AROMATIC

NANG3 Tschichibibin Rek

Ens
D
NazFe(CN) -
> O-NH
⑦ HBEY
PUNC *
> Ph-F Balzschmann Rekt

⑦ Cu2X2/Cuz(CN) 2 FRmechanism
PHN, U
Ruch
Ph-x/Phrew
HX/HCN
>
Sandmayou
ce FR mechanism
PHNOCO < Ph-X/Ph-CN Getteumann Rean
Slower than
MX/HON
Sandmayor
DILOHC 100atm
OH
Dow's
OH

Rashing
C °
I
250 se I C
I > °

Process
I M20 458 C
Process
D ② O
O SiO2 200atm
>

A on To
high H ,O SWEA
MPS
T ↑ Both are used for industrial
-

P
W

localised
C
I
spl
C
② - sp2-sp"bond Peups
of Phenol
.

O delocalized
-
> C
O
Phosgene
11
Get >
-

a -c -

Benzyne
er NH2 SEAE/EAS/AES
I NANHL
I Cine
n
LOTTE
>
+
O -
70 C
°
O Substitution -

↓ nigh wh T ↑
SNEA fast

IRNE
P-NHy NH3
IMPS M
i /~I E

A
-

al
I
/-⑦ land Comee
E Why
-

or
101
-x I

Benagne
· complex/Benzenonium ion
in Incl
alkylation
Q
no warrangement
as it is slow
2 FC-Acylation O
O 11
LA
+ MX
LA
H PH-H +
R- -
X > Ph-C-R
PH-H + RX > Ph-R +
R-T = 0 is RAE
12° 30
R managements possible
Ph--R
o
F(U < Br < I o
FC Catalyst
> called -
Sndg> Ind2 +
R-C-0--R A + RCOOH

LA : AlCy
>
BFy >
SbUg > FeCz > Ph-H 85

uk at ontho position
Intramolecular FC only
management due to
alkylation
BB
.

without Faster than

.

till memb
King
c =
Ha CHO iS HC + InC2 i) 9
NH CHO

#
> X / I
+ co
ZuCz /-
I
10
-X
+ HCN
ii) Myo L "Lot
C-

LI O
/
Getterman Koch
aldehyde synthesis Gettermann
Aldehyde Synthesis
 C
Fure radical addition
. 19 Shreo isomeus)
[O +
hu U
/-U
-
> -

1-Triple-6/Gammenina/Lindane/BHC
-/
h > Used in insecticide
gardening
- as

AlCly -C b is better in
OH
+
as

-
-
10) Ea >
Not
-

/-
④ air hu
/- - ④ a the product is
> 11
Lo O
in more rekt
② no -$
+ Mea# ↑
me
zurg
He and may
Cumine Tot undergo polyalkylation
·
Mined Acid Nitration son > H + HSOG

OIN-OH + H
* -
- -

-
↑
20
+ No , RAE Nitronium Ion
↓
"No 2 NOz
x ④ /- uson L- reson
10)
- +

10I1
+ No >
m
,
- -
- ↳
·
V. Stronk ener used as
acid than HNO
stronger
,
E Any
teclon HeSOG
MelOOM X
Base here
. Catalyst eg
. ,

HNOs
No, *
Any species producing used as
nitrating
HNOs =>M
N2OsENO2+, Nos
↓2SO4 +
MeCOONO2 ;
agent .
eg.
If HNO2 is used the NOT RAE. If HNOz is
CoHy =
CoDg =
CsT6
onidiles NO >
thether added then -
NO2

·
Getteumann Koch
Aldehyde Synthesis
④ O
-
All , RAE
HU + Allz H +
④
*
Co + H > H -
C= 0 +
< H -
C = 0

Halogenation of Benzene
·

Ph-H X} AnhyFeX3
+ > Ph-X Halobenzene

↑ cannot be
↓
-> Br
>
F2
X RAE ** produced .

sost
Benzene
Suphonation of
·

↑ + conc
hyson -LOS +
H20
Ho
↓ *
↑ HSO,
Ph-so
⑰
H2SOn + H S03
P
>
-

RSOy tHO -
so G
E
TL
30z+ Hz8
④
RDS
-
- - -
-
↳ C
·
Diff
bett
surphonation and Nitration

i) in Nitr
satalyst
in suphonation
Catalyst
no
H So ;
y
,
Rate : Nitru Suphi
in Nit while neutual E in Sulp .

i) the changed E
reveusible in serph" .

·) RDS ine. in Nitr

in nitr but in empht- -

iv) No Kinetic isotopic effect

Mesos but same for oleum
(super conc).
CoDo < Csts for conc .

