\

lliJ \ Compounds Containing Nitroge~

I POINTS TO REMEMBER (a brief concept) I
Nitro Compounds j
Nitroalkanea: Nitroalkanes are the derivative of alkanes or arenes in which one or more hydrogen atoms are
replaced by nitro (-N0 2) group .
The are represented by R - N0 2 , R2 - CH - N0 2, R3 - C - N02

General Methods of Preparation I

(l) From Nitration of Alkanea:

R - HO - N0 2 423 - 698 K l R - N0 2 +
H + H20
(Alkane) (Nitric acid) (Nitroalkane)
(2) From Alkyl halides :
R - X + Ag N0 2 ____,, R - N0 2 + AgX
(Alkyl halide) (Nitroalkane)
(3) From aalta of a halogenocarbo:a:ylic acids:

Cl - CH 2 - C - ONa
II + NaN0 2____,,
I\9 N - C~ - ~C- ON~+
2
7 NaCl~
H20
CH 3 - N0 2 + NaHC0 3
(Sodium salt of (Nitromethane)
a-chloro acetic acid)
(4) From O:a:idation of Amines:
R R
I KMn0 4 I
R - C - NH + 3(0) R- C- NO + H 2 0
I 2 I 2
R R
(tert-Alkyl amine ) (tert-Nitroalkane)
From Hydrolyals of a-Nltroalkenea :
C~ CH 3
I H+ or OW I
CH 3 - C = CHN02 + H20 _ _ ____,, CH 3 - C = 0 + CH 3 N0 2
(2-M ethyl-1-nitropropene) (Acetone) (Nitromethane)
(6) From O:a:idation of O:a:imes :
0
(0) I
R- CH= N - OH R CH = W - OH ~ RCH 2No 2
(Aldoxime) (1° Nitroalkane)

R
•
R
)c= NOH (0)

(Ketoxime) (2° Nitroalkane)

Reactions of Nitroalkanes
( 1) Reduction:
IH] IH] !Hl
R- N0 2 -Hp R-N=O ~ R - NHOH R - NH 2
-Hp
(Nitro- (Nitroso- (Substituted (1° amine)
compound) compound) hydroxylamine)

(2) Hydrolyai1:

• R - CH 2 N0 2 + H2 0 RCOOH + NH 2 0H
(1 ° Nitroalkane) (Carboxylic acid) (Hydroxyl amine)

{676)
 unds Containing Nitrogen
corrtP0 677
R
I R
2R - CH - NO 2 HCJ or H2SO4 I
• (2° Nitroalkane) I\ ~ 2 R - C = 0 + Np + H2O
. (Ketone) (N " .
Tertiary mtroalkanes are ttrous made)
1 , generally unafli t d
1

aaJogenation: ec e by HCI acid

j (3) H
: I Br
2R-? - N02 + 2Br2 + 2NaOH ~ I
H
R - NO2 T-
+ 2NaBr + 2H 2O
(I° Nitroalkane) Br
(Dibromo derivative)
R
I R
2R - ?-
N02 + Br2 + NaOH ~
R-
I
T-
NO2 + NaBr + H2O
H
(2° Nitro alkane) Br
(Monobromo derivative)
J

141 With Nit:u• acid:

0
I I ,f H 0
R - C - N+ I
J "-o-
+ HO - N - O
- ~ R-C-W
I
NO
,f
"- -
O
+Ho
2

(1° Nitroalkane) (Nitroform)

it
R - C = N/
OH
+ NaOH
I "-o
NO
(Red solution)
(Aciform)
(Blue Solution)
R R
I .fo I .fo
R-C-N + HO - N = 0 ~ R - C - N
I "-o I "- o
H NO
(2° Nitroalkane) (Blue solution)
• 3° Nitroalkane + HNO 3 ~ No reaction
(S) Condensation with Aldehydes and Ketones:
H H
I KOH/C2H50H I -H 0
C6 H5 - C = 0 + CH 3 NO 2 ----'"------\ C6 H 5 - C- CH 2 - NO 2 ~
I t.
1 (Benzaldehyde) OH
;1+ Amines I
I. Amines are the alkyl or aryl derivatives of NH 3 in which one, two or all three H-atoms attached to N-atom are
replaced by same or different alkyl/aryl groups.
• Aniline is an aromatic amino compound in which the nitrogen atom of amino group is directly attached to aromatic ring.
General formula ----1 CnH2n+3N

N. atom of NH 3 ----1 s p 3 hybridization

Pyramidal structure (sp 3 hybrid orbital= lone pair of e-)

Bond angle= H - N - H, C - N - Hor C - N - C is less than 109°28'

3
Nitrogen atom in aliphatic amines = bonded sp C
2
Nitrogen atom in aromatic amines = bonded sp C
Nucleophiles (Lewis base)

----....:,,. It forms coordinate and coordinate covalent bonds.

