Professional Documents
Culture Documents
Aliphatic PDF
Aliphatic PDF
Amines are derivatives of ammonia in which one or more hydrogen atoms are replaced by alkyl group.
Amines are classified as primary, secondary or tertiary depending on the number of alkyl groups attached to
nitrogen atom.
R R R
NH3
H
R NH2
H
R2 NH
H
R3 N
p–amine s–amine t–amine
(amino) (Imino) (Nitrilo)
General formula
Str ucture : Nitrogen atom is sp3 hybridised. It has one lone pair of electron ..
N
so the shape of molecule is pyramidal. R H
H
Isomerism : Amines show chain, position, functional isomerism and metamerism.
Ex. How many primary amines are possible from molecular formula C4H11N
(A) 4 (B) 5 (C) 6 (D) 3
S o l . (A)
Ex. Which isomerism present in n–propyl amine and isopropyl amine
(A) Metamarism (B) Functional group (C) Position (D) Position and chain
S o l . (C)
Ex. How many structural isomers are possible from molecular formula C3H 9N
(A) 2 (B) 3 (C) 1 (D) 4
S o l . (B)
Ex. Write the structures of amines having the molecular formula C4H 11N
Sol.
CH3 CH3
3° amine
(d) CH3 CH2 CH NH2 (h) CH3 N CH2 CH3
q General Met ho d of Preparat ion :
(1) Ammonolysis of alkyl halides and alcohol :
(a) From Ammonolysis of alkyl halide s [Hofma nn's ammonolysis] :
When an aqueous solution of ammonia is heated with alkyl halide all the three types of amines and
quaternary ammonium salt are formed.
NH 3 R X R X R X
R — X
HX
R—NH2
HX
R2—NH
HX
R3N R4NX
NH 3 R OH R OH
R—OH
Al O / 400 C
R—NH2
Al2 O 3
R 2— N H
Al2 O 3
R 3N
2 3
Note : (i) Quaternary ammonium hydroxide is not formed due to steric hindrance.
(ii) If excess of ammonia is used, then main product will be primary amine.
(2) By reduct ion :
LiAIH
4
(a) With RCONH 2 : RCONH 2
or Na/C H OH
RCH 2 NH 2
2 5
R—NC + 4H C H OH / Na RNHCH 3
2 5
LiAlH 4
(c) With Oximes : R CH N OH + 4H RCH2 NH2 + H2O
Na / C 2 H 5 OH
Sn / HCl
(d) With RNO 2 : RNO2 + 6H
RNH 2 + 2H 2 O
R—N=CO + 2 KOH
RNH 2 + K 2 CO 3
I
R Mg I + Cl NH2 R NH2 + Mg
Cl
(5) Gabriel phthalimide synthesis :
Phthalimide is first treated with KOH to obtain potassium phthalimide which is then treated with alkyl iodide.
Then alkyl phthalimide on hydrolysis yields alkylamine. This method is used in the formation of pure aliphatic
primary amines.
CO KOH
CO
NH
–H O NK
2
CO CO
(SN2) RI
COOH 2H2O
CO
R NH2 + NR
COOH CO
Phthalic acid
(6) By Hofma nn's bromamide react ion (Hofma nn's Hypobromite react ion) :
This is a general method for the conversion of alkane amides in to one carbon less primary amines. Ethanamide
is heated with bromine and excess of KOH.
KOH
CH3 C NHBr
: :
Mechanism :
O O O
:
R N—N2 H2O H2O
R—N=C=O R—N C—O
C alkyl isocyanate
OH
O
O
–CO2
R—N C—OH R—NH—C—OH R—NH2
OH
(8) Schmidt react ion :
In presence of conc. H2SO4 alkanoic acid reacts with hydrazoic acid (N3H) to yield alkylamine.
