Polynuclear Aromatic Hydrocarbons

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 1

 Polynuclear Hydrocarbons

Benzenoid Non- Benzenoid

Isolated Fused rings

Azulene

Linear Angular

Biphenyl

07/05/2017 Naphthalene 2
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage Phenanthrene
 I. Isolated Ring
Polynuclear Hydrocarbons

Biphenyl (diphenyl):

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 3

 Preparation of Biphenyl
a) Fittig reaction
2Ph-Br + 2Na ether
Ph-Ph + 2NaBr
soln
b) From benzene diazonium sulphate
Cu
N=N HSO4 + N2 + CuHSO4
EtOH
Biphenyl
c) From benzidine

NaNO2
H2N NH2 Cl N=N N=N Cl
HCl

Benzidine

H3PO4

Biphenyl
07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 4
 d) Ulmann diaryl synthesis
2 Cu
2 Ph-I Ph-Ph + 2CuI
2 Cu
2 H3C I H3C CH3
sealed tube

4,4'- Dimethyl-biphenyl
NO2 NO2

2 Cu
2 I
sealed tube

O2N
2,2'- Dinitro-biphenyl

e) By using Arylmagnesium halide

C OC l2
PhMgBr + PhBr Ph-Ph + MgBr2
07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 5
 Reactions of biphenyl
Biphenyl undergoes substitution reactions,

In biphenyl one ring act as electron donating group and the

other act as electron withdrawing group

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 6

 Resonance shows that O- and P- are the most reactive positions towards electrophilic
substitution.

The electrophilic substitution occurs in 4- position (major) and 2- position (minor) due
to steric effect of other benzene ring.

The 2nd substitution occurs in the empty ring in 2 or 4- position.

e.g.
NO2

conc HNO3
conc H2SO4 + NO2

2-Nitro-biphenyl 4-Nitro-biphenyl

conc HNO3
conc H2SO4
NO2 NO2

O2N NO2 + NO2 +

O2N
4,4'-Dinitro-biphenyl 2,4'-Dinitro-biphenyl 2,2'-Dinitro-biphenyl

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 7

 Biphenyl derivatives
(1) Benzidine (4, 4`-diaminobiphenyl)

H2N NH2

COOH COOH
(2) Diphenic acid

(3) Diphenyl methane

CH2
07/05/2017 8
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage
 Q. Show how could you prepare benzidine from
benzene?
• Answer
I
I
I2 conc. HNO3

HNO3 conc. H2SO4

NO2
I

Cu Zn/HCl
2 O2N NO2

NO2

H2N NH2

07/05/2017 Benzidine 9
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage
 Ulmann diaryl synthesis

COOEt COOEt COOEt COOH COOH

2  HCl
I
Cu

biphenyl- 2,2'- dicarboxylic acid

(Diphenic acid)

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 10

 oxidation of Phenanthrene or phenanthraquinone

COOH O
50% H2O2 K2Cr2O7
AcOH,  H2SO4
COOH O

phenanthrene Diphenic acid phenanthraquinone

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 11

 Oxidation of KMnO4

COOH COOH
KMnO4

COOH COOH

Diphenic acid pthalic acid

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 12

 with sodalime

COOH
Sodalime

COOH

Diphenic acid biphenyl

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 13

 CO2H NO2 Mirror NO2 CO2H Mirror
Cl H H Cl

NO2 CO2H CO2H NO2 H Cl H2N H

A B
Optically active Optically active

07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 14

 • When o- position contains two similar groups, the molecule
is optically inactive due to presence of plane of symmetry ..
for example
HO2C CO2H H3OC CO2H

Plane of symmetry

O2N CO2H H3OC NO2

Optically inactive due to presence of plane of symmetry

COOH NO2
O2N

F
HO2C NO2
Optically active Optically active
free rotation is possible F is a small atom so permit
by free rotation
07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 15
 Friedel- Crafte
CH2Cl
AlCl3
+ CH2

Benzyl chloride Diphenyl methane

2 AlCl3
+ CH2Cl2 CH2

Diphenyl methane
07/05/2017 Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Compounds...3rd stage 16
 1. Nitration
conc. HNO2
CH2 CH2 NO2
conc. H2SO4

