Organic

Chemistry
By

Dr. rer. nat. Zeinab

Mohamed

2020
Nomenclature of benzene derivatives
1. Mono substituted benzene derivatives
They are named by combining the substituent as prefix with word benzene
Cl Br I NO2

Chlorobenzene Bromobenzene Iodobenzene Nitrobenzene

A number of mono-substituted benzene derivatives have special name

CH 3 OH NH2 COOH

m e th y lb e n z en e h y d ro x y b e n z e n e a m in o b e n z e n e
T o lu e n e Phenol A n ilin e B e n z o ic a c id
SO 3H COCH 3 OCH3 CH=CH2

Bnzene A c e to p h e n o n e A n is o le S tyr e n e
s u lp h o n ic a c id
 2. Di-substituted benzene derivatives
For di-substituted benzene derivatives, the prefix Ortho, meta and para are used (o, m, p)
o R o

m m

Br Br NH 2
p
Br

Br
Br
o-dibromobenzene m-dibromobenzene p-dibromobenzene
CH 3 COOH SO 3 H
Cl

NO 2
o-chlorotoluene m-nitrobenzoic acid I
p-iodobenzenesulphonic acid
3. tri-substituted benzene derivatives
 In case of tri-substituted benzene o, m, p can’t be used
 The benzene ring is numbered starting from original substituent

Br CH3 NH2
NO2 Br
Br NO2

Br NO2 Br
1,2,4-tribromobenzene 2,4,6-trinitrotoluene 2,4-dibromoaniline
NO2
NO2
Cl
Br

Cl
Cl
2,4-Dichloro-1-nitro-benzene 2-Bromo-4-chloro-1-nitro-benzene
Preparation OH Benzene
HC CH
Acetylene


N Cl
N
EtOH H2 O

Soda lime/ 
MgBr
phenylmagnesium bromide
(Grignard reagent)
NH2 NaNO2/HCl
Mg
Br
COOH

Bromobenzene
 Electrophilic substitution reaction
1. Halogenation: means entering of halogen atom into benzene ring
Cl

Cl2 / AlCl3

2. Nitration: means entering of nitro group (NO2) into benzene ring

NO2

conc. HNO3 / conc. H2SO4

3. Sulphonation: means entering of sulphonic acid group (SO3H) into benzene

ring
SO3H

conc. H2SO4
(or Oleum)
 4- Friedel Craft's reaction

Alkylation Acylation

+ C H 3 C l/A lC l 3 + C H 3 C O C l/A lC l 3 + p h C O C l/A lC l 3

CH3 COCH3 CO

to lu e n e A c e to p h e n o n e B e n zo p h e n o n e
 Addition reaction

O O
O
CHO O
3O3 3H2/Ni 200oC
3 O
CHO oznolysis Reduction
O
O cyclohexane
Glyoxal
O O 3Cl2 / h 
benzenetriozonoide

Cl
Cl Cl

Cl Cl
Cl
Gammexane
 SO 3H
Scheme 1 NO2

CH3
b e n z e n e s u lp h o n ic
a c id n itro b e n z e n e

con c. H 2SO 4 con c. H N O 3 Cl

con c. H N O 3

to lu e n e C H 3 C l / A lC l3

C l2 / A lC l3
c h lo ro b e n z e n e
O O
O
CH O O
3O3 3H 2/N i 2 0 0oC
3 O
CHO o z n o ly s is R e d u c tio n
O
O c y c lo h e x a n e
G ly o x a l
O O 3 C l2 / h 
b e n z e n e tr io z o n o id e
C H 3 C O C l / A lC l 3
p h C O C l / A lC l 3 Cl
COCH 3
COph Cl Cl

Cl Cl
Cl a cetop h en o n e
ben zophenone Gam m exane
 Electrophilic substitution in benzene derivatives
Orienting effect of the substituent
-OH
1. e- donating (Repelling, Releasing) -R
o, p - directing NH2
NHR
G G G NR2
ph
E -SH
E+
+ NHCOCH3
X= Cl, Br, I
CH2Cl
E OCH3
2. e- attracting (withdrawing)
m- directing
-NO2
-CN
-CO
G G HC=O
-COOH
E+ COOR
SO3H
CCl3
E +NH3
+NR3
 Homologues of benzene
1. Alkyl benzene
They are aromatic compounds in which alkyl group attached directly to benzene
ring H C CH
CH3 CH2CH3 3 3
CH

Methyl benzene
Ethyl benzene Isopropyl benzene
Toluene
Cumene

CH3 CH3
CH3 CH3
CH3 CH CH CH3

CH3
o-xylene 3-methyl-2-phenyl-butane
p-xylene
 CH 3

T o lu e n e

P r e p a ra tio n

C H 3 C l / A lC l 3

M gBr CH3 M gBr

(C H 3 ) 2 S O 4 CH 3Br

p h e n y l m a g n e s iu m b ro m id e
G ig n a r d re a g e n t
CH 3Br / N a
W u r tz r e a ctio n