2 4
Conc. H SO
R—COOH + N 3 H R—NH2 + N2 + CO2
Mechanism :
O OH OH
HN3
R—C + H R—C R—C —OH
OH OH H—N —N N
–H2O
O
–H
R—C—O—H
–N2
R—N=C=O R—C
isocyanate N—N N
–H2O N—N N
R—NH2 + CO2
O H O O H O
R—C—N—OH + R—C—Cl R—C—N—O—C—R R—C—N—O—C—R
:
:
Hydroxamic acid
O O
H2O
R—N=C=O R—NH2
–CO2
Ni
C O + NH3 + H2 CH—NH2 + H2O
1° amine
Ni
C O + RNH2 + H2
CH—NHR + H2O
2° amine
Ni
C O + R2NH + H2 CH — NR2 + H2O
3° amine
Physical Proper t ie s :
(i) CH3NH2 is gas and C2H5NH2 is a volatile liquid.
N H N H N H N H N H N H
H H H R R R
(1° amine) (2° amine)
In 3° amine (due to absence of H–atom) H–bonding is not possible.
(iv) Boiling point : Due to small intermolecular association the b.p. of 1° and 2° amines are lower than
those of alcohols of comparable molecular weight. The boiling point of 3° amines which form no
H–bonds are near to those of alkanes of comparable molecular weight.
Boiling point molecular weight
(v) Solubility : Low molecular weight amines (< six carbon) are very soluble in water. The water solubility
of amines decreases with increasing size of alkyl group.
R
R H R R H R R H N R
N H O H N H N H O H N H R N H O R
H H R R R
(1° amine) (2° amine) (3° amine)
Order of solubility p– amine > s– amine > t– amine
Chemical Proper t ie s :
(i) Basic character of amines is due to the presence of lone pair of electrons on the N - atom.
(ii) Basic strength depends on electron donating tendency.
Basicity order in aqeous solution and in liquid phase.Et2 NH > Et3 N > Et NH2. Due to steric hindrance
in 3° amine, it is less basic, than 2° amine.
Steric hindrance of three –C 2 H 5 group protect the lone pair of nitrogen from the attack of H .
But i n gaseous phase basic order is R2 N H > R N H2 > R3 N > N H 3
Some other basic order of different amine if alkyl group would be change
Alkyl groups (R–) Relative base strength
(i) CH 3 – R 2 NH > RNH 2 > R 3 N > NH 3
(ii) C 2H 5 – R 2 NH > RNH 2 > NH 3 > R 3 N
(iii) (CH 3 ) 2 CH – RNH 2 > NH 3 > R 2 NH > R 3 N
(iv) (CH 3 ) 3C – NH 3 > RNH 2 > R 2 NH > R 3 N
Special point :
(I) Tertiary amine is less basic then secondary due to following reasons :
(i) Steric hindrance : In tertiary amines (R3N) , three alkyl groups attached to N are bulkier and as such
exert steric hindrance.
(ii) Decrease i n hydrat ion :
In tertiary amine In secondary amine
H
O
H H
H R2N
R3N H O H H
H O
H
Protonated t–amine can form H–bonding Protonated s–amine can form H–bonding with
with water molecule only at one point water molecules at two points
[less stable] (more stable)
3° amine are less stable as compare to 2° amine due to low hydration so less basic.
(II) The basic strength of aniline is less than aliphatic amines as the lone pair of electron present on N– atom
interact with the delocalized - orbital of benzene ring. Hence it is less available for protonation on N–atom.
The basic order nature for aniline, pyridine and pyrrole Pyridine > Aniline > Pyrrole
(2) React ions show i ng basic nature :
(a) It reacts with acids to form salts.
RNH 2 + HCl [RNH3]Cl
High temp.
R—Cl + NH3
2RNH 2
H 2 SO 4
(RN H 3 ) 2 SO 4–2 Alkyl ammonium sulphate
(b) Amines reacts with auric acid and platinic chlorides in presence of HCl to form double salts.These
double salts decompose on ignition to pure metal. Therefore the formation and decomposition of the
double salts is used for determining the molecular weight of amines.