Diphenyl methane 1-benzyl-4-nitrobenzene

conc. HNO2
conc. H2SO4 O2N CH2 NO2

bis(4- nitrophenyl)methane

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 17
Compounds...3rd stage
 2. Halogenation

Br
Br2
CH2 C
hv H
Diphenyl methane Diphenylmethylbromide

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 18
Compounds...3rd stage
 3. Oxidation

O
[O]
CH2 C
K2Cr2O7
H2SO4
Diphenyl methane
benzophenone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 19
Compounds...3rd stage
 II. Fused System

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 20
Compounds...3rd stage
 a) Naphthalene  

8 1

 7 2

OH 3 
 6
5 4 OH
 

1-Naphthol or -Naphthol
2-Naphthol or -Naphthol
Br Br

HO3S SO3H

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 21
Compounds...3rd stage
1,8- Dibromo-naphthalene Naphthalene-2,7- disulfonic acid
 Structure elucidation of naphthalene

1- Molecular Formula: C6H8

COOH
O
2- Naphthalene
COOH
Phthalic acid

C
So naphthalene contain the skeleton
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
C
07/05/2017 22
Compounds...3rd stage
 NO2

COOH

3- Naphthalene nitration
Nitronaphthalene O

COOH
Nitrophthalic acid

So nitro group is present in benzene ring

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 23
Compounds...3rd stage
 Naphthalene nitration Nitronaphthalene redn. aminonaphthalene

O
4-
COOH

COOH

Phthalic acid

The benzene ring in phthalic acid produced by

oxidation of aminonaphthalene is not the same
ring is that obtained by oxidation of
nitronaphthalene.
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 24
Compounds...3rd stage
 i.e. Naphthalene contains two benzene rings and
we can explain this by this equation

A B

HNO3
NO2 NO2 NH2

HOOC COOH
O A redn. A O
B B B A

HOOC COOH

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 25
Compounds...3rd stage
 The structure of naphthalene is confirmed by method of its analysis

1- Howarth method
O O

O
AlCl3 Zn-Hg/HCl
+

R HO R HO
R
O O O
Succinic anhydride

conc.H2SO4 Zn-Hg/HCl Se
-H2O 
R R R
O

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 26
Compounds...3rd stage
 Other way of cyclization

O O

AlCl3 SOCl2
+ O

R HO R Cl
R
O O O
Succinic anhydride

AlCl3 Zn-Hg/HCl Se
intramoluclar 
Friedel Craft R R R
O

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 27
Compounds...3rd stage
 • The reaction occurs if R is o- or p- directing group
such as NH2, NHR, OH, OR, R, halogen.

• If R is m- directing group (e.g. NO2, CN, COOH,

COCH3, SO3H) no reaction occur.

• The above reaction gives  -substituted

naphthalene.

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 28
Compounds...3rd stage
 Synthesis of 1-alkyl naphthalene

O O

O
AlCl3 Zn-Hg/HCl
+

COOH COOH
O
benzene Succinic anhydride 4-oxo-4-phenylbutanic acid 4-phenylbutanoic acid

conc. H2SO4 1) RMgX

-H2O 2) HOH

O HO R
R
1-tetralone 1- Alkyl naphthalene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 29
Compounds...3rd stage
 2- From -benzylidene – propenoic acid

conc. H2SO4
-H2O
OH
O O OH
-Benzylidene-3-propenpoic acid

Zn
-ZnO

naphthalene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 30
Compounds...3rd stage
 Chemical Reactions of naphthalene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 31
Compounds...3rd stage
 1. Reduction
Na
EtOH

1,4- dihydronaphthalene

Na
isoamyl alc.

