Organic compounds

containing Nitrogen
· Amines
·
Diazonium Salts
·

Cyanides & Isocyanides

·
Nitro alkanes

Nitro benzene
·
 Amines:
>
-

Amines are regarded as derivatives of ammonia in

which one , two or all three

hydrogen atoms are

replaced by alkyl or anyl group

.

+R

NH3 RNH2NHRN
1 amine 2amine 30 amine
Ammonia

curence : Occur in nature in proteins ,

vitamins, hormones &

alkaloids .

Uses Adrenaline
: & Ephedrine -
20 Amino group . (used to Blood pressure)
Antihistamine drug-Benadryl -3
°
Amino
group.
(treat allergies
Quaternary AmmoniumSaits -
Surfactants

Novocain -
Anaesthetic in dentistry

(synthetico acid)
Momenclature :

NH

e
10 amine 20 amine 30 amine
it
-Me
R-NH2 R-NH-R
R-R
Aniline 2-Methylaniline
CECH NA
Ethanamine
CH-NH-Ctb
N-methyl methanamine
ab-ab (or)
Benzamine
o-Toluidene

N-Dimethyl methanamine
(Ethylamine
N,
NH2 Ne

#
(Trimethylamine)
Cr-CHCR-NH2 C1-NH-c-c-r
- N,N-Dimethyl
Propanamine N-Methyl propan-l-amine benzeneamine
(Propylamine) a N-Ethyl-N-Methyl 4-Bromo aniline
(methyl
propul amine propan-l-amine p-Bromoaniline

CH-CH- Ct-NH-CH-CH Me-N- Me

Propan-2-amine in Me IN -H

Azimidine
N , N-Diethylbutan-1-amine
N-Methy propane-2-amine
(Isopropylamine)
ENU
Prop-2-en-1-amine
(Allylamine)
 NH-CO- CH NHz ↑
it
E
N
E - #
/
D

Acetanilide Cyclohexanamine N,
N-Dicyclopropyl
cyclopropanamine Piperidine

Structure :
wi

N Not C Sp3-spa
a

-
u
Sp3-sp3a

somerism, ula :
Cntan 3N +

(1) I somerism
Functional :

3 Functional Isomers .
SHgN represents

#Not +
1 NE
Hsa
+ CIN
n-Propylamine
41 %
Ethyl methyl methylamine
amine
(2) (39

(2) Chain Isomerism : (difference in carbon skeleton

of alkyl group attached to amino group .

-NB -+
((yH ,, N)
Butan-1-amine 2 -

Methyl
propan-l-amine

(3) Position Isomerism :

NB
-Ny (CHqN)
n-Propylamine Isopropylamine
Propanamine Propan-2-amine
(4) Metamerism :
diff alkyl groups attached to same functional group .

-Ni VNW KyHN]

9/p Write Isomeric amine with formula
CHgN.
"
.C
4
2 3
/NB
.B m
Ans
NH2
CH
.

N
n-Propylamine
opropylamine Ethyl methylamine
Trimethylamine

alp write s Isomeric amines with formula

C4H , N.
Aris
(i)
10 NA
()
(ii)
XM . (vi) - No-
20

(iii) (vii)NH-X
(iv) + Nr (viii) -
N-

,
o
30 L

:
Amines with diff substituents CHRAL 2013 Exhibit
on N are ,
Optical activitya

Unlike chiral carbon

compounds, most chival amines cannot be

!
is
resolved . Swo

another by process-
Enantiomeric forms

Nitrogen (b) Amine

rapidly interconvert

Inversion · (known
into

as
one

Flipping)

N 17
R2 Ry
IRz
R3
I

Planar
transitionne #I

Enantiomers .

9/p 5 Isomeric of Benzene

amines
CHAN containing Ring
.