 Uttam 's MHT-CET (Cherni.i·try;

678

Classification of Amine~=:] N ber of R/ Ar

b don um
(A) Classification ase \ - - - - - - -- - -· ~
\
::[; 3° amine
2° amine CH 3
1° amine
C 2 Hs"-., I
e.g. CH 3 - NH2
NH e. g . CH 3 - N - CH3
(Methyl amine) e.g. /
C2H s (Trimethyl amine)
(Diethyl amine)
types of R/ Ar
(B) Classification base d on
I
~ Mixed / Unsymmetrical amines
Simple ; Symmetrical amines (R or Ar different)
(R or Ar same) e.g. CH 3 - NH - C2Hs
e.g. CH 3 - NH - CH 3
(Ethyl methyl amine)
(Dimethyl amine)

IUPAC name
Compounds Common Name
Alkanamine/N-Al 1 alkanamine
Al 1 amine
(a) 1° Amines:
Ethylamine Ethanamine
( 1) CH 3 CH 2 NH 2
Isopropylamine Propan-2-arnine
(2) CH - CH- NH 2
3 I
CH 3
CH = CH 2 Allylamine Prop-2-en-1-arnine
(3) H2N - CH 2 -

(4)
@'NH, Aniline Aniline (or) Benzenarnine

@'CH,NH, Benzylamine Phenyl methanamine

(5)

(b) 2° Amines:
( 1) CH 3 - NH - CH 3 Dimethyl amine N, Methylmethanamine
(2) CH 3 - CH 2 - NH - CH 3 Ethyl methyl amine N-Methyl ethanamine
(3) C 6 H 5 - NH - C6 H 5 Diphenyl amine N-Phenylaniline
(c) 3° Amines: ..,
( 1) CH 3 - N - CH 3 Trimethyl amine N, N-Dimethyl methanamine
I
CH 3
(2) CH 3 - N = C2 H 5 Ethyl dimethylamine N, N- Dimethylethanamine
I
CH 3

(3) C 2 H5 - N - C2 H 5 Diethyl methyl amine N-Ethyl-N-methyl ethanamine

I
CH 3

(4) C6 H 5 - N - CH 3 N-N-Dimethyl aniline N-N-Dimethyl aniline or

I N, N-Dimethyl benzenamine
CH 3

L
 Containing Nitrogen
,i,,,,pvii"'is 679

.~ ods of preparation of Amin~

- tbod•
! I &{e
Reaction
i frOIXl .Alkyl halidea
R - X + NH 3
'I (ll (BYAmmon olysis ) Pres s u re 373 K R - NH 2 + HX
Alky l (ale. )
h a lides (1 ° a mine)
* R - NH 2 + R - X ~ R - NH - R + HX
(I o a mine) (2u a min e)
R

R - NI - R + HX
* R - NH - R + R - X tJ.
-=-)

(2o amine) (3o- amine)

* R3 N + R - X ~ R4 Ntx - (Q uaternary ammonium salt)
* Reactivi of al I halides - RI > RBr > RCI
From Alkyl Halides 0 O 0
121
(Gabriel Phthalimide II 11 11
synthesis)
©C
C °"

c/
N- H K~H
ac .
rc3Y \ -
~
C

c/
K ~ (8y \ - R
~
C

c/
II 11 11
0 0 O
(Phthalimide) (K-salt of phthalimide) (N-alkyl phthalimide)
0

cII - ONa d
NaOH
I

,I ©C C - ONa
II
+ R- NH 2
(1 ° amine)
aq.

