Class-XII Amines

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Class-XII Amines
P r o p e r t ie s
[ 1 ] S a lt f o r m a t io n
+ - NaOH
R NH2 + HX R NH 3 X R NH2 + H2O + NaX
Substituted ammonium salt

- NaOH
NH2
+ HCl +
NH 3 Cl NH2 + H2O + NaCl

Anilinium chloride
[ 2 ] A lk y la t io n
RX RX RX + -
R NH2 R2NH R 3N R4 N X

[ 3 ] A c y la t io n
T h e r e p la c e m e n t o f h y d r o g e n a to m o f -N H 2 g r o u p b y ac y l g r o u p is k n o w n as acy latio n .
O H O H
Base
H3C C Cl + H N C2 H 5 H3C C N C2 H 5
N-Ethylethanamide
T h e b as e stro n g er th an am in e, lik e p y rid in e is u s ed to rem o v es H C l so fo rm ed .
O C2 H 5 O C 2 H5
Base
H3C C Cl + H N C2 H 5 H3C C N C2 H 5
Ethanoyl chloride N,N-Diethylethanamide
O O H O H
H3C C O C CH3 + H N H3C C N
Ethanoic anhydride N-Phenylethanamide
Aniline
[ acetanilide ]
O
H O H
C Cl + H N CH 3 C N CH3
Methanamine N- methylbenzamide
Benzoyl chloride
[ 4 ] C a r b y la m in e r e a c t io n
Heat
NH2 + CHCl 3
+ 3 KOH NC + 3 H2O
+ 3 KCl

Heat
R NH2 + CHCl 3 + 3 KOH R NC + 3 H2 O + 3 KCl

Primary amine Isocyanide

/ Carbylamine
[ Foul smell ]
[ 5 ] R e a c t io n w it h N it r o u s a c id
[ N i tr o u s a c id i s p r e p a r e d i n s itu f r o m m i n e r a l a c id a n d s o d iu m n it r i te .]
NaNO 2 + HCl + - H2O
R NH 2 + HNO 2 R N2 Cl R OH + N2
+ HCl
Alcohol
Aliphatic diazonium salt

NaNO 2 + HCl -
NH2
+ HNO 2 +
N2 Cl + NaCl + H2O

Benzenediazonium chloride
B en z en ed iaz o n iu m c h lo rid e is stab le d u e to r es o n an c e.

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Class-XII Amines
[ 6 ] R e a c t io n w it h H in s b e r g ' s r e a g e n t
B e n z e n e s u l p h o n y l c h l o r i d e i s k n o w n a s H i n s b e r g 's r e a g e n t .
O O + O
KOH K
R N H + Cl S R N S R N
-
S

H O O O
H
Water soluble
1o amine
Acidic hydrogen potassium salt
N-alkylbenzenesulphonamide of sulfonamide
O O
KOH Water insoluble
R N H + Cl S R N S
precipitate
O R O
R
o N,N-Dialkylbenzenesulphonamide
2 amine
O
R N R + Cl S No reaction
R O
3o amine
O
+ O O
K
R N S
HCl
R N S
H2O R N H + Cl S
- KOH H O
O H O
1o amine
O O
H2O
R N S
KOH
R N H + Cl S

O R O
R o
2 amine
T h e s e d a y s b e n z e n e s u lp h o n y l c h l o r id e is r e p la c e d b y p -to lu e n e s u lp h o n y l c h lo r id e .
NH2
[ 7 ] E le c t r o p h ilic s u b s t it u t io n
Br Br
Br2 / H2O

Br

NH2 NH2 NH2 NH2

NO 2
HNO 3 , H2SO4 . 288 K
+ +
NO 2
Aniline NO 2 ( 47 % ) (2%)
( 51 % )

+ - +
NH 3 HSO 4 NH2 NH 3

H2SO4 453 - 473 K

Aniliniumhydrogensulphate -
SO3H SO3
Sulphanilic acid Zwitter ion

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Class-XII Amines
C o n t r o lle d B r o m in a t io n O O
xx
NH2 H N C CH3 H N C CH3 NH2
( CH 3CO ) 2O Br2 - +
OH / H
Pyridine CH 3COOH