Rate :

·
Desulphonation
-
(H >
-
D For D
iPs0 SUzH # &
< Steam/Hz0 /-
O L- O
1 O IM
> 101
M L/ On HC . -
P
· AES on other anomatic compoundes

goes to most e-rich position first.

of e density
same
Check steric hindurance

then check stability of

a comple
.

e-density
hinderance and same
>
-

If

x
I
EQ
I'll↑
/
/
--

I -
/--

Kll-- -
Ex
- /
I ↳ is more stable
-/
/-S
-
-
than I as in B
& o
tries cle is violated .

=> In sellphonation , i becomes major at

high temp

as the RDS is reversible and stable o complex can

easily be enyoumed
(But in Super Conc Hsoy both eversible)
is inreversible
,
but for B ,
it .

It does not rekt itself

=> Nitrobenzene is solvent for FCuck .

and solvates eactants

Mesitylene +
Sym
TNB 2
[O +
Craz
Alz

No change V

- L
transfer L>
-

/
101
·
1 +
,
--
- No2 mplen
↳ complex""
two
--
Cr
Forms
layer i ...
i ."
:
-
-
Sandwich .
⑥
* -- NOL HOMO-LUMO -
NO
complex
- I
-

101 > 1 O transition ,

like feuocne
-
Tos
.
 Me M > makes
- op reversible
- All3
+ HC + All
Los + Mec
D
>
101
- Me
but not mete .

and
(Meta-Yylene)
m
keeps piling upand
0. p moves back forth
> In
-
polac solvents -
off goes into -of
.
FC wekt
>
-

up of Phenol and Amilene

destroy
LA and hence do not
give
FC products.
and then
hydrolysed to
give
>
-

↑
They can
be protected by acetylation
LO + PUN OG > Ph-Ph
Guembeug Rek attack
before
.

N2 leaves

RKR
Di-Azo
Coupling
OH of Ph-on > Ph-of in basic med

Phn, O mildly,
-

/
/
o
# Very stooky activating
+
-/
=>
↓ = N-Ph attacks before
leaves N2 .

OH
PhNc GO
mild Ph-N
N
=
⑦
lol-T
-
/-
-

Orange-Red Dye
+ >
O basic OH
-
-x

↑Mez N Noe
& mathgl
t
>
Orange
303H h = N -
-

SOzH

w Go
N

I
Mez
I
Noe methys
> Yellow
t

h = N -

⑭ Go N = N Pana-end
-of -
-

1 on
(adye)
Noz
Anilene/Phenol di/HNoz > espective 0,
p , he products +
·* -
-
Fo
· Libermann's Nitroso Test

To
differentiate
(anomatic aliphatic
a) P ,
20 , 30 amines as well as

Red color
6) 1 Aromatic and aliphatic .
7
with ceic
"ROH
PHNOG
NANOL HE RNN ammonium
④ PHNH2
0-so ,
2
nitrate

Ph-N-Me
I/
> PN-N-NO ORNH"
5 > RN-NO
② -
H
-
Me

NM22 ④
⑧ Q

to
19
- REN > RzNHNOz
③ Ph-NMe
3 /
=
101

OH
of
/
Red
O
II
Green
* * Blue
NaNO2
1 11 L
H
--
n
>
LOS >
PHOT
3
- Naon

N
Y

· [ i
RGB test (labtest for phenol) on
La
Chloral C Dichloro
2 c = 0
Ht
> - I Diphenyl
azc
-

+
-

+ /
/ Trichloro ethane
LOL
C
10
Y
- DDT

in Inseticide

Caucinogenic .

no Me Bis Phenol-A
2 Ph-OH + Mecome I
not
-- on
(DYE)
on

zon-on +
1~
O
- <
o
H
/-
E-to-on
-
Phensephthalin

LOTT
!
-

people color with neutral teric Chloride sol

All Phenols
give
 -z
L
NH2

G
On
NH-Z I
z=
S0zH , NO2 ,
NO ,
X
, ,

H E- /

↓ Los
+
/~ 7
101 R , Ar NH2
lol A ,

3
-

·
Hoffman's Moutius
Rearrangement but
NMezCl Nee-Me
- Ph-NEtzOH
o A
> C= C
I A MrcC
1 O I
-
/ > E , CB
Los T
Benzidine Fis
Reamangement Rearrangement
· ·

NH2 Of
O-come

G
-
NH NH I

#As + oute
-
HC /

~
& *
/-
101 A -

LOL /
-I 7
-x
Cdoor) 201
-
Me
(sogin) 2 H
ot V St
win Intermolecular also

NH2
NH2 Benzidine
-----

-
I
- St
--
5-46
-
St

Vi li
* ipso wek" also possible

Both Aldo and Keto Pentose on

*
nos'-cho *-no
/ >
-

>
-
-

henose on ukn -

wek with
A Conc H , SO4
with concHISOn ,
A

④
A+ CONCH2SO n A + 2 <- Naphthol < People Dye (Molys Test tor laubs)

(Seliwanoff's Test)
A+
1 + 2
y
-X Or
CheyRed Before I min in fructose and

S min in
Resorcinol . after glucose .

