I.

Heteroaromatic compounds,
Organic halogen compounds
II. ALCOHOLS, PHENOLS ETHERS
Introduction
• General formula: CnH2n+1OH R-OH

• That is: aliphatic and aromatic compounds

containing a hydroxyl (OH) group.

• R = alkyl, substance is an alcohol.

• R = aryl, substance is a phenol.

Alcohols
• Major importance in biological processes.
• OH is one of the most important functional
groups in naturally occurring molecules.

• Carbohydrates (and their derivatives)

• Some amino acids

• Many steroids, terpenes and

pigments
Primary, secondary and tertiary
A chain of carbon atoms can be represented by R when
drawing the structure. This is referred to as an R group.

 Primary (1°) alcohols have one

R group attached to the carbon to
which the OH group is attached.

 Secondary (2°) alcohols have two

R groups attached to the carbon to
which the OH group is attached.

 Tertiary (3°) alcohols have three

R groups attached to the carbon to
which the OH group is attached.
Alcohols - Forces between
molecules
• Alcohols (like water) contain an OH group that can make
a hydrogen bond to other polar groups.

• Hydrogen bonding requires:

• a lone pair
• a polarised bond

 -
R O  +

H
Alcohols - Polarised bond

Region of negative
character.

R O
H Region of positive
character.

Polarised bond
due to electronegativity
differences.
 Alcohols – Hydrogen bridge

O R etc.
H
H
R O O
H R
H
O
R
A network builds up
etc. which needs energy to
break apart.
Alcohols and hydrogen bonding
The presence of the hydroxyl
group with its electronegative
oxygen atom means that
alcohols are polar. They can
therefore take part in
hydrogen bonding.

Hydrogen bonding between alcohol molecules means that

an alcohol’s boiling point is higher than that of an alkane of
similar molecular mass. For example, methanol (Mr = 32)
boils at 64.7 °C but ethane (Mr = 30) boils at -88.6 °C.

Alcohols can mix with water because their molecules can

form hydrogen bonds with water molecules.
 Alcohols - Boilingpoints
150
117
100 97
78
65
50
36
BP
0 0

30 32 44 46 58 60 72 74 Mol. Wt.
-42
-50
Boiling Pt.
-88 (Alkane)
-100 Boiling Pt.
(ROH)
Alcohols – Water solubility
10
1-butanol
8
6 Water
Solubility
4 (g/100 ml)
1-pentanol
2 1-hexanol
1-heptanol
0
10
1

Number of carbon atoms in molecule

Comparison of Alcohols with Alkanes
bp Solubility
Formula Name MW (°C) in Water
CH 3 OH methanol 32 65 infinite
CH 3 CH 3 ethane 30 -89 insoluble
CH 3 CH 2 OH ethanol 46 78 infinite
CH 3 CH 2 CH 3 propane 44 -42 insoluble
CH 3 CH 2 CH 2 OH 1-propanol 60 97 infinite
CH 3 CH 2 CH 2 CH 3 butane 58 0 insoluble

HO ( CH 2 ) 4 OH 1,4-butanediol 90 230 infinite

CH 3 ( CH 2 ) 4 OH 1-pentanol 88 138 2.3 g/100 g
CH 3 ( CH 2 ) 4 CH 3 hexane 86 69 insoluble

Hydrogen bonds profoundly affect physical properties

Alcohols - Synthesis
• Hydrolysis of alkyl halides:
- + Br -
H O C Br H O C

• Hydration of alkenes:
H H H2SO4
C C + H2O CH3 CH2 OH
H H
Alcohols can be made via reduction
• Carboxylic acids and aldehydes give
primary alcohols.
O
CH3 C
OH LiAlH 4
CH3 CH2 OH
O
CH3 C
H

• Ketones produce secondary alcohols:

O OH
LiAlH 4
CH3 C CH3 CH CH3
CH3
Making wine and cider
Alcohol has been produced
by fermentation of sugars
for thousands of years.

Sugar from fruit or grains

such as wheat and barley is
mixed with yeast and water,
which produces ethanol and
other compounds.

C6O6H12 2 C2H5OH + 2 CO2

 Alcohols –Chemical properties
• In dilute aqueous solution, alcohols are weakly
acidic
+
-
CH 3 O-H + O H CH 3 O + H O H
H H

[CH 3 O - ] [H 3 O +
]
Ka = = 15.5
CH3CH2 - OH [CH 3 OH] CH3CH2 - O

ethanol pKa ~ 16 ethoxy anion

Ethoxy anions cannot undergo resonance stabilization.