1,2,3,4-tetrahydronaphthalene
Naphthalene
Tetralene

H2
Ni

decahydronaphthalene
Decalene
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 32
Compounds...3rd stage
 2. Oxidation
O

CrO3
AcOH

O
1,4- naphthoquinone

CHO
1) O3
2) H2O/Zn
CHO
Naphthalene Phthaldehyde
O
O2
V2O3 O

O
Phthalic anhydride
COOH
KMnO4
H
COOH
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 33
Compounds...3rd stage Phthalic acid
 3. Addition of Cl2
Cl

Cl2

Cl
1,4- dichloro- 1,4- dihydronaphthalene

Naphthalene
Cl

excess Cl
Cl2

Cl
Cl
1,2,3,4- tetrachloro- 1,2,3,4-tetrahydronaphthalene
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 34
Compounds...3rd stage
 4. Electrophilic substitution reaction
Q: Naphthalene udergoes
electrophilic substitution at
position 1 not 2. Explain

At position 1; carbocation intermediate stabilize by two resonance

E E

E
1

Naphthalene

E
E

Naphthalene one resonance structure

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 35
So carbocation is more stable position 1 than 2
Compounds...3rd stage
 Examples of electrophilic substitution

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 36
Compounds...3rd stage
 NO2

conc. HNO3
conc. H2SO4

1- nitronaphthalene

Cl2 SO3H

conc. H2SO4
40°C

naphthalene-1- sulfonic acid

SO3H
conc. H2SO4
180°C

naphthalene-2- sulfonic acid

Naphthalene
Cl

Cl2
FeCl3

1- chloronaphthalene
COCH3

CH3COCl
AlCl3
CS2
1- Acetylnaphthalene
COCH3
CH3COCl
AlCl3
Dr.MohanadPhNO
Mousa2 Kareem.....Polynuclear Aromatic
07/05/2017 37
Compounds...3rd stage
2- Acetylnaphthalene
 Substituted naphthalene
• Activating groups direct the electrophile to the same
ring, while deactivating groups direct it to the other
ring.

Elctrodonating group
(EDG):
NH2, OH, OR, alkyl Electrowithdrawing group
(EWG):
NO2, CO, COOH, CN, SO3H
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 38
Compounds...3rd stage
 Homonuclear attack
Minor E
EDG E
EDG

E Major

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 39
Compounds...3rd stage
 Heteronuclear attack
E
E
EWG
EWG

Major E Major
E

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 40
Compounds...3rd stage
 Examples: OH OH OH
NO2
conc. HNO3
+
conc. H2SO4

NO2
NO2 Major
OH OH
conc. HNO3
conc. H2SO4

NO2 NO2 NO2 NO2

conc. HNO3
+
conc. H2SO4

NO2
Major Minor
NO2 NO2 NO2
conc. HNO3
+
conc. H2SO4
O2N
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 41
NO2 Compounds...3rd stage
 Naphthalene derivatives

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 42
Compounds...3rd stage
 1. Nitronaphthalene

• 1. naphthalene is prepared by direct nitration

NO2

conc. HNO3

conc. H2SO4
1- nitronaphthalene
Naphthalene

2. naphthalene is prepared by indirect method

NH2 N=N BF4

NO2
NaNO2 CuNO2
HBF4 
-N2

2- Aminonaphthalene
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 43
Compounds...3rd stage
2. Naphthols

• Preparation:
SO3H OH

conc. H2SO4 NaOH

40°C 300°C

Naphthalene-1- sulfonic acid 1- Naphthol

SO3H OH
Naphthalene conc. H2SO4 NaOH
180°C 300°C

Naphthalene-2- sulfonic acid

2- Naphthol
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 44
Compounds...3rd stage
 • Properties:

1- Reaction of  and - naphthols with aryl diazonium salt

H Ph H Ph
OH O N O N
N N
Ph-N=N-Cl
NaOH

2- phenylazo-1- Naphthol hydrazo form stable by intermol. H.B

Azo form

Ph Ph
N N
H
N N
H
OH O O
Ph-N=N-Cl
NaOH

2- phenylazo-2- Naphthol

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 45
Compounds...3rd stage
 2- Reaction of  and - naphthols with nitrous acid
H
OH OH O O
O
N N
HONO

1- Naphthol 2- nitroso-1- naphthol [1,2]naphthoquinone-2-oxime

O O
H
N N
OH OH O
HONO

2- Naphthol 2- nitroso-2- naphthol [1,2]naphthoquinone-1-oxime

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 46
Compounds...3rd stage
 3- Conversion of  and - naphthols to naphthyl ether
OR