Br
 Preparation of Cumene

CH3 CH2 CH2 Cl + AlCl3 CH3 CH2 CH2 CH3 CH CH3

less stable more stable
CH3 CH3
CH
CH3CH2CH2Cl

AlCl3

Cumene
Preparation of n-Propylbenzene
CH2MgBr
CH2MgBr CH2CH2CH3

(CH3CH2)2SO4 CH3CH2 Br

benzylbromide
 Reactions
A. Ring reactions
1. Hydrogenation CH3 CH3

H2 / Ni

methylcyclohexane
2. Halogenation
CH3 CH3 CH3
Cl
Cl2 / AlCl3
+

3. Sulphonation
Cl
CH3 CH3 CH3
SO3H
conc. H2SO4
+

o. p - toulene sulphonic acid

SO3H
4. Nitration
CH3 CH3 CH3
CH3
NO2 NO2
conc. HNO3 + conc. HNO3
conc. H2SO4 conc. H2SO4

o. p - nitrotoulene NO2 NO2

2,4,6-trinitrotoluene
CH TNT
5. Friedel craft’s CH3 CH3 3
CH3
CH3Cl / AlCl3 +

CH3

CH3 CH3

CH3COCl / AlCl3

COCH3
p-methyl acetophenone
major product
B. Side chain reactions
CH3 Cl Cl
CH2Cl CH CCl3

Cl2/ h 
Cl2/ h  Cl2/ h

Benzylchloride Benzalchloride Benztrichloride

NaOH NaOH NaOH

CH2OH CHO COOH

oxidation
CH3 COOH
Benzyl alcohol Benzaldehyde Benzoic acid

(O) / KMnO4

R COOH

(O) / KMnO4
Scheme 2
MgBr
MgBr

CH3 CH3
Cl
+
Br
(CH3)2SO4 CH3Cl / AlCl3
CH3Br / Na CH3Br Cl
Cl2/AlCl3

CH3 CH3 CH3 CH3

CH3
NO2 NO2 NO2
Reduction conc. HNO3 + conc. HNO3
conc. H2SO4 conc. H2SO4
COOH (O)
CH3Cl/AlCl3
NO2 NO2
CH3 CH3
conc.
CH3
CH3 CH3 H2SO4 Cl2/ h  +
SO3H
+

Cl Cl CH3
CH2Cl CH CCl3
CH3
Cl2/ h Cl2/ h

Benzylchloride Benzalchloride Benztrichloride

 Cl Cl
Aromatic Halogens
CH3

Preparation
chlorobenzene o-chlorotoluene
Cl
Sandmeyer reaction Cu 2 Cl 2

Br
Cu 2 Br 2
NH2 N N Cl

N aN O 2 / H Cl
HI
I
COOH

benzen ediazon ium

chlorid e H 3O+
CN
Cu 2 CN 2
T o p rep are m -d ich lo ro ben ze n e reduction CH 2 N H 2

benzonitrile
NO2
NO2 NH2 Cl b enzylam in e
Cl 2 /AlCl 3 red uctio n
i) N aN O 2 / H Cl
ii)C u 2 Cl 2
Cl
Cl Cl
m -d ich lo ro ben zene
1. Halogenation Cl Cl Cl
Cl
Cl2/AlCl3 Cl2/AlCl3
+

2. Nitration Cl
Cl Cl Cl
NO2
conc. HNO3 +
conc. H2SO4

3. Sulphonation NO2

Cl Cl Cl
SO3H
conc. H2SO4 +

SO3H
 4. Friedel craft’s
Cl Cl Cl Cl Cl
COCH3 CH3
+ CH3COCl/AlCl3 CH3Cl/AlCl3
+

COCH3 CH3
o, p- chloroacetophenone

-H2O
Cl H H Cl Cl CH Cl
O CCl3
HC Dichlorodiphenyltrichloroethane
DDT
CCl3
Chloral
trichloro acetaldehyde
Reaction with metals
Cl MgCl

Mg
Grignard

Cl

2 Cu / Ulmann

OH
Substitution of halogen with NU
Cl NaOH/ 500 o C

CN
Cu 2 CN 2

NH 3 or NaNH 2 NH 2
NOTE e- attracting group in the o , p – position increase the reactivity toward
nucleophile substitution

Cl OH

NaOH

e- attracting groupm in the p-position

make substitutionNOof Cl with OH very easy NU attack this
2 NO2 position easily

Cl Cl
Cl

O N O N
O O O N
O
 Cl
Scheme 3 Cl
CH3

NH2 +

CH3
NH2
CH3Cl
AlCl3
OH
i)NaNO2/HCl
Cl2/AlCl3 NaNH2 ii) Cu2Cl2

H/ 
NaO
Cl Cl Cl
Cl CH Cl
CH3
CCl3 CCl3CHO CH3Cl/AlCl3
+
Dichlorodiphenyltrichloroethane
DDT
HNO3 CH3COCl
Cl Cl H2SO4 AlCl3 CH3
NO2 H2SO4
+ Cl Cl
Cl Cl
COCH3
SO3H
NO2 +
+

COCH3
SO3H