(i)N (ii als (iii)Ne

a (v) UN-CH (1) CE-NHz
I
F Tl
an
2
Methylbenzene 3-Methyl N-Methyl
4-Methyl Phenylamino
amine benzene amine benzene amine methane
benzene amine
 Methods of preparation of Amines :

(1) Reduction of Nitro compounds :

(a)
Pd/Pt/Ni
Reduction in acidic medium : RNH

GIM)
or
a
R-NO2 +
RNa

Eq
: (H)
FeCI

at
RNO
Nitrobenzene

(b) Catalytic hydrogenation

⑭
:

R -

NO +
3 H
/Pt
, R -

NH +
210

CHz-NO + 3+ -
CHNHz + 2
Ho

(2) Reduction of Cyanides (nitriles) : -

R-CENO Ron ine

NaCHg)/EtOH
Mendius reaction

CHICN * CHICHINt
Acetonitrile Ethyl amine

II

CHyCN >
CHICHNt

Benzonitrile Benzylamine

(3) Reduction of Isocyanides :

(Isonitriles)

RNEC
therCoRNH containing
linked to
-

CHz Nitrogen .

IHCH3
ty pot
-
 (4) Reduction of Amides :

R-NH (Amides
R-*-N + +
4)
ther R-CNTo R CH
-
= N OH
-
(Oxime)
LiAIH4

to
>
RCHINty
R-CHINz (AZIDES)

cab--NH 1 &>
-P
Eg :
+ 4 (t) -
CHICHNt
+
HO R-CH2Nt
* cetamide
Ethylamine
O

CHy-C -

NH + 4(H) CHyCHzNtz

Benzamide

(5) Hofmann's ammonolysis of alkyl halides :

X +
NH-RRN + Nu

RNHN A N In
1amine 2amine 30amine Quaternary Salt

16
Hoffmann'sDromamideDegradation Reagent Nate i
:

Naobs

only 20 amines can be prepared

-

aromatic
Caliphatic &

RCONH + 4 NaOH +
Br -RNA +
NacCo + 2NaBr +
240
* mide Amine
(19
(1 c less than amide)
Egi
CH--NH2 B CNA
(22) (12)
n NaOH + Brz
-
EtNub
CH-c-c-NUBr A
CCCN
Aniline

Butanamide Propanamine
(UC) (3C)
N with 1
bond &
2 Nonbonding
Mechanism :
epairs

R E Re R ↓ it rene

Cotr
R
lamine
 (7) Gabriel phthalimide reaction :

be
only aliphatic 10 amines can
prepared.

#
phthalimide

a I
pot.
salt of
phthalimide
phthalimide

# mine

Aromatic1 amines can't be prepared by this method .

· C-X Bond in Haloarene possess partial double bond character ,

: Phthalimide anion can not break C-Xbond in Haloarene .

(8) Schmidt Rearrangement :

NIH [instead useIt

be

C
RCOOH ,
+ mixture of NaNz + Conc thsoy can

of Ng + con.
oa
Carboxylic Hydrazoic
acid acid

(9) Lossen Rearrangement :

R-Coon
R-N-OIR-N )
R-NO R
=

Carboxylic (0) Isocyanate

acid
Hydroxamica
(10) Clitius rearrangement :

Road a

(11) Reductive amination of aldehydes & Ketones :

R- = 0 +

-Nr]See
 Roth Dialkylketimine iamine

NOTE :

If primaryamine used instead of Ammonia ,

20 amine obtained.

+ -CNN
N-isopropyl aniline
(20 Amine)

(2) From alcohols : (Sabation & Mailhe Method] [Industrial Method

EtOH +
HNB ENR EENU
OM LElamine
Diethyl
Ethyl amine
amine

Three amines mixture separated by FRACTIONAL DISTILLATION.

alp

t C

·,
"

t
CH B

d EtMgc + cl-NB- >

EtNE +
MgC

Ans .

Q ②
M Brc
A
/N
.

A
.

B . CN
lot P .
CONTE
E
petab
B .

"
-Tur
⑬
A
. EatCood
MBr D

B i
NoH .
.

Na
E

c .

Mor F .
/NB
 Physical properties
:

H-Bond
Lower aliphatic amines gases fishy odour
>
-
-
·

aliphatic amines with 3or more C atoms-liquids -------H-

↑ Ni--H- R
R
solids
Higher members
· -

colored due to atmospheric oridation

Aniline-colorless liquid-gets
.

Bp + 12 % 30 (1920 have more B P

.
due to
H-Bonding)

· Amines >
- Soluble in Ho (H-Bonding)
solubility ↓ with ↑ in molecular mass .