 Acid Strength

Compound Formula pKa

hydrogen chloride HCl -7 Stronger
acid
acetic acid CH 3 CO2 H 4.8

methanol CH 3 OH 15.5
water H2 O 15.7

ethanol CH 3 CH2 OH 15.9

2-propanol (CH 3 ) 2 CHOH 17
Weaker
2-methyl-2-propanol (CH 3 ) 3 COH 18 acid
Alcohols – Chemical Reactions
• Dehydration
H2SO4
C C C C + H2O
180° C
H OH

• Esterification (with inorganic acids)

CH 3 CH 3
CH 3 COH + HCl 25°C CH 3 CCl + H2 O
CH 3 CH 3
• Ether formation
2-Methyl-2- 2-Chloro-2-
propanol methylpropane
CH3-OH + Cl-CH3 CH3-O-CH3 + HCl
 Oxidation of alcohols
CH3 OH OX. H C H OX. H C OH
O O

methanol  methanal  methanoic acid 

CH3 CH2 OH OX. CH3 C H OX. CH3 C OH
O O
ethanol  H C H
ethanal  H ethanoic
C OH acid
O O
primary alcohol aldehyde carboxylic acid

H OX.
CH3 C CH3 CH3 C CH3
OH O
2-propanol propanone

secondary alcohol ketone

Phenols
• Molecules where the hydroxyl group is
bound to an aromatic ring are phenols.
• Phenols display similar hydrogen bonding
properties as alcohols.
• The OH bond is polarised, solubility and
boiling point are affected.
• The simplest phenol is phenol itself.
OH
 Phenol Derivatives

OH OH OH
Cl

CH3
OH

o-chlorophenol m-cresol hydroquinone

Most often they are designated by trivial names

 Phenols - Properties
• Phenols differ from alcohols as they are slighty acidic.

• A solution of phenol in water is known as Carbolic Acid.

• This was used 130 years ago by Lister to kill bacteria.

• Lister’s use of this antiseptic revolutionised surgery.

Phenols -Acidity
• Phenols are slightly acidic.
• pKa for phenol is about 10.

OH O

H +
 Stability of the phenolate anion
O O O O

O  -

- -

-
The phenolate anion is stabilized by the delocalization of the negative
charge.
Comparison of Alcohols with Phenols

Phenols are stronger acids than the alcohols

 Effect of other substituents on
the acidity of phenols

Electron withdrawing groups increase acidity

Phenols - Reactions

• Reaction with a base

-
OH O Na+

NaOH
H2O +

The product is a salt, sodium phenolate

Oxidation of phenols
OH O
OH O
OX.

1,2-dihydroxybenzene 1,2-benzoquinone
OH O

OX.

OH O
1,4-dihydroxybenzene 1,4-benzoquinone

phenol quinone
II. THIOLS
 First Things First: Thiols Smell Bad

Open a textbook that discusses thiols and one of the first things they’ll mention is their vile
stench. Hydrogen sulfide (H2S) is responsible for the smell of rotten eggs and bad breath,
among other unpleasant things. Thiols contribute to the smell of skunks and “skunky” beer.

Thiols Are More Acidic Than Alcohols

We’ve seen that alcohols are relatively acidic (pKa’s of about 16-17). Thiols are more
acidic than alcohols by an average of about 5 pKa units or so ( pKa of about 11 for the thiol
pictured below). Remember that pKa is logarithmic, so that means they’re about 105 times
more acidic.
Why might that be?

When understanding acidity trends it greatly helps to think about the stability of the conjugate base. In the case of sulfur,
the negative charge will be borne on a larger atom (sulfur > oxygen) and that negative charge dispersed over a greater
volume. Greater volume = more diffuse charge = greater stability.
III ALDEHYDES, KETONES
AND QUINONES
ALDEHYDES, KETONES AND QUINONES
Functional group: carbonyl group
C
O
O
ALDEHYDE R C carbonyl group is attached to a
H primary carbon

O O O
CH3 CH2 CH2 C CH2 CH C C
H H H

KETONES R CH2 C CH2 R’ carbonyl

carbonyl group
group bridges
bridges
secondary
secondary carbons
carbons
O
O

carbonyl group is within a

QUINONES ring structure attached to
sp2 hybridized carbons
O
 Structure and polarization of the carbonyl group
H
C O lone pairs

