Carboxylic Acids & Acid Derivatives & Amine Page # 19

AMINES
1. BASIC NATURE OF AMINES

1. Aniline is less basic than ammonia. The phyenyl group exerts- I (inductive effect, i.e., it withdraw
electrons. This results to the lower availability of electrons on nitrogen for protonation.
2. Ethylamine and acetamide both contain an amino group but acetamide does not show basic
nature. This is because lone pair of electrons on nitrogen is delocalized by resonance with the carbonyl
group which makes it less available for protonation.
O O
+
H3C — C — NH2 H3C — C = NH2

3. The compound with least ‘s’ character (sp3 hydrolized) is most basic and with more ‘s’ character
(sp-hydrilized) is least basic. Examples in decreasing order of basicity are :
:

:
(i) CH3NH2 > CH3 — N = CHCH3 > CH3 — C = N
(sp3) (sp2) (sp)

(ii) CH3CH2CH2NH2 > H2C =

CHCH2NH2 > HC  CCH2NH2

(iii) (CH3)2NH > CH3NH2>NH3 > C6H5NH2

Electron withdrawing (C6H5—) groups cause decrease in electron density on nitrogen atom and

there by decreasing basicity.

(v) CH3CH2NH2 > C6H5CONH2 > CH3CONH2

2. METHODS OF PREPARATION
1. Hafmann’s bromamide reaction : Amines (only primary) can also be prepared by Hoffmann
degradation. In this method the amine will have one carbon atom less than the amide. The reaction
proceeds via formation of nitrene.
O
R — C — NH2 + Br2 + 4KOH RNH2 + K2CO3 + 2KBr + 2H2O

Mechanism of above reaction has been proposed as given below :

Br2 + KOH K+O—Br + HBr
Mechanism
2NaOH + Br2 NaOBr + NaBr + H2O

O O
– –
(a) R — C — NH2 + OBr R — C — N — Br + OH

H
O N-bromoacetone
O
–
(b) R — C — N — Br | OH— R — C — N — Br + H2O
–H2O
Rearrangment
H

H2 O
R — NH2 + CO2 R — N = C = O (Isocyanate)

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2. Curtius, Schmidt and Lossen Rearrangment : These reaction are basically rearragment reaction
in which carbon migrates from carbon to nitrogen with the formation of an isocyanate. In these
migration i.e., 1, 2 shift, migrating group is an alkyl or aryl group and leaving group may be
— Br in Hoffmann rearrangement
— N2 in curtius and Schmidt rearrangement
O
—
Lossen rearrangement
R—C—O
The isocyanate formed on hydrolysis gives amine.

(a) Curtius Reaction : Acid chloride on treatment with sodium azide give acid azides which on pyrolysis
gives isocyanates on hydrolysis gives corresponding amines.
RCOCl + NaN3 RCON3 + NaCl
O O O
:

R—C—N=N=N R—C—N—N N R — C = N — N2

R N — N2 R—N=C=O
C alkyl isocyanate
O
H2O

H2 O
R — N = C — OH R — N = C — O—
OH OH
O
R — NH — C — OH R — NH 2 + CO2
–CO2
(b) Schmidt Reaction : Carboxylic acid reacts with hydrozoic acid in presence of concentrated H2SO4
to give isocyanates.
O OH OH
+ NH3
R—C +H R—C R — C — OH
OH
H — N — N+ N

–H2O

O
R — C — OH
–H+
R—N=C=O R—C
isocyanate H — N+ N
+
–H2O N —N N

R — NH2 + CO2

(c) Lossen Reaction : Hydroxylamine on treatement with acid chloride gives acyl derivatives of hydroxyl
amine the acyl derivatives exist in two tautomeric form keto form called hydroxamic form and enol form
called hydroximic acid. The hydroxamic form.
OH
R — COCl + NH2OH R—C=N + HCl

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O O
R — C — NHOH R — C = N — OH
Keto form the The hydroximic
hydroxamic from form (enol form)

The hydroxamic form (keto form) forms o-acyl derivatives of hydroxamic form which on heating with
bases forms isocyanates and finally amines upon hydrolysis.

