1. LiAlH 4 2. H
+

CH3

C NH 2 + H2 H

Ethanamide (2o amide)

Ethanamine (1o amine) H CH 3 CH 3 C NH H
N-methylethanamine (2o amine)
+

ii. CH3

CH3 1. Na H 4 C NH 2. H
+

H2

N-methylethanamide (2o amide)

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Reduction of nitro compound Reduction of nitriles Reduction of amides Hoffmann¶s degradation of amides

Hoffmann¶s degradation of amides 
n warming a primary amide with bromine in solution of Na H, a primary amine is formed.  This reaction is used to synthesise primary alkyl and aryl amines.
Br , Na H R NH
amide

RNH
amine

+

-

H 

The elimination of carbonyl group is shortening the length of carbon chain by one carbon atom atom.

hapte 19 : Amines

19.1 : Int oduction 19. : omenclatu e

19. : Physical P ope ties 19.4 : P epa ation 19.5 : hemical p ope ties

19.4 Reduction of nit o compound Reduction of nit iles Reduction of amides offmann¶s deg adation of amides

Example :

-

+

-

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

Reaction with acyl chlorides 
1° and 2° amines are acylated to form N-substituted amides
H 2 R N H + Cl C CH 3
1 amine
o

H R N C CH 3
2o amide
+

RNH3 Cl -

+

Nitrous acid Bromine water
Formation of dye

R
2 R N H + Cl C CH 3 2o amine

R O R N C CH 3
3o amide
+
+ R2NH 2 Cl

- 

3° amines are not acylated because they do not have a H atom attached to N atom.

hapter 19 : Amines

19.1 : Introduction 19. : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : hemical properties

19.5 eaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

Reaction with acid anhydride 
1° and 2° amines are acylated to form N-substituted amides
H N H
1o amine
+

H

H3
acid anhydride

H3
+

N
o

H3
amide

H3

H

Nitrous acid
N H+

Bromine water
Formation of dye

H3
acid anhydride

H3
+

N
3o amide

H3 H

o

amine

H3 

3° amines are not acylated because they do not have a H atom attached to N atom.

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

Reaction with benzenesulphonyl chloride Hinsberg¶s test 
This reaction is used to differentiate between 1°, 2° and 3° amines.

Nitrous acid Bromine water
Formation of dye

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

1° amines amines 
Benzenesulphonyl chloride reacts with a 1° amine to form a white precipitate (N-substituted sulphonamides)Acidic hydrogen
H R-N-H 1o amine
+

O Cl-SO Na O R-N -S-

OH

H O R-N -S-

(-HCl)

Nitrous acid Bromine water
Formation of dye

O N-substituted benzenesu phonamides (precipitate) 

N-substituted sulphonamides have an O acidic hydrogen, N-H.NaOH water soluble salt  Therefore, it dissolve in aqueous NaOH.
(clear solution)

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

2° amines amines 
Benzenesulphonyl chloride reacts with a 2° amines to form a white precipitate (N,N-disubstituted sulphonamide)
R' R-N-H 2 amine
o
+

O Cl-SO

OH

R' O R-N -SO N,N- is stituted benzenesulphonamides ( recipitate)

(-HCl)

Nitrous acid Bromine water
Formation of dye 

N,N-disubstituted sulphonamides do not No react on Na have an acidic hydrogen, N-H.H  Therefore, it dissolve in aqueous NaOH.

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

3° amines amines 
3° amine do not gives visible reaction with benzenesulphonyl chloride

Summary of Hinsberg¶s test:
NaOH

1° amines solution 2° amines dissolved 3° amines

white precipitate white precipitate

clear
NaOH

Nitrous acid Bromine water
Formation of dye

do not

do not give any visible change

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

Reaction with nitrous acid (NaNO2 + HCl) 
Nitrous acid (HNO2) is a weak and unstable acid.  It is always prepared in situ, by treating cold sodium nitrite (NaNO2) with an aqueous solution of a cold dilute hydrochloride acid (-5°C).  Nitrous acid reacts with all classes of amines

Nitrous acid Bromine water
Formation of dye

Nitrous acid test can be used to distinguish: ‡ 1° aliphatic and 1° aromatic amines ‡ 1° and 2° aliphatic amines

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

1° amines (Aliphatic) amines 
Primary aliphatic amines react with nitrous acid to yield highly unstable aliphatic diazonium salts
H R-N-H 1 amine
o

NaNO2, HX -5 to 0 C
o

+

[ R-N

NX ]

-N2

R

+ +

X

Nitrous acid Bromine water
Formation of dye Observation :

aliphatic diazonium salt (unstable)

carbocation

Formation of gas bubbles (N2)

C=C

+

ROH

+

RX

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

1° amines (Aromatic) amines 
Primary arylamines react with nitrous acid to give arenediazonium salts
N
2

N2 Cl
NaNO2, HCl

cold

+ NaCl + H2O

Nitrous acid Bromine water
Formation of dye

arenediazonium salt

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

1° aliphatic amines and 2° aliphatic amines Primary aliphatic amines Secondary aliphatic amines Form a mixture of alkenes, alcohols, alkyl halides and nitrogen gas. Form secondary Nnitrosamines as yellow oil, which is stable under the reaction conditions.

Nitrous acid Bromine water
Formation of dye

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

Reaction with bromine water

Identification test Aniline reacts with aqueous bromine to yield white precipitates NH2 group is an activating and orthopara directors group
NH2 3Br2(aq) Br NH2 Br

Nitrous acid Bromine water

room temperature Br

+

3HBr

Formation of dye

(2,4,6-tribromoaniline) Observation: White precipitate formed

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride

Formation of dye Primary arylamines react with nitrous acid to give arenediazonium salts which are stable at 0 rC Arenediazonium salts also undergo coupling reaction with aromatic compounds with strong electron donating group, such as ±OH and ±NR2 at the para position to yield azo compounds Azo compounds are usually intensely coloured and relatively inexpensive compounds, they are used as dyes

Nitrous acid Bromine water
Formation of dye

Chapter 19 : Amines

19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with : Acyl chloride Acid anhydride
Benzenesulphonyl chloride
N N: X
+

OH

N=N (orange)

OH

CH3 N CH3 N=N (yellow)

CH3 N CH3

Nitrous acid Bromine water
Formation of dye

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