Benzene

Brominehasthesame
Electrophilic substitution Chlorination exact process
Anhydrous Alls
Or t HCl
neggunger

Steph Alls Cla s Alclatt Clt

Cl
Steph Tacet H
Cl Oh Ht
Step3
It

Steph Alda Ht s Alls All Catalyst Regenerated

2 Electrophilic Substitution Nitration

Amos
0

41
heat under
I H2O

50 C temperature
Steph Anos 242804 Not 24804 1730
Step2 TNOat NG
NO
Step3 19 At

Steph Htt 24804 t H30t 2172804 H2O

3 Electrophilic substitution Alkylation
Anhydrous All Clt
easel Hel
heat

Steph Atoll t Alls CHI t ALCLE

Steps
Toast 9
at
At
Steps 113
step4 Alely Ht ALC's HCL

4 Electrophilic Substitution Acylation

p g ee
Anhydrous

heat
Afb
O
f Hel

Steph R Ch t Alls
H
Alcott R Et
Steph Tat O 90
R

tf 9 00 At
steps R R

Steph Alea Ht Alas Hel

5 Hydrogenation of Benzene

342 Nickel
2000C
temperature
6 Oxidation of Benzene side chains
Uts Acidified kmnoufhe.at coat
OR hotalkanine
byAt KMnoy
eltzeltzeltzeltz followed alt

All carbon side chains become carboxylic Acid Groups

Be

Eltz
ee
or

de
e
lets lets no
Br
gavelsas
catalyst
or Braasreagent Ahsas lets Ots
e
egg
Gas
Br
I D or

j
reagent
Meg as
qq.gg 8
Clagatalysy
lets lets
no lb as UN
eh
Gegg Eltz
Or reagent light e 0
N
Nor OHall
O C R
1 Nitration of Phenols
Ott OH OH
Dilute ANO no
RoomTemperature
NO2
OH OH
conc 112804 lone ANO ON NO
50C Heatunderreflux
NO

2 Chlorination Bromination of Phenols Test for Phenols

OH

BB
Room
Br Fr gyphite Ppt
Temperature

OH Whiteppl
Room ee T BALL
Temperature

Cl

3 Reaction with Na or NaOH

O'Nat Ott oNat
H2O a NaOH Na s t 4242
a Narcos

No Reaction
M Acid Nature Of Phenols
Phenol WaterEthanol
Stronger Acid
OH O
Reason The negativechargebecomes part
Ht
of the delocalised e structure
Thisforms a more stable anion
Atzeltzolt CHzeltzo At This is not the casewhenobserving
ethanol

SPECIE Bluelitmus NaOH Narcos

Alcohols stays bae action Noreaction
Phenols Goes red saltformed Noreaction
carboxylicAcids goespeg saltformed saltformed

1 Formation of Acyl Chlorides

O O
BR e PCB heat t H3PO3
a 3r e
OH El
O O
R e room R C
PCL temperature t Helt PCL30
OH
 O
r heat in Pyrading R
e a sock e 802 HCl
as solvent
a

2 Reaction Mechanism Addition Elimination

4,0
r
Thi ee a r É tee
Niue gene a
Nue

i Allreactions below 80110W this mechanism

OH
Nuc 420 OH R OH my R Ny

Hydrolysis with cold water

R É el H2O femme R
ed
OH Hel

Hydrolysis with NaOH

R É Ch t NaOH
ROOM
temperature
R É O Nat t Ct

Acyl chlorides with alcohols esterification

R E bl t eHzeltzeltzOH
ROOT
temp
R ÉO CHzeltzCH3 t HCl
D Acyl chlorides with phenols esterification
Ott
Phenolis dissolvedin NaOH to
at Na KHz make Phenoxide whichis a
stronger nucleophile
O'Nat
R É el R É o Nacl

a
Benzoyl chloride with Phenol Esterification

OH it ee É o
Room
temperature HCL

a
Acyl chlorides with Ammonia

R É Ch t NH3 ROOM
temperature
R É NHz All
L amide

a
Acyl Chlorides with Amines

R É Ch t CHseltznitz R É N CHzCH3 HCL

Amide
1 Nitration of chlorobenzene
ee

Conc ANO
ConcentratedHasan 102
50C Heatunderreflux
NO2

Halogenoarenes do not undergo hydrolysis unlike halogenoalkanes

Halogenobenzenes are deactivating yet are 2,4 directors Theexception
to the rule

e Basicity in amines
NH3 t H2O NHyt OH They actas basesbecausethelone
lH3llt2NH2 t H2O
MHz
t H2O
i eazy past g
NH3
t Ott f pairon nitrogenforms dative
bond with the Ht ion

whichone is more basic

MHz
CA3CH2NHz NH3

NH3 MHz
it
veinductive standardreaction ThelonepairontheNitrogen
react Hasno Rgroups atombecomespartofthe ering
Passey attached
making it thehardestone to
react
 2 Chlorination Bromination of Amines
Nitz
Ppt
BB
Room Trigyphite
Temperature

Whiteppl
tf
Nitz
Room ee
302 Temperature
BALL

Cl

3 Acyl Chlorides with Amines

R É Ch t CHseltznitz R É N CHzCH3 HCL

at
Amide

4 Formation of Phenols
MHz Nater OH
dilute ANOzand
diluteHCl water
5 heat it over
60
phenylamine diazoniumsalt phenol

MEN
diazonium structure
5 Coupling reaction
NEN
NEN OH

diazonium salt azodye

Process

OH NaOHCag O

O NEN
NEN OH

6 Formation of Amines

1 Nucleophilic substitution of Alkyl Halides with Ammonia

R Br NH EFFIE R NHa HBr

2 Reduction of nitriles
Nats in ethanol
pen R CH2MHz
heat underreflux
3 Reduction of Amides

r f yy
it
liality indryether
heat under reflux
p eHz MHz
 M Reduction of nitrobenzene
Nor NHz
Sn t concACL
heat

1 Reduction of Amides

p f my
liautu in dryether
heat
R CHz NHz

2 Hydrolysis of Amides

Hydrolysis
Ch
R E R t H2O R OH R MHz
Y
we dont add water hydrolysis happens with an acidoralkali
dilute HCl
heat under reflux
R É OH R NH3

R Em r
É
H
É naan can
R ÉO R NHz
Room temperature
 Why are carboxylic acids more stable than phenols and alcohols

O
R e ont t H2O R C E Hoot

d triboted in the resonance hybrid it makes

R c ftp the anion more stable as charge is distributed over
ge

Relative Acidities of Carboxylic Acids

Note The more the charge spreads over a molecule the stronger
it becomes

O O
ee É c ont se ce É c on a d c doit
Cl Cl Cl

Clatoms take electrons away from the coat The more the Cl groups
the more the charge is distributed therefore resulting in a more stable
anion

O
ee É c on at É C
OOH
eh C
OOH

H H CH3

Alkylgroups are electrondonatingThe more alkyl groups attached to the

primary carbon the lesser the charge is distributed resulting in a weaker
acid