=> Basic Nature of

mines :

Lewis Bases
donate L.p of
Nitrogen
>
-
.

strength of
Kob
Base x

RNA EN + Oh

Let
"D =

* Basic nature of amines can be explained by three factors .

(1) Inductive Effect :

C + I Effect)

N 20 amine lamine
3amine

:. Basic nature of amines in

gas phase (or)
in
non-polar solvents :

3> 2 > iamine [due to +I Effect of

alkyl groups (e-donating]

In aqueous solution ,
steric factor & Hydrogen Bonding also influence basic nature of amine .

(2) Hydrogen bonding

to
:

R-N2 +

forms more no of H-Bonds

protonated Famine
.

->

: More E is released.

to
Hence more stable product obtained.

R +

protonated 20 amine
 + BRoamine
(forms less no of -Bonding as

... Basic Strength order

10 20 30 amine
as
per H-Bonding : > >
°

11 - 20 x 1 = 3
7 NH3
lay)
Seaic
factors
Bulky alkyl groups hinders the donation of LP by Nitrogen Cr -3032"-i > N13

:.
<
gas]
onl
Basic nature based
: 17273° amine
205
-2338-1 >
NHz
steric factor
aq

=> In aqueous solutions , net effect of all the above three factors to be considered.

:
Resulting order of basic nature in 20 301amine
TS
ag solutions : >

this valids all aliphatic amines

, Except Methylamines .

Eg
(2H5]N >
(GH5)N >
(H) NH e
20 30 10

(i) Steric factor is negligable

for Methyl amines , basic nature follows the order ,
27 (ii) H-Bonding is more in 10 amines .

*
Anylamines are less basic than alkyl amines due to involvement
ofLip of Nitrogen is
withFe's of
delocalization Benzene Ring
. Hence Lp is not
freely available for donation . (-I Effect of
phenylgp)

t
Anilinium ion
Aniline
(more stable) Cless Stable)
5 Resonating 2 Resonating
structures structures

t
ResonatingStructures of Aniline = 5

Y
⑦

Resonating structures of Anilinium ona

Anilinium
ion

Basic nature of Amines in

agsol" :

20 > 30 > 10 >

NH> CUNt2
Aniline .
 Acetamide - Show Basic
does not nature .

Up N is delocalised by Resonance
cr
of
Chi
on

o
so less for
available protonation .

Basic nature < EDG (+ I & + M

Effect)
EDG >
- Stabilizes cation , & ↑ Basic strength
G distabilizes cation
ENG >
-
,
& ↓ Basic strength
(withdraws ef

Eg :

i
NH2

R-NHz < NHz

>
- *
un

+I

NH
Aromatic
NH-"C-NH2 aliphatic
a
HN - CH3 <
>
NHz >

amine amine

Guanidine
Highly Basic
(Steric Repulsion)
No Resonance

> Lik I 0 O
Anas DN-n
#
>I T
Piperidine
it
Pyrrole

Bridged N
Na
is more Basic E >
M
cone
·a
Lip of Nitrogen
ENH NE >
- EWG
should involve in

E 7
d elocalisation to
Aniline
N-Methyl Benzamide aromaticity
Benzylamine N,
N-Dimethyl aniline (Resonance)
get

(Aliphatic) aniline (Gret

(Resonance)
(Resonance)

Ortho Effect :

Ortho substituted anilines less basic irrespective of o-position .

are
always group present at

·
Eg
.2 .

I Mi
a
P-Toludine o-Toludine
- NO
(Hyper ,
0-Nitto aniline
[I)
Conjugation) Aniline
9 which one is more basic in blu Aniline & Benzylamine ?
A
10 . .

mine
Basic
Strength :

HC-H-Nin <
H =

CANR
> HCEC
Sp3 Sp >
- 50 % S character
>
- more E N .

=>
eactionwithais,Ex ammonium halide
Alkyl

CENU + HC1 >

-
Anci
Methylammonium chloride

-Ne + - >
Enz
Anilinium chloride

=>
kylation (Hoffmann's ammonolysis)
:

RX
RNH2-RyNH >
E Ru -
RX

lamine 20 amine 3° amine QuaternarySalt.