N-Phenylethanamide Br Br
( Acetanilide )

C o n t r o lle d N it r a t io n O
O
NH2
xx
H N C CH3 NH2
H N C CH3
( CH 3CO ) 2O - +
HNO 3 , H2SO4 , 288 K OH / H
Pyridine

NO 2 NO 2
T h e lo n e p a ir o f e lec tr o n s o n n itr o g en is le s s a v ailab le fo r d o n a tio n to b e n z en e r in g b y
r e s o n a n c e . T h e r e f o r e , a c t i v a t i n g e ff e c t o f - N H C O C H 3 g r o u p i s l e s s t h a n t h a t o f a m i n o
grou p .
Ex pla n a ti o n s
A n ilin e a n d o th e r a r y l a m in es ar e c o lo u r le s s b u t g e t c o lo u r ed o n s to r ag e d u e to
atm o sp h eric o x id atio n .
A lc o h o ls are m o r e so lu b le th an am in e in w ater b ec au se, alco h o ls are m o re p o lar th an
am in es an d fo rm stro n g in term o lecu lar h y d ro g en b o n d s th an am in e.
T h e in ter m o lec u la r a s s o c ia tio n is m o r e in p r im ar y a m in e th a n in s e c o n d a r y am in es a s th er e
are tw o h y d ro g en ato m s av ilab le fo r h y d ro g en b o n d fo rm atio n in p rim ary . T ertiary am in es
d o n o t h av e in term o lec u lar ass o c iatio n d u e to ab sen ce o f h y d ro g en ato m av ailab le fo r
h y d ro g en b o n d f o r m atio n . T h e r ef o r e, th e o r d er o f b o ilin g p o in ts o f is o m er ic am in es :
P rim ary > Sec o n d ary > T ertiary
o o o
T h e b asic ity o f am in es in g aseo u s p h ase : 3 am in e > 2 am in e >1 am in e > N H 3
H
xx +
N + H
+
N

[ Base ] [ Conjugate acid ]

R
T h e stab ility o f su b s titu ted am m o n iu m io n :
+ + +
R NH 2 +
T h e p o sitiv e c h ar g e g et n eu tralis ed b y R HN R NH 3 NH 4
t h e + I e ff e c t o f a l k y l g r o u p s . R R

In aq u e o u s p h a s e th e s ta b ility o f s u b s titu ted a m m o n iu m c atio n d e p e n d u p o n b o th th e +I

e ff e c t o f a l k y l g r o u p a n d s o l v a t i o n b y w a t e r m o l e c u l e s . T h e g r e a t e r t h e s i z e o f t h e i o n
les s er w ill b e th e s o lv a tio n a n d les s s ta b ilis e d is th e io n .
CH3
S o th e b a s ic ity o f m e th y l s u b s titu te d H3C NH H3C NH2
H3C N NH3
am in e s in aq u e o u s p h as e : CH3
CH3
W h en alk y l g ro u p is b ig g er m eth y l g ro u p , 2o 1o 3o
th ere w ill b e s ter ic h in d r a n c e to
H -b o n d i n g w it h w a te r , s o th e s ta b il it y C2H5
H5C2 NH H5C2 NH2 NH3
o f s u b s titu ted a m m o n iu m io n d ec r ea s e s . H5 C2 N
S o t h e b a s ic ity o f e th y l s u b s titu te d C2H5
am in e s in aq u e o u s p h as e : 2o 3o C2H5
1o