H
C s-bond O lone pairs

H
p-bond

Electronegativity: O > C
H + -
C O
H m Polar chemical bond
 ALDEHYDES

Soluble in water: forms hydrogen bonding with

water since the polarized carbonyl oxygen can
serve as a „hydrogen acceptor”

H + -
C O aldehyde-water
+
H H -
stronger acceptor
stronger H-bond
O
H
+
 Comparision of the physical properties of
aldehydes with alkanes and alcohols
London forces- Dipole-dipole interactions

CH3 CH3
H H
CH3 CH3 + C O- + C O-
H H
-89 oC -21 oC

H-bond -
+ O CH3
H - H
+
O
CH3 65 oC
THE TYPE AND MECHANISM FOR REACTIONS OF THE
CARBONYL GROUPS
NUCLEOPHILIC ADDITION (AN)
The double The oxygen is nucleophilic (partially
bond is negative) and tends to associate with
„unsaturated”, electrophilic (E: positively polarized
therefore it or charged molecules or atoms)
tends to add
reactants.
+ -
C O
The carbon is electrophilic (partially
positive) and tends to associate with
nucleophils (Nu: negatively polarized or
charged molecules or atoms)

The general mechanism:

+ + - Nu
C O- + E Nu C
OE
THE REACTIVITY OF CARBONYL GROUP

nucleophilic
at oxygen
electrophiles H+ or E+
add here
.. - .. -
O: :O :
+
C C
+
nucleophiles
attack here
Nu:
electrophilic
at carbon
Nucleophilic Addition to Carbonyl
Basic or Neutral Solution

.. _
.. :O:
O: an
+
-:Nu slow
C
alkoxide
C ion
Nu
.. _ ..
:O: :O H
fast
C + H2O C

Nu or an adding acid Nu

Good nucleophiles and strong bases

(usually charged)
 Nucleophilic Addition to Carbonyl
Acidic Solution: Acid Catalyzed
+ more reactive to
.. :O H
O: fast addition than the un-
+
+ H C protonated precursor
C

..
.. + :O H
O H slow
+ C
C :Nu

Nu
(+)

Acid catalysis speeds the rate of

addition of
- weak nucleophiles and
- weak bases (usually uncharged).
 Addition of Cyanide: :C N:
Buffered to pH 6-8
.. _
:O : :O :
_
R C R + CN R C R

CN
.. _ ..
:O : :O H

R C R + H2O R C R

CN CN
a cyanohydrin

In acid solution there would be little CN-,

and HCN (g) would be a problem (poison).
 Addition of Water

O O H
+
H
C + H 2O R C R'
R R'
O H
aldehyde or ketone
favored a hydrate

hydrates are unstable

most hydrates revert to an aldehyde and cannot be isolated
or ketone as soon as they form in most cases
O H
O
R C R' + H 2O
C
R R'
O H
 WATER ADDS TO THE CARBONYL GROUP OF
ALDEHYDES AND KETONES TO FORM HYDRATES
H catalyzed by a
+ trace of acid
O H
.. H .. .. ..
+ H H H
:O :O :O :O
C C
O+ :O a hydrate
.. H .. H .. H
O H
.. .. H
H O H
H
.. +
O H
H ..

for most compounds the equilibrium

favors the starting materials
and you cannot isolate the hydrate
 ACID CATALYSIS

RECALL
H
+
O
..
H
.. H + ..
:O :O H :O H

Acid catalysis enhances the reactivity :Nu

of the carbonyl group - nucleophilic
weak nucleophiles
addition proceeds more easily.
can react
 SOME STABLE HYDRATES
these also indicate that hydrates are possible

-
Cl O Cl OH
Cl C Cl C OH
- +Cl H
Cl H
chloral chloral hydrate
-

OH
O
OH
 Addition of Alcohols
TWO MOLES OF ALCOHOL WILL ADD

addition of one mole

O O H
H+
R C R' + ROH R C R' hemiacetal
O R
addition of second mole
O H O R
H+
R C R' + ROH R C R' + H O
O R O R H
an acetal
 ACETALS AND HEMIACETALS