0
* Advantage: Over alkylation avoided.
* Limitation: Can't prepare aromatic amines as aryl halides do n
unde bstitution.
From oximes, Al anides, amides and Nitr reduction :
(a) From oximes - H

* R- J= N - OH + 4 [HJ Na /e thanol R - CH 2 - NH2 + Hp

(Aldoxime) (1 ° amine)
Na/ ethanol
* R - C = N - OH + 4 [HJ R - CH - NH 2 + H 2 0
I I
R R
Ketoxime 2° amine
Na /ethanol
(b) From * R- C =N + 4 [HJ R - CH 2 - NH 2
Alkyl cyanide s / (Alkyl cyanide) (1° amine)
nitriles -
LiAlH 4 / diethylelhe r
(c) From Amide s - R - CO - NH 2 R - CH2 - NH 2
(Amid e) 1° am ine
Sn / con e.
(d) From Nitro
Compounds - ~ R - NH
R - N0 2 + 6[HI 2 + 2H 20
O
(Nitrocompoun ~ (I a mine)
Ether
(e) From Amide -
* R - CO - NH 2 + Br 2 + 4NaOH ~ R - NH 2 + Na2 C0 3 + 2NaBr + 2H20

(By Hoffmann (Amide) (Amine)

Bromarnide de adation
 680 Utt am 's MHT-CET (Che ... .
.. ,1s1ry)

Lower aliphatic amines are colourless

Order of BP of iso meric a mines I" > 2" > :r gases with fishy odour.

B.P. of a mines are higher th an a lkenes ,____-;, Amines with three or more C-atorn
but lower than a kohols a nd carboxy lic are liquids while higher are SOlicla.
acids.

Soluble in ether. a lcohols. benze ne s Pure aryl amine are colourless

liquid oxidized by air to get
Aliphatic amines - upto 6 -carbon atom are
soluble in H2O (Hydrogen bonding)
Reactions of Amines I
(1) Baaic nature:
• Amines donates lone pair of electron, hence are lewis bases.
• Also it accepts proton from acid, hence are Bronsted Lowry bases.
+
R- NHl t HX ~ RNH3X
+
RNH3X ~ R - NH 2 + NaX + H O
2
(I° amine)
• Amines are weak bases
R - NH2 + H2O ~ RNH3 + OH
(Weak base) (Strong base)
(2) Action of nitroua acid:

R - NH 2 + NaNO 2 + 2HC1 ~ [R - N2Cl] + NaCl + 2H O

+ -
2
(l°amine)

R - N2Cf + H2O ~ R - OH + HCI + N2 f

(Alcohol)
• NaN0 2 + HCI
~NH + HO - N = 0 273 _ 278 K ➔ R 2N - N = 0 + H O
2
(2° amine) (N-nitroso amine)
• R3 N + HNO 2
NaN02 t HCI
273 - 278 K > [R 3NH] + NO~
(3° amine)
(Nitrite salt)
(3) Acylation of aminea:
H 0

l
I II
R- N:
I
+ Cl - C - R
(Aoid
-----i
7I ?I ]
R-N-C-R
l
0
II
~ R - N - C - R + HC!
H
chlori?e) H CI I
(Amine) H
(4) Alkylation of aminiea: (Amide)

R- NH 2 R- X R2 NH R- X
- HX > R3 N R- X +
(1 ° amine) - HX
(2 ° amine) HX ➔ R2NX -
{3" amine)
(Tetra-alkyI
(5) Hoffman elimination: ammonium halide)
+ +
c 2H5 - N(CH 3 b r + AgOH A!½o ~ H2o C2H
5- N(CH J oii + Agl
33
+ l\
C2H5 - N(CH 3b ow~ CH2 = CH2 + (CH3)3 N + H2O

(Ethylene) (Trimethyl amine)

ma·or minor
 d Containing Nirrogen 681
·)IIIP011n J
,,
I
161--,;;.;
f{OffJllall
Carbylamine teat /
~
Iaocyanid t
e e■t.
.
t-H-I 2 + CHCI] + 3KOH ~ R _ NC + 3 KC
R- • I + 3H 2 0
(Alkyl isocyanide)
0
0
1~~ -
111 \J
0
11
Cl + H - N - C.., H