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Class-XII Amines
A n i l i n e d o e s n o t u n d e r g o F r i e d e l -C r a f t s r e a c t i o n (a l k y l a t i o n / a c e t y l a t i o n ) d u e t o s a l t
f o r m a tio n w ith a lu m in i u m c h lo r i d e , th e L e w is a c i d , w h ic h is u s e d a s a c a ta l y s t .D u e t o th i s
, n itro g en o f an ilin e ac q u ir es p o s itiv e c h ar g e an d h en c e ac ts as a str o n g d eac tiv atin g
g ro u p fo r fu rth er r eac tio n .
B e s i d e s t h e o r t h o a n d p a r a d e r i v a t i v e s , s i g n i fi c a n t a m o u n t o f m e t a d e r i v a t i v e i s a l s o f o r m e d
d u r i n g n itr a tio n o f a n ili n e .B e c a u s e , i n th e p r e s e n c e o f m i n e r a l a c id s ,th e a n ilin e r e a d ily
fo r m s an ilin iu m io n s . T h e a n ilin iu m io n is a str o n g elec tro n w ith d ra w in g g ro u p , w h ic h
d irec ts th e elec tr o p h ile to w ar d s m eta p o sitio n .
+ -
NH2 NH 3 NO 3 NH2
Ring deactivator
HNO 3

NO 2

A n ilin e is les s b asic th an am m o n ia, b ec au se th e av ailab ility o f elec tr o n o n

xx
n itr o g en ato m o f a n ilin e d ec r eas es d u e to d elo ca lis atio n o f elec tro n b y NH2
reson an ce
I n c a s e o f a l i p h a t i c a m i n e d u e t o + I e ff e c t o f a l k y l g r o u p , t h e xx Aniline
elec tro n d en sity o n n itr o g en a to m in c r ea ses , a s a resu lt b a s ic R > NH2
stren g th in c reases. Aliphatic amine

A m in e s a r e le s s a c id i c t h a n a lc o h o l s , b e c a u s e N -H b o n d is le s s p o l a r t h a n O -H b o n d . T h e r e f o r e , a m in e
r e l e a s e s H + i o n w i t h m o r e d i ffi c u l t y .
A ro m atic am in es are in so lu b le in w ater b ec au s e, th e p h en y l g r o u p is b u lk y in s iz e an d h as
- I e ff e c t . A s a r e s u l t , i t s h y d r o g e n b o n d i n g w i t h w a t e r i s n e g l i g i b l e .
-
M eth y lam in e fo r m s a s o lu b le h y d r o x id e o n r ea c tin g w ith w ater . T h e O H io n s r eleased b y
3+
th e h y d ro x id e c o m b in e w ith F e io n s o f fer ric c h lo r id e to g iv e fer ric h y d ro x id e o r
h y d r a ted fer ric o x id e w h ic h is b ro w n in c o lo u r .
xx
+ -
H3C NH2
+ H OH H3C NH 3
+ OH
3+ -
2 Fe + 6 OH 2 Fe(OH) 3 or Fe 2O 3. 3H2O ( Brown ppt )

Basicity of
NH2 In c a s e o f a r o m a tic am in es , th e b a s ic ity
NH2 NH2
d ep en d s u p on :
NO 2 [ i ] I n d u c t i v e e ff e c t o- > m - > p-
[ i i ] R e s o n a n c e e ff e c t , o b s e r v e d
at o - & p - p o s itio n s.
NO 2
NO 2 o-Nitroaniline
m-Nitroaniline
p- Nitroaniline
T h e elec tro n w ith d r aw in g su b s titu en ts o n ar o m atic r in g r ed u c e th e b a sic ity o f s u b s titu ted
a n i l i n e s . T h e - R e ff e c t o f n i t r o g r o u p i s o b s e r v e d m a x i m u m a t o r t h o a n d p a r a p o s i t i o n s . T h u s ,
m -n i tr o a n ili n e i s r e la t iv e ly m o r e b a s ic c o m p a r e d to o r t h o a n d p a r a i s o m e r s a s it w i th d r a w s
e l e c t r o n s t h r o u g h i n d u c t i v e e ff e c t ( - I e ff e c t ) o n l y . O u t o f o - n i t r o a n i l i n e a n d p - n i t r o a n i l i n e , - I
e ff e c t i s f o u n d t o b e s t r o n g e r i n o r t h o i s o m e r s a s c o m p a r e d t o p a r a . T h u s , o - n i t r o a n i l i n e
e x p e r i e n c e s a s t r o n g - R a n d - I e ff e c t a n d i s l e a s t b a s i c .