–2
2R NH2 + PtCl4 + 2HCl [RNH3]2PtCl6
(RN H 3 ) 2 PtCl 6–2 Pt
(c) Reaction with H 2 O : It forms alkyl ammonium hydroxide with water ammonium hydroxides are used
for precipitation of IInd and IIIrd group cations in qualitative analysis
RNH 2 + H 2 O (RNH3)OH
Base
FeCl3 + 3[RN H3 ]OH
Fe(OH)3 + 3[RN H 3 ]Cl
Brown ppt
AlCl3 + 3[RNH 3 ]OH
Al(OH)3 + 3[RN H 3 ]Cl
White ppt.
CrCl3 + 3[RNH 3 ]OH
Cr(OH)3 + 3[RN H 3 ]Cl
Green ppt.
(3) Reaction with alkyl halides :
Alkyl amine reacts with alkyl halides and form sec., ter. amines and quaternary ammonium salt.
HX RX RX
RNH2 + R—X R 2 N H R 3N R4NX
HX
Special Point :
Separation of 1°, 2° and 3° amines :
KOH
C6H5SO 2Cl + 2° amine Product insoluble
3° amine does not react with benzene sulphonyl chloride.
(iii) Hofmann method : In this method mixture of amines is separated by using ethyl oxalate.
1° amine + ethyl oxalate solid product
2° amine + ethyl oxalate liquid product
3° amine + ethyl oxalate No reaction
(4) Acetylation : Acetylation takes place when alkyl amine combines with acetyl chloride or acetic anhydride.
(N –alkyl acetamide)
(N –alkyl acetamide)
(5) Benzoylat ion (Schot ten bauma nn react ion) :
COCl CONHR
NaOH
+ H NH R + HCl
R—NH 2 + NOCl
RCl + N2 + H2O
(8) Reaction with phosgene :
R—NH 2 + COCl 2
R N C O + 2HCl
Alkyl isocyanate
(9) Reaction with halogen : The hydrogen atoms of the amino group are replaced by halogen atoms in presence
of alkali solution.
NaOH
R—NH 2 + Br 2 R—NH—Br + HBr
or KOH
N– bromo alkylamine
NaOH
R—NH—Br + Br 2 R—NBr 2 + HBr
H H H
R NH2 + O C R R N C R
H O
2
RCH NR (Schiff's base)
OH
[O ] H2O
R — C H 2 N H 2 R—CH NH RCHO + NH3
KMnO 4 / H H
(Aldimine)
[O] H O
R 2 CHNH 2 R2C NH
2
R2C O + NH3
H
(Ketimine) (Ketone)
R 3 CNH 2
[O]
R3CNO2 (Nitroalkane)
Wit h H 2 SO 5 (Caro's acid) Or H 2 O 2 /Fe +2 (Fenton reagent) :
O
[O]
RCH 2 NH 2
R—CH 2—NH—OH + RCH NOH + R C NHOH
:
Cl Dichlorocarbene
Cl –HCl
R—NH2 +:CCl2
:
R—HN—C R—N C—Cl R—N C
Cl
H H
S S
HgCl 2
R NH2 + C S R NH C SH R N C S + HgS + 2HCl
Alkyl isothiocyanate
S S
HgCl 2
R2NH + C S R2N C SH No reaction
S
R3N + C S No reaction.
(A) These forms salt will acids (B) Gives alcohols on hydrolysis
(C) Gives carbyl amine reaction (D) Gives musturd oil test
S o l . (C)
( 1 5 ) Reaction with HNO 2 (NaNO 2 + HCl or H 2 SO 4 ) :
(a) Primary amines react with nitrous acid to produce nitrogen gas [seen as bubbles]
CH 3 NH 2 + HNO 2 C H 3— O — C H 3
(b) R 2 NH + HONO R 2 N—NO + H 2 O
N–nitroso amine (Yellow oily layer)
This is called libbermann's nitroso test
(c) R 3 N + HONO R3NHNO2 Trialkyl ammonium nitrite (Soluble in water)
Points to Remember :
(i) Nitrosoamines are carcinogens (Cancer causing agents)
(ii) Amines can have chiral N-atom but cannot be resolved into enantiomeric forms because of rapid inversion
of one enantiomeric form into the other.