R R OH ROH R OR
ROH
C O C C
OR OR
H aldehyde H H

hemiacetal acetal

R R OH ROH R OR
ROH
C O C C
OR OR
R ketone R R
(hemiketal)* (ketal)*
*older term *older term
 R OH + H 2S O4 R O H Like a
+ hydronium
H ion
R
H O
+
.. .. H + ..
:O :O H :O H

R C R R C R R C R
.. O+
O H .. R
H .. R ..
first R O
:
addition H
.. H
ACID CATALYZED :O H
FORMATION OF A
R C R + R O+
HEMIACETAL .. H
:O
..
hemiacetal R
 Cyclization of Monosaccharides
only sugars seem to make
stable hemiacetals a hemiacetal
O OH
H
1
H C 1C

2 2
H OH H OH

3 3 :O:
HO H HO H

4 4
H OH H OH
5
.. 5
H O H
..
6 H 6
CH2 OH CH2 OH

glucose glucopyranose
 Addition of N-Nucleophiles
- Formation of an imine occurs in two steps: addition
followed by elimination

•• ••
(1) addition
•• H
••

O -

••
••
O H

••
O
•• (1) + (1) ••
C + H2 N- R C N -R C N -R
H H
TCAI
addition product
•• H
••

O
•• (2) •• ••
N -R

••
C C N + H2 O
R
H a Schiff-base
(2) elimination
 Addition of N-Nucleophiles
Ammonia, 1° aliphatic amines, and 1° aromatic amines react with the
C=O group of aldehydes and ketones to give imines (Schiff bases)

O +
H
CH3 CH + H2 N CH3 CH =N + H2 O

Ethanal Aniline An imine

(A S chiff base)

+
H
O + H2 NCH 3 NCH 3 + H2 O

Cyclopent- Methylamine An imine

anone (a S chiff base)
 Keto-Enol Tautomerism
A carbon adjacent to a carbonyl group is called an a-carbon, and a
hydrogen atom bonded to it is called an a-hydrogen.

a- hydrogens

O
CH3 - C- CH2 - CH3
a- carbons
A carbonyl compound with an a-hydrogen is in equilibrium with a
constitutional isomer called an enol (an alkene + an alcohol)

O OH
CH3 - C- CH3 CH3 - C= CH2
Acetone Acetone
(keto form) (enol form)
STABILITY OF THE KETO-ENOL FORMS
 STABILIZING AN ENOL FORM

CH3 C CH2 C CH3 CH3 C CH C CH3

O O OH O
24% 76%

H Conjugated double bond

O O plus H-bond formation with a
six-membered ring
stabilize the enol form
C C
CH3 CH CH3
 Acidity of a-Hydrogens
Hydrogens alpha to a carbonyl group are more acidic
than hydrogens of alkanes, but less acidic than the
hydroxyl hydrogen of an alcohol

Type of Bond pK a
CH3 CH2 O-H 16
O
CH3 CCH2 -H 20

CH3 CH2 -H 51
 Acidity of a-Hydrogens
a-Hydrogens are more acidic because
- the electron-withdrawing inductive effect of the
adjacent carbonyl group weakens the C-H bond and
- resonance delocalization of the negative charge
stabilizes the resulting anion

O
CH3 - C-CH2 - H + A-

O O -

CH3 - C-CH2 CH3 - C= CH2 + H- A

Resonance-stabilized enolate anion

 Enolate Anions
- enolate anions function as nucleophiles in
carbonyl addition reactions
•• - •• ••
•• -
••
••

••

••
••
O O

••
O nucleophilic
addition C
R + C R
R R
R R R
R R R
An enolate A ketone A tetrahedral carbonyl
anion addition intermediate

- the special value of this reaction is that it results in

formation of a new C-C bond
 The Aldol Reaction

O H O
N aOH
CH3 - C-H + CH2 - C-H
Ethanal Ethanal
(Acetaldehyde) (Acetaldehyde) O
OH a

CH3 - CH- CH 2 -C- H
3-Hydroxybutanal
(a -hydroxyaldehyde)

The product of an aldol reaction is a -hydroxyaldehyde

 QUINONES
Oxidation-reduction:

VITAMIN K
Structure: 2-methyl 1, 4 naphtoquinone
derivative
IV. NITROGEN-CONTAINING ORGANIC
COMPOUNDS

AMINES and
N-containing Heterocyclic compounds
The Effect of Nonbonding Electrons and
Multiple Bonds on Bond Angles