Eg
H
:in & a

N-Methul N , N-Dimethyl
Aniline Trimethyl
aniline aniline anilinium iodide

clation
=> :

Cr Col
clER R-NH- -R + HC ag NaOH
NH--CH3 N-phenyl acetamide
RNA
>
-
.

it
=

I
Acid chloride Schotten-baumann (Acetauilide)
reaction.

CN
+ -21- >
C-NH H--CH5
N-Methyl acetamide d Benzoylation
Et
(or) N-phenylbenzamide
N-Methyl ethanamide (Benzanilide)
NH- CH3-

10,
I

Acylation &
Benzoylation of phenol &
↓ (Acetanilide)

Aromatic amines (1192 >

- Scholten-Baumann Real
 (Scholten-Baumann Real
mechanism
:

Ar-Nitr
H i Ar
=> Carbylamine
-
reaction (Isocyanide Test) :

(shown by all lamines Caliphatic & aromatic

· (C -
> Reaction Intermediate

RNH2 +
CHCb +
3KOHa
>
- RNC + 31C +
3H0
Isocyanide CoffensiveSmell

CHINA +
CHC + 3 KOH
Ca-CINEC 3kC +
+ 310

Methylamine
(i)

NEC

+ Cha + 310H -
# + 34C1 +
310

Aniline Phenyl Isocyanide

(10)

=
eaction >
with Nitrous acid:(HNO) :

(NaNo HC) +

*>
NotHa
I
ROH N2 + HC
RNM
+

Alkyl diazonium Alcohol

Alkulamine
chloride
(10)
Cunstable)

CHICHINE >
-
NaNOHC
Ch EtOH + N2 + HC

Ethul amine Ethanol

(10)

CHCCN NO C CH -

OH + N2 + Ha

n-Propylamine HIsopropyl
(10)
C -
⑦
2+ -

c
alcohol

1 carbocation &oCarbocation

# "Thermann's
nitroso reaction (Shown by : 20 amines ,
forms Yellow oily nitroso compound)
MO N =0-
RaNH +
RN-N
= 0
-

Nitrous acid Liquid)

2 amine Nitroso comp (yellow oily
# I (shown
Niazotization :
by only aromatic lamines
i
NaNH
-
0-5%
+ Nac + 2
Benzene
diazonium
Chloride
* *

(CSO
=> deaction with Benzene sulphonyl chloride
* :

beng's reagent Luseful

.
to distinguish 19293amines
-
- GH5-R-mR
(i)
H BR .

R -N-H
.

a NaOH
-

+
soluble in
# i -
Compound-- >
alkali
I
10 amine acidic 20 - NaOH

H
N-alkylbenzene Compound ->
insoluble in

sulphonamide 30 >
No reaction
alkali

alkali)
.

(soluble in

(i) R N
-
-
H +
- -

GHy
-

R-insoluble in ak a

20 amine N, N-Dialkyl benzene

sulphanamide
R

(iii) R-N +
- X -

30 amine

=>
Electrophilic
substitution reactions of Aniline :

Nr is o-9p-directing & Ring activating group.

Br
me
3 Bra
~

e
directing
Be 2, 4 , 6 - Tribromoaniline (white ppt)

-
e
Anilinium
hydrogen sulphonalidid Twitterion
sulphate
(p-Aminobenzene (Dipolarion)
sulphonic acid)

conc

CONCHNO3
B
so -
-
No M- Nitro
-Nitro
aniline aniline
P-Nitroniline
(51 % ) (47 %) (2 %)
 >
Bra
i oriont -

I
CBCUH
-

P-Bromoaniline
P-Bromo

-
acetanilide (major)
(major
pyridine

is Noz
P-Nitroaniline

Aniline doesnot undergo Friedalcraft reaction (auylation & acetylation) because

of salt formation with AICI

CHINH
+
AICI- >
CHAICT

Nitrogen of aniline aquires +re

charge ,
acts as strong ENG ,
It reduces e-density in benzeneGing & deactivates it .

Hence aniline doesnot undergo Friedal craft reaction.

Reaction with
Reagent
Grigh :

&

H
R -

N -

H +
RMgX - RH +
mg/2
RNH +
RMgX-R-H +
MgN
3 aliphatic amines do not react with G .
R &Absence of I attached to
Nitrogen atom)
reason

Salts
zonium :
(GH
Eg :
GHyNc
Benzene diazonium chloride
⑦
N22Diazonium group Ne Better leaving group
* ci , Br, I,
-
N, HSOr ,
BEY etc.