H O H O
R — C — N — OH + R — C — Cl R—C—N—O—C—R

:
O
H2O
RHN2 R—N=C=O R—C—N—O—C—R

:
O

3. By reduction of nitrothane :
Sn + HCl
C 2H 5NO 2 + 6[H] C2H5NH2 + 2H2O
Nitroethane Ethylamine

4. By reduction of methyl cyanide :

Na + C2H5OH
CH3CN + 4[H] CH3CH2NH2
Methyl Ethylamine
cyanide

5. By reduction of acetamide : Ethylamine is obtained by reduction of acetamide with sodium and

absolute alcohol or LiAlH4 in ether or hydrogen in presence of nickel catalyst.
Na + C2H5OH
CH3CONH2 + 4[H] CH3CH2NH2 + H2O
Methyl cyanide Ethylamine

6. By reduction of aldoxime : Aldoxime on reduction with hydrogen and nickel catalyst or sodium
and absolute alcohol or LiAlH4 in ether yields ethylamine.
CH3CH = NOH + 4[H] CH3CH2NH2 + H2O
Acetaloxime Ethylamine

7. By the hydrolysis of ethyl isocyanate : Ethyl isocyanate on heating with caustic potash solution
undergoes hydrolysis forming ethylamine.
C2H5NCO + 2KOH C2H5NH2 + K2CO3
Ethyl
isocyanate Ethylamine

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8. By the acid hydrolysis of ethyl isocyanide : Ethyl isocyanide undergoes hydrolysis with a
mineral acid and forms ethylamine.
C2H5NC + 2H2O C2H5NH2 + HCOOH
Ethyl
isocyanate Ethylamine Formic acid

9. By Schmidt reaction :
C2H5COOH + N3H C2H5NH2 + N2 + CO2
Propionic acid Hydrazoic
acid Ethylamine

In this reaction the acyl azide (RCON)2 and alkyl isocyanate (R —NCO) are formed as an intermediate.

10. By the action of chloramine on Grignard reagent : When chloramine reacts with ethyl magnesium
iodide, the formation of ethylmine occurs.

C2H5MgI + ClNH2 C 2H5NH 2 +Mg

Ethyl magnesium Chloramine
Iodide Ethylamine Cl

11. By Gabriel’s phthalimide reaction :

CO KOH CO
NH NK
CO –H2O CO

C2H5l

COOH 2H2O CO
C2H5NH 2 + NC 2H 5
COOH HCl CO
Ethylamine

Phthalic acid N-Ethyl Phthalimide

12. Laboratory preparation of ethylamine : Ethylamine is prepared in the laboratory by Hofmann’s

bromide reaction. Proprionamides is heate with bromine and pottassium hydroxide solution.
C2H5CONH2 + Br2 + 4KOH C2H5NH2 + 2KBr + K2CO3 + 2H2O

Propionamide Ethylamine

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3. PHYSICAL PROPERTIES
(a) It is a colourless inflammable liquid. It’s boiling point is 19ºC.
(b) It has fishy ammonical odour.
(c) It is highly soluble in water. Its aqueous solution is basic in nature and turns red limus blue.
The solubility in water is due to hydrogen bonding with water moelcules.

4. CHEMICAL PROPERTIES
(i) Basic nature : It is more basic than ammonia. Following reactions prove its basic nature
(a) It forms ethyl ammonium hydroxide when dissolved in water.
C2H5NH2 + H2O C2H5NH3OH

Ethyl ammonium
hydroxide

Ethyl ammonium hydroxide ionises to give OH– ions

C2H5NH3OH C2H5 + —
NH3 + OH

(b) It reacts with acids to form salts.

C2H5NH2 + HCl C2H5NH3Cl or C2H5NH2.HCl
Ethyl ammonium chloride
or
Ethylamine hydrochloride
C2H5NH2 + H2SO4 (C2H5NH3)2 SO4
Ethyl ammonium sulphate
(c) Its aqueous solution behaves like ammonium hdyroxide. The aqueous solution of ethylamine
precipitates iron, chlromium and aluminium as hydroxides when salts are treated with it.
3C2H5NH3OH + FeCl3 Fe(OH)3 + 3C2H5NH3Cl
Ethyl ammonium Ferric Ferric Ethyl ammonium
hydroxide chloride hydroxide chloride

(d) It’s hydrochloride, like ammonium chloride, forms double salts with PtCl4 and AuCl3
2C2H5NH3Cl + PtCl4 (C2H5NH3)2 PtCl6
Ethylamine
Chloroplatinate

C2H5NH3Cl + AuCl3 C2H5NH3AuCl4

Ethylamine auric
Chloroplatinate
These double salts decomposes on heating to pure metal and this method is used to determine
the molecular mass of amines.
(ii) Reaction with alkyl halides (Alkylation) :
Ethylamine reacts with alkyl halides and form secondary, tertiary amines and quaternary ammonium salt.