By experiment, the H-X-H bond angle decreases

on moving from C to N to O:
H
C O
H H H N H H
H H H
109.5O 107O 104.5O
Since electrons in a bond are attracted by two nuclei,
they do not repel as much as lone pairs.
Therefore, the bond angle decreases as the number of
lone pairs increase.
 ..
Ammonia N The structure
H
H R 107o
H of amines
H
Amines:
.. .. ..
N N N
R1 R1 R1
~107o ~107o
~107o
H H R3
H R2 secondary R2
primary tertiary
R4

N
A -
R1
~109.5o
quaternary R3
R2
• Amines are classified as
• Primary (1°), secondary (2°), or tertiary (3°) amines:
amines in which 1, 2, or 3 hydrogens of NH3 are
replaced by alkyl or aryl groups
• Quaternary amines (4o): ions in which nitrogen is
bonded to four carbons and bears a positive charge

CH3 CH 3 -
+ Br
CH 3 - NH 2 CH3 - N CH3 - N- CH3
CH3 CH 3
Methylamine Trimethylamine Tetramethylammonium
(a 1° amine) (a 3° amine) bromide
(a 4° ammonium salt)
• Amines are further divided into aliphatic, aromatic, and
heterocyclic amines.
• aliphatic amines: amines in which nitrogen is bonded
only to alkyl groups
• aromatic amines: amines in which nitrogen is bonded
to one or more aryl groups

CH 3 CH3
N H2 N-H CH2 - N- C H3

Aniline N-Methylaniline Benzyldimethylamine

(a 1° aromatic (a 2° aromatic (a 3° aliphatic amine)
amine) amine)
• heterocyclic amines: amines in which nitrogen is one of
the atoms of a ring

N N N N
H H H
Piperidine Pyrrolidine Pyrrole Pyridine
(heterocyclic (heterocyclic
aliphatic amines) aromatic amines)
 Physical Properties

CH 3 CH 3 CH 3 NH 2 CH 3 OH
MW (g/mol) 30.1 31.1 32.0
bp (°C) -88.6 -6.3 65.0

Amines are polar compounds

• both 1° and 2° amines form intermolecular hydrogen bonds
• N-H----N hydrogen bonds are weaker than O-H----O
hydrogen bonds because the difference in electronegativity
between N and H (3.0 - 2.1 =0.9) is not as great as that
between O and H (3.5 - 2.1 = 1.4)
 Physical Properties
• both 1° and 2° amines form intermolecular hydrogen bonds
• NH3 forms 4 H-bond
.. -
N
H+ H+
+H +H H+
N H+
.. .. -
N
+H H+
H+

.. - .. -
N N
+H H + +H  H+
H+ H +
 Physical Properties
• both 1° and 2° amines form intermolecular hydrogen bonds
• 1° forms 3 H-bond

.. -
N
H+ H+
R +H + R
N
.. .. - H
N
+H R
H+

.. -
N
+H R
H+
 Physical Properties
• both 1° and 2° amines form intermolecular hydrogen bonds
• 2° forms 2 H-bond

.. -
N
R H+
R +H R
N
.. .. - R
N
+H R
R
 Physical Properties
• both 1° and 2° amines form intermolecular hydrogen bonds
• 3° forms NO H-bond

.. -
N
R R
.. - R
N
R
R+ R
Arrange the isomeric primary, secondary and tertiary amines
in order of increasing boiling points. Explain your answer.

3o < 2o < 1o
Hydrogen bridge between amine molecules.
H
1o R 2o R N R' 3o
N R'
H H H
R N H
R N R"
H
H N R R N R'
R N H H No hydrogen
bonding!
H
R N R'
H
 Basicity of Amines
All amines are weak bases and aqueous solutions of
amines are alkaline:

H H
•• + - ••

••
••

CH3 - N + H- ••O- H CH 3 - N - H O- H
••

H H
Methylamine Methylammonium
hydroxide
Characterization of the basicity of amines in aqueous
solutions as an equilibrium process:

+ -
[CH 3 NH 3 ][OH ]
Kb = K eq [H 2 O] = = 4.37 x 10 -4
[CH 3 NH 2 ]
 Basicity of Aliphatic Amines
Amine Structure pKb pKa
Ammonia NH 3 4.74 9.26
Primary Amines
methylamine CH 3 NH2 3.36 10.64
ethylamine CH 3 CH2 NH2 3.19 10.81
cyclohexylamine C 6 H11 NH2 3.34 10.66
Secondary Amines
dimethylamine (CH 3 ) 2 NH 3.27 10.73
diethylamine (CH 3 CH 2 ) 2 NH 3.02 10.98
Tertiary Amines
trimethylamine (CH 3 ) 3 N 4.19 9.81
triethylamine (CH 3 CH 2 ) 3 N 3.25 10.75
The lower is the pKb the stronger is the base
 Effect of substituents on the bases

STRONGER BASE

Electron-donating groups
R N: strengthen a base.