M (Orcinol) Bielt's test

&
A+ 11 t Greenish Brown
101 >

Cambo made
e
XX on
on

Pentose and Henose .

II -
B + 11 t Blue Color
 Of
- come oie
of Wintergreen
OH OH
H _ coome
L
cook - /- wor
L
I
-_
COOH Meon ,
> D
- -

LOS = Pain
mecoas

I OI 1 relieving
-
> -

O
- -
Salicylic Acid
Salicylic Acid
Aspirin Methyl Salicylate .

OH
N-Me N-Me
OH
I Cook
Phon ,
H
↑ cooph ACOACy
& -
L-
O I 101
I- - / OH
Salicylic Acid
Antiseptic Salol OH ·
OAC · OAC
Heroine
Mouphine
Wohe's
Dequadalion
-

CHO
-
CH = N-UH -CNL
CHO
H OH H OH
W
AC
H

noI
ACOAG
HO H
WHEOH
> HO H 7
AcO H
AqOH , H
as solvent
OH
of Dehydraget
M
OAC
t
M

on
M

H on
H OAC

CHIOH
6C crose
and
acetylating CH2OAz CHIOH
Glucose agent 5C
-

upguadation
CHO
· Killiani Fisher's
CHO

on
"on
-

I↑
H OH
HCN snC HC
H30
7 H
HO H 3 3

M OH

H on

CHIOH

Schotten Baumann Rek

(Benzanilyde)
·

PHNH2 + Phcoc < PNCONUPL + He

[Benzoylation]
Cumine Perovide
·
Hydrogen O
in -On Me
Ph-CH-Mec Oairhr/cuD > PhOH
+ If
... ,
Me-C-Me 0/
-

It
me
Cumene ② n -

~ Me use
H
Guten
co
·
Ph-c-Me Pk- C-Me -
H2O
b-o-H > Pho-C-Me
RD)
die
 differentiate 1 2. 30 Amines
Hinsberg's
·
Test To , ,

di Kon
PhSO C PHSO, NHR + HC > PUSOzK + NHcR
RNH2 #
>
>

↳ KOH
Ph- _ R + H20
Hinsbeug Reagent ·
Soluble Salt

KOH RNH
R2NH + PhSO, C LPHSONR , +HE > PhSOzK +

In soluble

④
PhSO, U > PHSO ,NR,
48 Rai PHSO,NR2 + RO
RIN + &
A
Soluble Insoluble

·
Gabriels Pthalimide Synthesis
=> Best method to prepare 10 Amine because separation and purification eg.
not

contaminated with other degene

=> Product is never

COOH
O
II O
/-
i
YO 20
-
- on
NH3 > +
NHz
-
101 > 1 0 LNH H2O -/

-
D
- X LOOM d Insolb
solb
P thalic Acid pthatiniede
cook
Kot H30 x
+ NHT
O
I O > 101
Il
-cook Sold
-x Ensolb
/ -
NE ,
Lo R /
- X S-

-101 N -
R ↑ thalimide
&
- - - Alkyl
i i

e · ①
o O
n Ev
-
④ -
-
RNHz
X1000

+
↑ Cook TNRH
↓
/
Ron
-
e
Xcook
+
↳ 1 000
L

RNH2

> + H > OCNH >

R3N > RaNX
While RX + NHy RNH2

contaminated with 20 , 3040 products .

Limitations
PLNM , cannot
be turned as 0 Mez2-Nh , cannot formed as be
④
Nut substrate and good enough base
Net cannot attack out
.
as 3
askene as
will product .
 Hoffmann's Degradation
·
Hoffmann's Bromomide Rek or
Hy pobromide or

10 Amide and imide give kn D /H comes from KOD/KOH (both)

> Only
-
-

7
O
II
KOH + Brz
> R-NH2 E
R-C-NH2 or KOBr X R- N4) -
c= 0

on 1-co more Br fOH

- 4 moles

l
·
R-ic D on
- -
↑ Stable
Kon consumed
Rose-
-

BrBr -Br
O

more to e
↳
Rs

"EN-(
O
R-N = C= 0

C
On >
R-C
R-"Y-NH-Br -
Hot
>
-
o

Me -
N = C = 0
in Stc
No
change
.
Cz onidises
Regioselective or configuration of Methyl
Iso yanate NHL -NHy to N2
↳ One position preffered .