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Page # 24 Carboxylic Acids & Acid Derivatives & Amine

C2H5NH2 + C2H5I (C2H5)2NH . HI

Diethyl ammonium
iodide

(C2H5)2 NH + C2H5I (C2H5)3 NHI

Triethyl ammonium
iodide
(C2H5)2 N + C2H5 I (C2H5)2NI
Tetraethyl ammonium
iodide

(iii) Reaction with acetyl chloride or acetic anhydride : Acetylation takes place when ethylamine
combines with acetyl chloride or acetic anhydride.
C2H5NH + ClOCCH3 C2H5NHOCCH3 + HCl
Acetyl Acetyl ethylamine
chloride or
N-Ethyl acetamide

C2H5NH2 + (CH3CO) 2O C2H5NHOCCH3 + CH3COOH

Ethylamine Acetic anhydride N-Ethyl ethylamide

(iv) Carbylamine Reaction

+ –
RNH2 + CHCl3 + 3KOH R—N C : 3KCl + H2O
an isocyanide
(foul smelling)

Nucleophilic RNH2 attacks electrophilic intermediater [:CCl2] dichlorocarbene.

This reaction is used for the detection of primary amines.

Mechanism

Cl
:

R — NH2 + : CCl2 R — HN — C
Cl

H
—HCl

+ –
R—N C R — N = Cl — Cl

(v) Reaction with sodium : Hydrogen is evolved when ethylmine is heated with sodium.
2C2H5NH2 + 2Na 2C2H5NHNa + H2
Sodium derivative
of ethylamine

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(vi) Reaction with Grignard reagents : Ethylamine reacts with Gragnard reagents to form alkanes.

2C2H5NH2 + RMgX R — H + C2H5NHMgX

Grignard Alkane
reagent

2C2H5NH2 + CH3MgI CH4 + C2H5NHMgI

Methyl Methane
Magnesium iodie

(vii) Hofmann’s mustard oil reaction : Carbon disulphide reacts with ethylamine in presence HgCl2 to
form ethyl isothiocyanate which has a mustard oil like smell.
C2H5NH2 + CS2 + HgCl2 C2H5N = C = S + 2HCl
Ethyl isothiocyanate
(viii) Reaction with aldehydes : Ethylamine reacts additively with aldehydes to form -hydroxyl
amines which are changed to Schiff bases with the elimination of water molecule.

H
C2H5NH2 + O = C — CH3 C2H5 — N — C — CH3
Ethylamine Acetaldehyde
–H2O

C2H5N = CH — CH3
Ethylidene ethylamine
(Schiff's base)

DISTINCTION BETWEEN PRIMARY, SECONDARY AND TERTIARY AMINES

Test Primary amine Secondary amine Tertiary amine

1. Action Test CHCl3 and Bad smelling carbyl-amine No action. No action.

alcoholic KOH. (Isocyanide is formed)

2. Action of CS2 and Alkyl isothiocyanate is No action. No action.

HgCl2. (Mustard Oil formed which has pungest
test smell like mustard oil.

3. Action of Nitrous acid. Alcohol is formed with Forms nitrosoamine which Forms nitrite in cold which
evolution of nitrogen. gives green colour with on hearing gives nitrosoamine
phenol and conc. H2SO4 which responds to
(Liebermann's test.) Liebermann's test.

4. Action of acetyl Acetyl derivative is Acetyl derivative is No action.

chloride. formed formed

5. Action of Hinsberg's Monoalkyl sulphon-amide Dialkyl sulphonamide is No action.

reagent is formed which is soluble formed which is insoluble
in KOH. in KOH.

6. Action of methyl 3 molecules (moles) of 2 moles of CH3I to form One mole of CH3I to form
iodide. CH3I to form quaternary quaternary salt with one quaternary salt with one
salt with one mole of of mole of secondary amine. mole of tertiary amine.
primary amine.