Aryl low Jemp (0-5 )

%
diazonium salts are stable at due to Resonance .

⑦
N=N
S
⑦
N=N GEN

N
Preparation : Diazotization .

t
Nthotc Mt
Chemical properties :

r
[

#za
l
-
-

SH,
I
# warm

content

>Baschimanurea
-
HBF4
+
N+

+ +
2
H (Replacement

3
by -

Replacement

(Replacement
by H
:
OH)

by - su)

-NE
Benzene

fluoroborate

(Stable at Room T)
(insoluble in to

Y p-HydroxyazobenzeneCoupling
alkaline reactionsset

MINN
acidic P-Amino azobenzene
(Yellow dye)

Colour of due is due to extended

conjugation.
 Cyanides & Isocyanides

Hydrogen Cyanide Exist as a Tautomenic mixture Commen Name : Alkyl cyanide

IUPAC name :
Alkane nitrile
H-CNH-NEC
[In naming Cof-CN also countest
R -
CEN = R- NEC

Alkylcyanide Alky Isocyanide

Common Name IVPAC name

Common Name IVPAC name

Methylisocyanide Methylcarbylamine
CBCN >
- Methyl cyanide Ethane nitrile CNC -

(Acetonitrile) (Methyl isonitrile) (Carbylamino methane

CHzCN- Ethyl cyanide Propane nitrile

CHIN ->
Ethylisocyanide Ethyl Carbylamine
[propionitrile) (Ethyl isonitrile) (Carbylamino ethane)

Separation
Methods :

reaction of
I Grignard Reagent with cyanogemhride :

RMgX + CICN >

- RCN +
Mg(X)4

Eg CrMgBr
:
+ CON- >
CrCN +
Mg(Br) Cl

Tudehydration of Aldoximes
(2) :

R-CH =

N-OHEOR-E R-CEO
CH-CH
= N-OH
-C-CEN

tohavea
3)

(major

(major

Reaction [Isocyanide Test]

(4 -bylamine

Ar-NE & 2-NAL

CHCIz + KOH KC
CBNA + >
-
Cl-NC + 60 +

(5) meyer reaction

-and Mattermann reaction

a
(6) RCOOH +
NH- >
RCOONER
Choo NH
- CON I a
+

acetate
 Physical properties :

B .

p : RCN > RNC (dipole moment)

4D3D

RCN : Lower members -

soluble in to

RNC : soluble in organic solvents only

Chemical properties :

(1) Hydrolysis :

-conc acid partial hydrolysis

R
>
-

(a)
R-CEN RoO
_
dil acid Complete hydrolysis
>
-

(b) Isocyanides undergo hydrolysis only in acidic medium to form lamine & Formic acid.

R-NEC +
H-RNA + HLOOH

lamine ForMicACID

(2) Reduction :

R-CEN + 4CtR-CHINE ,0

R N
-
=c + 4(H) R -

NH-CH3
20

Stephen reduction reaction .

Such
R-CEN- R-CHENH EDRCHO + NB
HCI

(3) Reaction with Grignard Reagent :

R-CEN +
RMgX- > R- NMgx R-R
=

Ketone

H-CN +
RMgX >
- H-Ec vMgXERcro
=

Aldehyde

(4) Oxidation :

RNC +
HgO >
- RNCO +
Hg

CINC
+
HgO >
-
CLINCO + Hg
Methylisocyanate
MIC

NITRO ALKANES:
#TROBENZENE

RCH
RN
R
CHz-NO2
-

NO2
R-N
-

&

o ambident group R-O-N = 0 =

R 20 Nozz
Nitro alkane Nitroalkane
Nitro alkane
RONO >
-
Alkyl nitrite Alkyl nitrite Nitro alkane

CHz-ONO-> Methyl nitrite

No
NO2

e 2-Nitrotolene 1
TotNO2
3-Dinitrobenzene
Nitrobenzene ,
 Isomerism :