(iii) The Schiff's bases formed by reaction of 1°-amines and aldehyde/ketones are also called anils.
(iv) The mixture of 1°, 2°, 3° amines can be distinguished by Hoffmann's test or Hinsberg's reagent or
carbylamine test or nitrous acid test.
(v) In Hoffmann test CS2 + HgCl2 are used and in Hinsberg test benzene sulphonyl chloride (C6H5SO2Cl)
is used.
ANILINE (C 6 H 5 NH 2 )
Aniline is also called aminobenzene or phenyl amine. Aniline was first prepared by Unverdon 1826 by the
distillation of indigo which is called anil in spanish and hence the name aniline. In aniline —NH 2 group
is directly attached to benzene ring.
General Met ho ds of Preparat ion :
(1) Lab method : Aniline is prepared in the lab by reduction of C6H5NO 2 with Sn + HCl.
(i)Sn HCl
C 6 H 5 NO 2
(ii) NaOH
C6H5NH 2 + H 2O
(i) Fe HCl
C 6 H 5 — N O 2
(ii) NaOH
C 6H 5 —NH 2 + H 2 O
(3) From Phenol : Aniline is obtained when phenol is treated with ammonia in presence of ZnCl2 at 300°C.
ZnCl
C6H5OH + NH3 2
300 C
C6H5NH 2 + H 2O
(4) From benzamide (Hofmann's reaction): Aniline is formed when benzamide is treated with Br 2 and KOH.
Conc.
C 6 H 5 COOH + N 3 H C6H5NH2 + N2 + CO2
H 2 SO 4
(Hydrazoic acid)
(6) From chloro benzene : Aniline can be manufactured by the action of ammonia on chloro benzene in
presence of cuprous oxide (Cu2O).
:
N H N H
H H
Order of basic strength : RNH 2 > NH 3 > C 6H 5 NH 2
(iv) Electron withdrawing group decreases the basic strength where as electron donating groups increases
the basic strength
NO2 CH3
p C6H4 < C 6 H 5 NH 2 < p
NH2 C6H4
NH2
(v) Aqueous solution of aniline is neutral to litmus
(A) React ions due to —NH 2 group :
(1) Basic nature : Aniline is weak base but it forms salt with strong acids. It a accepts a proton.
:
C6H5NH 2 + HCl C6H5NH3Cl Aniline hydro chloride
(A) (CH 3 ) 3 N (B) (CH 3 ) 2 NH (C) (CH 3 ) 2 N (D) (CH 3 ) 2 N
S o l . (B)
(2) Alkylation :
Aniline reacts with alkyl halides forming secondary, tertiary and quaternary ammonium salts depending on the
concentration of alkyl halides.
(N–methyl aniline)
C 6 H 5 NH — CH 3 + CH 3 I C 6 H 5 N(CH 3 ) 2 + HI
(N,N–dimethyl aniline)
C6H 5N(CH 3)2 + CH 3I C 6 H 5 (CH 3 ) 3 N I
O O
O O
(4) Carbylamine reaction : When aniline is heated with CHCl 3 and KOH it gives isocyanide having unpleasent
smell which can be easily detected.
HgCl
C 6 H 5 NH 2 + S C S 2
H S
C 6H 5N C S
2
Phenyl isothiocyanate
If the above reaction is carried out in presence of solid KOH diphenyl thiourea is formed (Used as accelerator
for vulcanisation of rubber).
C6H5NH2 C6H5NH
+ S=C=S C S + H2S
C6H5NH2 C6H5NH
C6H5NH
C S + HCl C6H5 N C S + C 6 H 5NH 3 Cl
C6H5NH
(6) Reaction with aldehydes : Aniline condenses with aldehydes to form schiff's base.