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 Page # 26 Carboxylic Acids & Acid Derivatives & Amine

5. GENERAL CHEMICAL PROPERTIES OF AROMATIC AMINES

5.1 REACTION WITH NITROUS ACID

1. Primary Amines : Primary amines react with nitrous acid to produce diazonium ion as follows.
ArNH2 + HNO2 Ar — N N:
R — NH2 + HNO2 R— N N
But the diazonium ions of aliphatic amines are very unstable and produces carbocation
immediately, which can produce different products.
–N2
R— N N R+ (Carbocation)

+
+ –H– (Hydride shaft)
N Cl N3 + Cl + H 3C CH2 H 3C CH2
H3C N
+
–H
Cl–

OH Cl
H3C H 3C H 3C CH2 CH 3 CH3
1-chloropropane prop-1-ene
propan-1-ol H3C H3C

OH Cl
propan-2-ol
2-chloropropane

H 3PO 2
Al — H

KI
Ar — I

CuCl(CuBr)
ArCl/(A,Br) (Sandmeyer reaction)

Ar — N N
Ar — F

H2O/H+
Ar — OH
CuCN
Ar — CN (Sandmeyer reaction)

ROH
Ar — OR

6. RING REACTIONS OF AROMATIC AMINES

NH2 — NHR and —NR2 strongly activate the benene ring toward electrophilic substitution
1. Haogenation : For monohalogenation, —NH2 is first acetylated, because
H3C — C — N —
O H

is only moderately activating and is o and p-director in nature

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NH2 NH2 NHCOCH3 NHCOCH3 NH2

Br Br
Br2 Ac2O Br2 H2O
H2O OH–
Br Br Br
2. Sulfonation :
+
NH2 NH3 HSO4 NHSO3H NH3

H2SO4 180ºC 180ºC

H2 O 3 hours

–
Anilinium Sulfate Sulfamic acid SO3
Sulfanilic acid
(a dipolar ion)

The dipolar ion structure of sulfanilic acid account for its (a) high melting point, (b) insolubility in H2O
and organic solvents, (c) solubility in aqueous NaOH, (d) insolubility in aqeous HCl.

H2N CO2H

will not exists as a dipolar ino since, –COOH is too weakly acidic to transfer an H+ to the weakly basic
–NH2 attached to the electron withdrawing benzene ring. When attached to an aliphatic C, the NH2 is
sufficiently basic to accept H – from COOH.

O O

NH 2 HN CH 3 HN CH3 HN2

CH 2CO)2O HNO3.H2SO4 OH –
heat

aniline N-phenylacetamide N-(4-nitrophenyl)acetamide NO2

4-nitroaniline

H X
N NH 2 NH 2
X
and

(i) The Hinsberg Test

Ths test can be used to demonstrate whether an amine is primary, secondary or tertiary. Primary
amines react with benzenesulfonyl chloride to form N-substituted benzenesulfonamides. These, in
turn, undergo acid-base reactions with the excess potassium hydroxide to form water - soluble potassium
salt. Acidification of this solution will, cause the water-soluble in the next stage, cause the water-
insoluble N-substituted sulfonamide to precipitate.

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Page # 28 Carboxylic Acids & Acid Derivatives & Amine

Acidic hydrogen

H O H O
–
OH
R—N: + Cl — S :N — S
(–HCl)
H R
O O
1º amine

KOH

+
O K O
H HCl
:N — S :N — S
R O R O

Water insoluble salt Water soluble salt

(precipitate) (clear solution)

Secondary amies react with benzenesulfonyl chloride in aqueous potassium hydryoxide to form insoluble,
N - N-disubtituted sulfonamides that precipitate after the first stage. N3N–
Disubstituted sulfonamides do not dissolved in aqueous potassium hydroxide.

R'

O R' O
OH–
R H + Cl — S :N — S
(–HCl)
O R O

Water insoluble salt

(precipitate)

If the amine is a tertiary amine and if it is water insoluble, no apprated change will take place in the
mixture as we shake it with benzenesulfonyl choride and aqueous KOH. When we acidify the mixture,
the tertiary amine dissolves because it forms a water soluble salt.

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