RI
OH NaOH

OR

1- Naphthol ROH
conc. H2SO4

OR
RI
NaOH

OH

OR
1- Naphthol ROH
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 conc. H2SO4stage 47
Compounds...3rd
3. Naphthylamine

• Preparation:
1- Naphthylamine

NO2 NH2

conc. HNO3 Zn/HCl

conc. H2SO4

1- Nitronaphthalene 1- aminonaphthalene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 48
Compounds...3rd stage
  Preparation:
2- Naphthylamine

Bucherer reaction

OH NH2
NH3
NH4HSO3

- Naphthol - naphthylamine

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 49
Compounds...3rd stage
Mechanism

OH OH O
NH4HSO3

H H
- Naphthol SO3NH4 SO3NH4
NH NH2 NH2
NH3 -NH4HSO3

H H

SO3NH4 SO3NH4 - naphthylamine

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 50
Compounds...3rd stage
 4. Halogenated naphthalene

• A) Preparation of 1- halogented naphthalene

Br

Br2
FeBr3

1- bromonaphthalene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 51
Compounds...3rd stage
 • B) Preparation of 2- halogenated naphthalene via Sandemeyer

NH2 Cl
N Br
NaNO2 N CuBr
HCl
0°C , -N2

2- Naphthylamine

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 52
Compounds...3rd stage
 Questions:
Convert 2- naphthol to:

• A) 2- bromonaphthol
• b) Naphthalene -2- carboxylic acid
• C) 1,2- naphthaquinone-1- oxime
• D) Ethyl –naphthyl ether

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 53
Compounds...3rd stage
 5. Alkyl naphthalene
• Synthesis of 1- alkyl naphthalene
O
O

AlCl3
COOH
+ O

Benzene O 4- oxo-4-phenylbutanoic acid

Succinic anhydride

Zn-Hg/ HCl
COOH

07/05/2017
4-phenylbutanoic acid
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
54
Compounds...3rd stage
 • Synthesis of 2- alkyl naphthalene
O O

AlCl3 Zn-Hg/HCl
+ O
H3C H3C HO
O O
Toluene Succinic anhydride

Zn-Hg/HCl
conc. H2SO4
-H2O H3C
H3C HO O
O

Se

H3C H3C

2- methyl naphthalene
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 55
Compounds...3rd stage
 6. Naphthaquinones
• There are six possible naphthaquinones, but only common are 1,2;
1,4; 2,6- naphthaquinones

O O
O

O
1,2- Naphthaquinone O
1,4- Naphthaquinone

2,6- Naphthaquinone
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 56
Compounds...3rd stage
 Preparation of naphthaquinones

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 57
Compounds...3rd stage
1,4- Naphthaquinone:

CrO3
AcOH

O
Naphthalene 1,4- Naphthaquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 58
Compounds...3rd stage
1,2- Naphthaquinone:

NH2 O
OH O
K2Cr2O7
H2SO4 or PbO2

1- Amino- 2-naphthol 1,2- Naphthaquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 59
Compounds...3rd stage
2,6- Naphthaquinone:

OH O
PbO2
benzene
HO O

2,6- dihydroxynaphthalenel 2,6- Naphthaquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 60
Compounds...3rd stage
 7. Naphthoic acid

COOH
COOH

2- Naphthoic acid
or
1- Naphthoic acid - Naphthoic acid
or
- Naphthoic acid

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 61
Compounds...3rd stage
 Preparation of 1-naphthoic acid

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 62
Compounds...3rd stage
From bromonaphthalene

Br MgBr COOH

Mg 1) CO2
dry ether 2) H

1- bromonaphthalene 1- naphthyl magnesium bromide 1- Naphthoic acid

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 63
Compounds...3rd stage
From 1- naphthylamine
Cl
NH2
N N CN

NaNO2
CuCN
HCl

1- Naphthylamine
COOH 1- naphthonitrile

H2O
H

1- Naphthoic acid

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 64
Compounds...3rd stage
From 1- acetylacetophenone