O Benzylidene aniline
(schiff's base)
C6H5NH2 + HCl C6H5NH3Cl
NaNO2 + HCl HNO 2 + NaCl
C6H5NH3Cl + HNO2 C 6 H 5 N 2 Cl + 2H 2 O
6 5C H OH
C 6 H 5 N 2Cl C 6H 5 N=N—C 6H 4 OH [p-hydroxy azobenzene (orange dye)]
6 5C H NH
2
C 6 H 5 N 2Cl C 6H 5N=N—C 6H 4 NH 2 [p-amino azobenzene (aniline yellow)]
N2 C6H5
OH
Naphthol
C6H5N2Cl
10% NaOH
(Red colour)
( 1 0 ) Oxidation : Aniline forms a number of products depending upon the nature of oxidising agent:-
[O ] [O ] [O ]
—NH 2 —NHOH —NO —NO 2
S.N. Oxidant Pro duct
1. Acidic KMnO 4 Aniline black (a dye)
2. Alkaline KMnO 4 Azobenzene C 6H 5 N = NC 6 H 5
3. Neutral KMnO 4 Azobenzene + Nitro benzene
4. Caro's acid (H2SO 5) Nitrobenzene + Nitroso benzene
5. CF 3 COOOH Nitrobenzene
C H OH
2 5
3 H PO
2
C6H6 Benzene
HCOOH
Na/NaOH
2H
Cu Cl /HCl
2 2
C6HCl
5 + N2 + HCl
Cu Br /HBr
2 2
C6HBr
5 + N2 + HCl Sandmeyer reactions
Cu (CN) /HCN
2 2
C6HCN
5 + N2 + HCl
KI (aq.)
C6HN
5 2Cl
C6HI
5 + N2 + KCl
4NaBF /
C6HF
5 + BF3 + NaCl Balz–Schiemann reaction
Sodium tetrafluoro
borate
2 HO
C6HOH
5
Cu
C6HCl
5 Gattermann reactions
+4H
C6HNHNH
5 2 (Phenyl hydrazine)
SnCl2 + HCl
N2 C6H5
OH
10% NaOH
(Red colour)
SnCl /NaOH
2
C6H6
C H OH
6 5
C6HN
5 N— C6H4OH
p-Hydroxy azobenzene (Orange dye) Coupling
C6H5NH2 reactions
C6HN
5 N C6H4NH2
p-Amino azobenzene (aniline yellow)
(B) Reactions due to benzene ring :
:
NH2 NH2 NH2 NH2 NH2 NH2
:
: /3 /3
/3
:
Resonance hybrid
Note :
(i) In aniline 2, 4, 6 or ortho and para positions are electron rich so electrophile attacks here.In aniline 3,
5, or meta position is electron deficient so nucleophile attacks here.
(ii) The benzene ring of aniline undergoes halogenation, sulphonation and nitration.
(iii) The NH2 group is o-, p-directing.
(1) Halogenation : Chlorine and bromine react with aniline and form trichloro and tribromo aniline respectively
NH2 NH2
NH2
Br Br Cl Cl
+ 3Br2 or 3Cl2 Polar solvent
e.g. (H 2 O )
or
Br Cl
2,4,6– Tribromo aniline
(white ppt.)
NH2 NH2
Br
NH2 +
Note :
However, monobromo or chloro derivative of aniline can be prepared if -NH2 group is first protected by acetyl
group. Here the reactivity decreases due to -I effect of acetyl group.
NHCOCH3 NHCOCH3
Br
+
NH2 NHCOCH3 Br
CH3COCl Br2
H2O
(Acetanilide)
NH2 NH2
Br
+
Br
o– andp–Bromo aniline
(2) Nitration :
(a) Direct nitration : The direct nitration of aniline by conc. HNO3 and conc. H2SO4 give meta-nitroaniline.
Due to positively charged N, m-position becomes electron rich as compared to o, p–position.
NH2 NH3HSO4 NH2
H 2 SO 4
HNO 3
N O 2
– H 2 SO 4
NO2
(b) Indirect nitration : In indirect nitration amino group is protected by acetylation to give acetanilide,
which on nitration and subsequent hydrolysis give o- and p- nitro-aniline.