1 .
Chain Isomerism :
15 ( C
-

C
-

No
-

aNo
1- Nitrobutane 2-Methyl-1-nitropropane

.
2 Position Isomerism : NO Y
1- Nitropropane . Nitropropane
2

.
3 Functional Isomerism : ~
No2 On = o

Nitroethane nitrite
Ethyl

Preparation :

AgNOz CHICHNO2

-T
major
Hy-( +y
CHICHONO
major

Ct-CHHNO Cr-CU >

+
CH Cfragmentatione
2

Physical properties :

Nitroalkanes are colorless , pleasant smelling liquids.

soluble in
organic solvents
,
less soluble in
tho

Chemical properties :

(1) Reduction :

NO
Ethanamine

C+
> -Cr-NH
Ethyl amine

(2) Hydrolysis : 1920 Nitroalkanes undergoes hydrolysis in Basic medium

10 Nitroalkanes oridation in
undergoes Acidic medium.

R-C-NO2 R-NO Ron

aldehyde

R-CH-NO R Not
Il

>
RCOR +

Ketone

R-CE-NO2 RNO Ron + NO

2

(3) Action with (Victor Meyer's Test) Refer prop of alcohols .

HNO2
>
-

(4) Halogenation :

CBNO On
NO
chloropicain/
Nitrochloroform (Teargas)
 CRENO
lon
-N
C-c-No
+

Nitro ethane

(lonitro paraffin)

(5) Acidity : (Nitroacanes with all show tautomerism

N
0

Nitroform Aci-form
C =
NO C
=
N
[Nitrolic form) Faci form exists
(Pseudo acid form)
strong acid mainly in alkali (NGOLD]

=> No tautomers

C
10920 Nitroalkanes -

weakly acidic due to Jautomerism .

Acidic character of 1920 Nitrocompounds is attributed to stabilization of carbanion .

B u tthese compoundsbehea
of strong alkalies .

(6) Action of heat :

R-CH-CRNOBR-CH =
CH + HNO

CrNO2 - N +
2002 + 312

(7) Condensation with aldehydes :

CH-C
= o +

-No
B t -CH,

Distinguishing tests for 10 , 20 30

,
amines :

(1) [Reaction
Hoffmann's mustard oil reaction with
CS2 followed by Hg <2]

10 amine 20 amine 30 amine

R-NH S
+ c= S
c S
RNH + S
RN S
= = =
+ =
CES
10 20
↓ ↓ ↓
NHR
SRSH No reaction
S = c -
SH
↓ Hgc
↓ Hg42 No
ppt
HgS + 2Hcl + RNCS

Blacpt

(2) Reaction with KMnOp :

10 >
- Ald & Ketones are formed
-
amines - 20 >
- Tetra alkyl hydrazine is formed.
& 30 >
- No reaction
 i)
aazn crcra

BicH
= NH Hot 0
+Ketone

(ii)
RV
R HD RN-N-Rz
20

(3) Reaction with Caros acid (1505)

CH3-CH-Cr-NE CH-C-CHNHO -E C
Hydroxamic
acid

RNH L RNOH (Dialy hydroxyl amie

easted
RN
GDie
a

NITRO BENZENE: -No (oil of mirbane)

(used as perfume in
soaps

↑no
so ?
Conc. SO4

uming sou
No

No
Electrophila

Properties :

·
Most-Yellow crystalline solids (Nitrobenzene - liquid-bitter almonds)
insoluble inHo soluble in organic solvents.
·

Heavier toxic .
than highly
·

tho ,

On strong heating , polynito compounds explode violently used

Explosives .
·

as
,

Selective reduction :

· m-Nitro
aniline
 Reductions :

Mccor) Inle
~
, Mine

I
acidic medium

Paine
Catalytic hydrogenation
#
(or) PE(On

medium n
In/NHyCl In/NHyc

(
>

↓·
-

entral
Nitroso
N-phenyl
hybroxyl amine

In dust

alkaline medium
(aq NaOrD
.

Hydrazobenzene

- LiACORN O
Azobenzene

Azoxybenzene

Phenyl on
hydroxylamine p-Aminopheno

Electrophilic substitution reactions of Nitrobenzene :

NO group is meta directing & ring deactivating.

· Rea"
(-No is withdrawing)

NOTE : No .
of Isomers with CHgN
NH-Chz

as
C-NHz NH2

lot ⑳ ·