COCH3 COOH

I2/NaOH

1- Acetylacetophenone 1- Naphthoic acid

2- Naphthoic acid can be prepared by the same above methods

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 65
Compounds...3rd stage
 Anthracene

1 9 8
2 7

3 6
4 10 5

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 66
Compounds...3rd stage
 • Anthracene has 4 isomers:

I
II

07/05/2017 Resonance I,Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

II are more stable,stage
Compounds...3rd contain 2 benzene rings. 67
Synthesis of anthracene

• 1. Friedl Crafts
CH2Cl
AlCl3
+
ClH2C

Benzyl chloride
-2H

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 68
Compounds...3rd stage
Anthracene
 • 2. Elbe reaction

Pyrolysis

CH3
Anthracene
o- Methyl- benzenophenone
or o- Benzoyl- toluene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 69
Compounds...3rd stage
 • 3. From 1,4- Naphthoquinone
O O

O 1,3- Butadiene O
1,4- Naphthaquinone
O

CrO3 Zn
AcOH

O Anthracene
9,10- anthraquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 The above method showsCompounds...3rd
presencestage of naphthalene in anthracene 70
 • 4. From benzene and phthalic anhydride

O O

+ O AlCl3

O HOOC
Phthalic anhydride
O

H2SO4 Zn
-H2O

O
anthraquinone Anthracene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 71
Compounds...3rd stage
 Chemical reactions

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 72
Compounds...3rd stage
 • 1) Diels Alder

O O


+ O O

O O
Anthracene Maleic anhydride Endo- anthracene- maleic anhydride adduct

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 73
Compounds...3rd stage
 • 2) Addition of one molecule of O2

O
+ O2 O

Anthracene Anthracene epoxide

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 74
Compounds...3rd stage
 • 3) Halogenation of anthracene

X X

X2 -HX
X= Cl or Br

Anthracene X

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 75
Compounds...3rd stage
 • 4) Oxidation of anthracene

Dil HNO3

O
Anthracene 9, 10- Anthraquinone

In using dil. HNO3 only to obtain 9,10- anthraquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 76
Compounds...3rd stage
 • 4) Reduction of anthracene

Na
isopropanol

Anthracene 9, 10- Dihydroanthracene

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 77
Compounds...3rd stage
 Anthraquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 78
Compounds...3rd stage
 Preparation

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 79
Compounds...3rd stage
 O

Dil HNO3
K2Cr2O7

O
Anthracene 9, 10- Anthraquinone

O O

+ O AlCl3

O HOOC
Phthalic anhydride
O

H2SO4
-H2O

O
anthraquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 80
Compounds...3rd stage
 Chemical Reactions

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 81
Compounds...3rd stage
 Zn/ 
Distillation
or
Zn/H/150°C
Anthracene

O O

Sn/HCl/AcOH

O 9- Anthrone

OH

Zn/ NaOH

OH
Anthraquinol
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 82
Compounds...3rd stage
 • Nitration

O O NO2 O NO2

HNO3 HNO3
H2SO4 H2SO4

O O Major NO2 O
1- nitro-9,10- anthraquinone 1,5- dinitroanthraquinone
+
NO2 O NO2

O
1,8- dinitroanthraquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 83
Compounds...3rd stage
 • Sulphonation
O O O SO3H
SO3H
Oleum
+
160°C

O O O
Anthraquinone-2-sulfonic acid small
Major

Anthraquinone does not undergo Friedl Craft reaction

•Preparation of 2-amino-anthraquinone
O O
SO3H NH2
NH3


O O
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 Anthraquinone-2-sulfonic acid 2- amino-anthraquinone 84
Compounds...3rd stage
 Alizarin
O OH
OH

O
1,2-dihydroxyanthraquinone
Alizarine
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 85
Compounds...3rd stage
 Preparation
O O
SO3H
Oleum, H2SO4
160°C

O O
Anthraquinone 9,10- anthraquinone-2- sulfonic acid
1)NaOH, 

2) [O]

O OH
OH

O
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
Alizarine
07/05/2017 86
Compounds...3rd stage
 Preparation of Alizarine Blue
O OH O OH
OH OH
1) conc. HNO3
conc. H2SO4
2) [H]
NH2
O O
Alizarine
O OH
OH
1) Glycerol/ H2SO4
2) PhNO2
N
O