NO2 NO2
S o l . (D)
(3) Sulphonation : Aniline reacts with fuming H 2SO 4 to give sulphanilic acid.(p-Amino-benzene sulphonic acid)
NH2 NH3HSO4 NHSO3H NH2
SO3H
Sulphanilic acid
NH2 NH3
(Zwitter ion)
SO3H SO3
(4) Cataly t ic hydrogenat ion :
Aniline undergoes hydrogenation in presence of Ni at high temp. to form amino cyclohexane.
NH2 NH2
Ni
+ 3H2
High Tem p.
(5) Mercuration : When treated with alc. solution of mercuric acetate aniline undergoes mercuration.
NH2 NH2
HgOCCH3
+ (CH 3COO) 2Hg + CH3COOH
O
o– Amino phenyl
mercuric acetate
Te st s of ani li ne :
Carbylamine test : Aniline gives carbylamine test or Isocyanide test.
H
(A) R C N H 2 O ......... (B) R X NH 3 .........
Na
(C) R CH NOH [H] .........
C 2 H 5 OH
LiAlH 4
(D) RCONH 2 4[H] .........
Sol. (A)
3. Which of the following is not an ambident nucleophile?
(A) –ONO (B) –OCH 3 (C) –CN (D) –CNO
Sol. (B)
4. An organic compound (A) on reduction gave a compound (B) Upon treatment with HNO 2, (B) gave ethyl
alcohol and on warming with CHCl 3 and alcoholic KOH, (B) gave offensive smell. The compound (A) is
(A) CH 3 CN (B) C 2 H 5 CN (C) CH 3 NH 2 (D) CH 3 NC
Sol. (A)
5. Silver chloride is soluble in methylamine due to the formation of :
(A) [Ag(CH 3 NH 2 ) 4 ]Cl (B) [Ag(CH 3 NH 2 ) 2 ]Cl (C) [Ag(CH 3 NH 2 ) 3 ]Cl (D) [Ag(CH 3 NH 2 )]Cl
Sol. (B)
6. Hinsberg's reagent is:
(A) benzene sulphonamide (B) benzene sulphonic acid
(C) benzene sulphuryl chloride (D) benzene sulphonyl chloride
Sol. (D)
CH3
O
7. + CH 3 NH 2 Product ; product is :
O
CH3
(A) O (B) O
NCH3
HO NHCH3
OH
NH
(C) H C CH3 (D) None of these
3
O
CH I moist
3
A
excess Ag O
B C
2
N
H
(A) (B) (C) N (D)
H3C CH3
H
2CH3I Ag2O/H2O CH3I
+ + +
Sol. N N I N OH N N I
H H3C CH3 H3C CH3 H3C CH3 H3C CH3
CH3
H
Ag2O/H2O
+
N penta-1,3-diene
(more stable)
H3C CH3
CH3
Hence,(A) is the correct answer.
9. A compound X with seven carbon atoms on treatment with Br 2 and KOH gives Y. Y gives carbylamine
test and upon diazotisation and coupling gives azodye. X is :
(A) C 6 H 5 CONH 2 (B) CH 3 —(CH 2 ) 5 —CONH 2
CH3
CH3—C—CH2—CH2—CONH2
(C) (B) CH 3 —O—C 6 H 4 NH 2
CH3
Sol. Since Y gives coupling reaction after diazotization, it suggest that Y can be aniline or benzene ring substituted
aniline. Since Y has been obtained from Hofmann bromamide it means it has —CONH2 group with benzene
ring. Hecne, it is C 6 H 5 CONH 2. Hence (A) is the correct answer.
10. Methyl ethyl propyl amine forms non-superimposable mirror images but it does not show optical activity
because :
(A) of rapid flipping (B) amines are basic in nautre
(C) nitrogen has a lone pair of electrons (D) of absence of asymmetric nitrogen
Sol. The interconversion of d and -forms are so fast that it is not possible to isolate these. Hence, (A) is the
correct answer.
CH3 CH3
Rapid
C2H5 N •
• •
• N C2H5
C3H7 Inversion C3H7