H
I - s ~
0- 11
S - N - C H + HCI
II
0
2 s

(Benzene sulphonyl (Ethyl

(N -Ethylbenzene sulphonyl amide)
chloride) amine)
g1,ctr0philic aromatic substitution:
181 (al sromination -
'

r6'
(Aniline)
+ 3 B,,
Br2 water
NH2

V
BrJyBr
+ 3HB,

Br
(2, 4, 6-Tribromoaniline)
(o} Nitration -

J:2
6'
(Aniline)
Cone. HN0 3 /conc H2 S0 4
288K

NO 2
+
UNO 2
(m-Nitroaniline)
+
lJ
NH 2
h N 02

(o-Nitroaniline)

(p-Nitroaniline)
(c} Acetylation -
0

6 '
II
¢~OCH, ¢'
6'
NH - C- CH

(CHF0}20 Cone. HN0 3 / cone H2 S0 4 H' o,OH

Pyridine 288K
(Aniline) (Acetanilide)
N02 NO 2
(p-Nitroacetanilide) (p-Nitroaniline)
(d} Sulphonation -

(Aniline)
(Anilinium hydrogen
Cone. H2 S0 4
(453 - 473}K
·¢' S0 3 H
Sulphate) (Sulphanilic acid)

IN
®o·
"Preparation of Diazonium Salts
+
J

-
iazonium salts have general formula ArN 2X
wheile, Ar ~ aryl (- c H ) group and X ----t er, Br-, i-, NO 3 , HSO~ , BF; .,etc.
6 5
® Aromatic primary amines (aryl amines) on reaction with nitrous acid in cold , forms arene diazonium salts . This
reaction is called diazotization reaction.

Q
+ -
NH 2 1

6
(Aniline)
+ NaNO, + 2HCI
(273 - 278) K

(Benzene diazonium chloride)

+ NaCl+ 2Hp
682
U1tam 's MI-I T- CET (Chernist

,---__ - - - --
-
-
t-- __ Method r --
Reactions
~ - ~ l~~ement of Dia!_~nium gro l!_P..:__
( I ) Re pl a ceme nt by
- - - - - --
* Sandmeyer reaction:
- C l, - Br, - CN + CuCI/ HCI
Ar N2 x - Ar - Cl + N2i
+ CuCN/H CN
Ar N2 x - Ar- CN + N2i
* Gatterman reaction:
+
Ar N x - Cu/H CI . Ar
2
Cl+ N2i
(2) Re place ment by - I +
Ar N2 x - + KI ~ Ar - I + N2 + KX
+
ArN X- HBF4 Ar - ~ 2 BF4 ~ ArF + BF 3 + N2j
(3) Replacement by -F
2
(Balz Schiemann
reaction )
(4) Repla cem ent by - H Ar - N; x - + H3 PO 2 + H2O ~ ArH + N2i + H 3 P0 3 + HX
(Re duction)
Ar - N; x - + CH 3 CH 20H ~ ArH + N2i + CH 3 CHO + HX
(S) Re placement by
Ar - N; x - + H20 dil H2S04 , Ar - OH + HX + N2
OH
(6) Replacement by
HBF4 C H N BF Na N0 2/ Cu
- N0 2 C6 H 5 - N~x - 6 5 2 4 l'l
C 6 H 5 N0 2 + NaBF 4 + N2

2 + Ar' H ~ Ar - N = N - Ar + H+
(B) Coupling Reaction ArN+X
(Azo coupling):
(Azo compound)

e .g . Q-N= NCr + Q -oH__()l__l_:_, 0 -N N-Q--oH + HCl + H,0

a

(Benzene diazonium (Phenol) (p -Hy dro>..'}'azo b enzen e)

chloride) (Oran ge d ve )
Importance of Diazonium Salts:

Oiazonium salt a re s trongly coloured like Used for pre paration of all p ri m ary
red, orange, yellow, blu e a nd a re u sed on a mines .
dye.
Importa nce
Used in synthesis of organ ic
of
compounds.
Diazo niurn sa lt

The compound whi_c_h cann~t b~ prepared / They are inte rmediates fo und which
by direct electrophil1 c sub st1tut1on ca n be can be used to introdu ce gr. like - CN ,
pre pared by re place ment of di azo group . - OH , - C l, - Br, -F in a romatic ring.

ooo