R (MF C gas)
over other

Curtis
Degradation
·

R
ONHNHL
R-NH2 hydrolysis
-
c <
-

④ NaN3 >
R
P c > R-NH2 ② NANO He
-
-

② OH/H20
N

W
Q
O
Go i
hydrolysis
C ( RDs
· &Il - d -

RNN-N, i
-

C
-
④
-
-SO
R-N = C y

e
=

---N-WEN

Losseyn Dequadation
·
① Mecod
4
N e > RNH2
R-
-

O
I H ② on
> R-NH2 N
R-C-NH-OH
N
Q+ 04- hydrolysis
-H hydrolysis -
RDS
-
H

Coac
L
> RuN =

Ca
us
(o
He
G
R
-

DAL
-

C
=
0
-R N = -

e
q-N-On
-

B ,

- RDS

·
Schmidt Degradation
O
HNz hydrolysis R-N = C =
0

R--on >
RNH2 M
M2SOn

RN -
OH
HQ I 10 *
R-C-OH-
Na
·
On M--NEN
R-
I
OH
3
N N
·
-
-
H -
 · Schmidt Reaction
O O OH
HNz II tauto
-" -R
I
3 <
R-C-NHR R C N-R
R - =

He SO n Dehydrating
Agent d

-H ④
- R-C N-R
&
Enfor
=
H >
OM R
H2O -
I
a
-

- >
R-

i
-

R-

O OH
KOH
Me - - BV2
> Me-i-NH= > Me-CHO

Bril "M z CHO

O

Mez-C-C-NHL c -c =
c - -Ne "Me-CHICHO
O O
I 19 II KOD
- Ph-CH2-CN R-C-NH > C-C-ND2
Ph-CEC -
C-NH2 ,
BVz
O
KOH
Uc is
1/
NH -
c - NH 3 NHL -NH2 better OA
, , BV2 >
-

than Br,
Naok
=>
Uz
> NU2 -NH2 N2
Oil Rek
·
Hoffmann's Mustand
mustered oil with CS
Lab test for 1 Amine which gives smell of , & HGC >

Es ng-4
A
2444
R-NH2
> R-N = C =
S +
MgSL +
-

+ +

↳
-
a
-
-

A
Y
n Rate &
-
Ha
, R - N
-
G
- >
-[Hq density on N
-
s

(Hoffmann's Cambyl Test)

Isocyanide Test Amine
·

>
-
Lab test for 1 Amine which
gives foll
smelling subs with Cully , on

> HOF HLOOM

> RNH
-

+ KON > R-NC +

R-NH2 +
CHUz
↓ T

it is poisonous
ca > as
.

↓ -
c
RDS
H4
'I
4
>
- > R- N- CO
Tc
↓ ↳
-
u
· Riemmen Tiemann Rek
If can used
OH
① Kon Salicylic
i
Or then
/I > I
1 + CHUz S-- CHO + acid is
O
--X
② H
101 - -
major
T
-C
'
may
-

g -- O
--
Ortho Maj because

o
---

Braz
-
II
L CH formation
/
IO
i) Chillate
-E
stable
ii) O more
⑦
hav

is
d
More New

- 2. 44
go
I is 2 outho and I pana
i -
I CH-44
N
C-
probablity
RDS IMPS -
/- c more
-
-

I
-

>
.

Oh >
-
quatio
Naok > kon

↑ of
rig Not
as smaller
-
W
/-
IMPS
density
&II RDS
3
"I -1 O I is change

an Tar
-↑
Para I
# i) Steuic hidrance
·
Or OH

-one ↓ one
Vanillene
KOH
⑱-
10 chay 10 !
+ >
Ht vanilla esse
e
--

ins
Kolbe Schmidt Rek
-0
·
At

a
off
④ KOH Of
I
7 X cook + C KOH < P
/ -
+ CO2 1 O I
LOS Ont LOS
Toon NaOH O > l
O
O
·, o
O I
<
-Il OK -m
... LOH P
- D
-

1
e
ono / * COOH
C- a H -

I
<
↓
C
II E
#
>
L01
-

-C
size
KOH
very large ap
-

temp ~
sizet
-

60
%
O < > less
energy
so las hindered pana major change density *
<
p
-

Chillation hinderance ↓
60 to 168c O> P >
-
Ortho stable due to

160° from Ortho para stable

high Temp CO2 haves
> 0 < p > at ,
,