Alizarine Blue

Alizarine blue is used for dyeing wool by blue color

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 87
Compounds...3rd stage
 Phenanthrene
6

1 5
10 9

4
2 1 6 8
10 14
3

7 2 13
9 5 7
11
8
3 4 11 12

12 14

13

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 88
Compounds...3rd stage
 Position of double bond

The most stable

3 benzenoid rings

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 89
Compounds...3rd stage
 Preparation of phenanthrene

• 1) Howrth method
O
O
COOH
AlCl3 Zn-Hg/HCl
+ O

O
Naphthalene Succinic anhydride

COOH
conc.H2SO4 O Zn-Hg/HCl

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 90
Compounds...3rd stage
 Preparation of 1- alkyl phenanthrene:

R R
O 1) RMgX OH Se
2) HOH

• Preparation of 2- alkyl phenanthrene:

O R
O
R COOH
AlCl3 Zn-Hg/HCl
+ O

O
Naphthalene
R R R

COOH
conc.H2SO4 O Zn-Hg/HCl

Se

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 91
Compounds...3rd stage
 • 2) Posher synthesis
COOH
CHO CH2COONa

Ac2O Zn-Hg/HCl
NO2 +

NO2

COOH COOH

NaNO2/H2SO4

NH2
N2HSO4 Cu

07/05/2017
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic Phenanthrene 92
Compounds...3rd stage
 Chemical Reactions

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 93
Compounds...3rd stage
 Na/EtOH

9,10-dihydro-phenanthrene

1) O2 CHO
2) H2O
CHO

Biphenyl-2,2'-dicarbaldehyde

Br2
Br

Br

9,10-dibromo-9,10-dihydro-phenanthrene

Br
Br2
FeBr3

9-bromo-9,10-dihydro-phenanthrene

H2O2
AcOH COOH
COOH

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 94
Compounds...3rd stage
Diphenic acid
 Benzil-Benzilic rearrangement
COONa
Ph C O NaOH Ph C OH
Ph C O Ph

Benzil Benzilic acid salt

Mechanism

OH OH O
Ph C O HO Ph C O C O Proton C O
transfer
Ph C O Ph C O Ph C O Ph C OH
Ph Ph

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 95
Compounds...3rd stage
 O COOH
NaOH
H OH
O

Phenanthraquinone 9-hydroxy-9H-flourene-9-carboxylic acid

Mechanism

O OH COOH
HO O
O
O O

COO

Proton
transfer OH
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 96
Compounds...3rd stage
 Phenanthraquinone

• Preparation

O
K2Cr2O7
H2SO4
O

Phenanthrene Phenanthraquinone

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 97
Compounds...3rd stage
 Condition necessary for aromaticity
Any compound to be aromatic, it must be;
• 1. Cyclic
• 2. Planner
• 3. All atoms must be SP2
• 4. All double bonds must be conjugated
• 5. Obey Huckle rule which state that any aromatic compound must
contain 4n+2 pi electrons where n 0,1,2,3,…

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 98
Compounds...3rd stage
Examples

n=1 n=2
 electron  electron

n=3
 electron
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 99
Compounds...3rd stage
 Examples of non- benzenoid aromatic cmpound

All are aromatic( cyclic, planner,1, and agree with

Huckle rule: 4n+2= 6 (n=1)

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 100
Compounds...3rd stage
 Examples of non- aromatic

Not aromatic; both contain Sp3

Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic

07/05/2017 101
Compounds...3rd stage
 Not aromatic Not aromatic Aromatic; cyclic, planner,
Does not obey Huckel rule Does not obey Huckel rule obey Huckel rule
4n+2=8; n=1.5 4n+2=4; n=0.5 4n+2=2; n=0

Aromatic Not Aromatic

Aromatic
4n+2=10; n=2 8 pi electrons
4n+2=14; n=3

Aromatic Aromatic
Dr.Mohanad Mousa Kareem.....Polynuclear Aromatic
07/05/2017 102
4n+2=10; n=2 Compounds...3rd stage 4n+2=10; n=2