S o P K b o f o -n it r o a n il in e > p -n it r o a n il in e > m -n it r o a n i lin e

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Class-XII Amines

B e n z e n e d ia z o n iu m C h lo r id e
NaNO 2 + HCl -
NH2
+ HNO 2
D ia z o t is a t io n
+
N2 Cl + NaCl + H2O

Benzenediazonium chloride
B en z en ed iaz o n iu m c h lo rid e is stab le d u e to r es o n an c e .

C o u p lin g d o n o t H3PO 2
+ +
D i a z o n iu m io n b e in g a w e a k e le c t r o p h ile ,c a n c o u p le

o c c u r in str o n g H2O
H + N2 H3PO 3 HCl

acid ic m ed iu m
+
w ith a s tr o n g ly ac tiv ated ar o m atic s y s tem .

NH2 NH3 CH 3CH 2OH

+
H + N2 + CH 3CHO
+ HCl
H
-
OH

CuCl / HCl
Less Cl + N2
a c tiv a te d
ar o m atic
s y s tem CuBr / HBr
OH O
- Br + N2

-
OH
+
H CuCN / KCN CN + N2

+ -
N N Cl Cu / HCl
Cl + N2 + CuCl

-+
O Na
In s tro n g ly a lk alin e m e d iu m , th e c o n c en tratio n o f

N
KI
+ N2 +
d ia z o n iu m io n ( a c t a s e le c tr o p h ile ) d e c r e a s e s

N
I KCl
an d c o u p lin g rea c tio n d o es n o t o c c u r.

HBF 4 + - D
NaOH N2 BF 4 F + N2 + BF 3

OH

N H2O
N
OH + N2
+ HCl

HBF 4 + - NaNO 2
NaOH
N2 BF 4
Cu D
NO 2 + N2 + NaBF 4

N
H OH
+
N -
N N OH ( Orange dye )
HO Coupling reaction

H NH2 N N NH2 ( Yellow dye )

-
HO Coupling reaction p-Aminoazobenzene

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Class-XII Amines

P r e d ic t t h e p r o d u c t s
NC + 3 KCl + 3 H2 O
NH2 + CHCl 3
+ alc. KOH
?

- + N2 + H3PO3 + HCl
+ ?
+
N2 Cl H3PO2
+ H2O

NH2
NH2
+ Conc. H 2SO4
? HO 3S

-
N2 Cl
+
+ C2H5OH
? + N2 + CH 3CHO + HCl

Br

NH2
+ aq. Br 2 ? Br NH2 + 3 HBr

Br

O
NH2 + ( CH 3CO) 2O ? NH C CH3 + CH 3COOH

- (i) HBF 4 NO 2 + NaBF 4 + N2

?
+
N2 Cl
(ii) NaNO 2 / Cu D

+ -
H3C CH 2 CH 2 NH 3
H3C CH 2 CH 2 NH2 + HCl
? Cl

CH3 CH3
+
H3C N CH3 + HCl ? H3C NH
Cl
-
CH3

P Kb v alu e PhNH 2 > PhNHCH 3 > Et NH2 > Et2 NH

B asic stren g th Et2 NH > CH 3NH 2 > Ph N Me 2 > PhNH 2

B asic stren g th p -T o lu id in e > A n ilin e > p -N itr o a n ilin e

B as ic str en g th in g as eo u s p h as e Et3N > Et2 NH > Et NH 2 > NH3

B o ilin g p o in t Et OH > Et NH 2 > Et 2 NH

So lu b ility Et NH 2 > Et2 NH > PhNH 2

Et2 NH > Et NH2 > NH3 > PhNH 2

B as ic str en g th
+
+ + - + N
+
N
- + -
N N N N N N

+
R es o n a tin g s tr u c tu res o f d iaz o n iu m io n .

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Class-XII Amines

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