WEAKER BASE

Electron-withdrawing groups
R N: weaken a base.
DISSOCIATION CONSTANTS FOR SOME SIMPLE AMINES

pKb
electron ..
donating NH3
group
4.75
increasing
.. base strength
CH3 NH2 3.34
.. pKb is smaller
CH3 NH 3.27
CH3
CH3 trimethylamine is
out of sequence -
CH3 N: 4.19 probably a steric and/
or a solvation effect
CH3
 Basicity of Aromatic Amines
Aromatic amines are considerably weaker bases than
aliphatic amines. Compare the basicity of
cyclohexylamine (aliphatic) and aniline (aromatic):
pKb = 3.34
Kb = 4.5 x 10-4 +
NH2 + H2 O NH3 OH-

Cyclohexyl- Cyclohexylammonium
amine hydroxide

pKb = 9.37
Kb = 4.3 x 10-10 +
NH2 + H2 O NH3 OH-

Aniline Anilinium hydroxide

 Basicity of Aromatic Amines
• Aromatic amines are weaker bases than aliphatic
amines because the lone pair of electrons moves
from the nitrogen into the aromatic ring.

H H + H H + H H + H
N H N N N

Interaction of the electron pair on

nitrogen with the pi system of the
aromatic ring
CYCLOHEXYLAMINE AND SOME ANILINES
decreasing
base pKb base strength
..
NH 3.30 cyclohexylamine
2
electron
donating
..
CH 3 NH
2 8.90 p -methylaniline

..
NH 9.37 aniline
2

..
O N NH 13.0 p -nitroaniline
2 2

electron
withdrawing
 SOME CYCLIC AMINES
pKb
.. decreasing
pyrrolidine 2.73 N H sp3 basicity

..
piperidine 2.88 N H sp3

cyclohexylamine ..
3.30 NH2 sp3
pair outside of the ring
sp2
pyridine 8.75 pair is not involved
N:
in resonance

.. see next slide

pyrrole 14.27 sp2
N H pair is involved
in resonance
 The basic pair is In
the resonance system
PYRIDINE ( in a 2p orbital).
pKb 8.75

. . . .
. . weak
: base
. . N : . . N H

strong
base The basic pair pKb 14.27
(in an sp2 hybrid) PYRROLE
is not involved
in resonance
 Reactions of the amines

1. Acting as a base:
H
H
H N + HCl H N H Cl-
H
H
ammonium-chloride (salt)

R
R
R N + HCl R N H Cl-
R
R
trialkylammonium-chloride (salt)
 Reactions of the amines

2. Acting as nucleophile in an alkylation reaction:

R
R
R N + Br-CH2-R R N CH2-R Br-
R
R
3. Acting as nucleophile in an acylation reaction:

O R O
R
R N + Cl-C-R R N C-R Cl-
R
R
SYNTHESIS OF AMINES FROM ALKYL HALIDES

R _ C l + N H3 _ R_NH2 Primary (1°)

HCl

_ _
R C l + R NH2 R_NH_R Secondary (2°)
_
HC l

_ _ _
R Cl + R N H R _ R_N_R Tertiary (3°)
H Cl
R

.. R +
R _ C l R _ _
+ N R
R_N_R C -l
R Quaternary
R (4°)
Reaction of the aliphatic amines with nitrous acid
Primary amine:

R NH2 + HNO2 R OH + N2 +H2O

alcohol plus nitrogen gase
Secondary amine:

R R
NH + HNO2 N-N=O + H2O
R R
N-nitrosoamine
(yellow oily liquid)

Tertiary amine: No reaction

Reaction of the aromatic primary amines
with nitrous acid
+
-
NH2 HCl N N Cl + 2 H2O
+ HNO2

Diazonium salt

It is used in the
synthesis of different
aromatic compounds