ORGANIC CHEMISTRY

1
 Chapter 8: ARENES

Benzene

2
 CRITERIA FOR AROMATICITY
To be classified as aromatic, a compound must
meet both of the following criteria:
• It must have an un-interrupted cyclic p cloud
above & below the plane of the molecule
• The p cloud must contain (4n + 2) p electrons (n
= 0, 1, 2…)

un-interrupted
cyclic p cloud 6pe=4x1+2

3
Aromatic:

(+)
(-) (+)

N O S
H 4
NOT aromatic: NOT (4n + 2) p e

(.) (-)

(+) (.)

4pe 5pe 7pe 8pe

Interrupted
cyclic p
cloud

5
6
Exercise
Which of following compounds and ions are aromatic?

7
Aromatic:

8
 NOT aromatic:
Not (4n+2):

(4n+2) but have interrupted cyclic p cloud:

9
 NOMENCLATURE OF
MONOSUBSTITUTED BENZENES
Name of substituent + benzene

10
Names have to be memorized:

11
 NOMENCLATURE OF DI- &
POLYSUBSTITUTED BENZENES

Alphabetical order, 1-position for the 1st stated substituent

12
 1 of the substituents can be incorporated into a name:

Names
incorporating
2 substituents

13
Alphabetical Lowest possible
order numbers

14
PREPARATION OF BENZENE

Petroleum Bezene

15
 REACTIONS OF BENZENE

Typical reaction for

aromatic compounds NOT
AROMATIC
Addition
product

AROMATIC

Electrophilic aromatic Substitution

substitution (SEAr) product
16
ELECTROPHILIC AROMATIC SUBSTITUTION

17
Halogenations of benzene

18
Reaction mechanism: electrophilic substitution

Catalyst regeneration 19
Nitration of benzene

20
Sulfonation of benzene

Reversible reaction
21
Reaction mechanism: electrophilic substitution

22
Friedel-Crafts Alkylations of benzene

23
24
Carbocation
rearrangement

25
26
Friedel-Crafts Acylations of benzene

27
Reaction mechanism: electrophilic substitution

28
Rearrangement

29
Exercise Complete following reactions:

30
31
 REACTIONS OF SUBSTITUTED
BENZENES

Reaction rate and

regioselectivity depends
on the electronic effect of
original substituent.
32
Relative rates of electrophilic substitutions:

Electron- Electron-
donating withdrawing

33
+I,
+C, - I,
Relative reactivity -C,
+H

Electron-donating Electron-withdrawing

Activating Deactivating

ortho/para-directing meta-direcring
34
35
36
 EFFECTS OF SUBSTITUENTS
ON ORIENTATION
E/D
group

Only for
halogen
group

37
E/W
group

38
E/D
group

39
E/W
group

40
Designing the synthesis of a substituted benzene requires
careful consideration of the order in which the substituents
are to be placed on the ring

41
 THE ORTHO-PARA RATIO

Increase in Decrease in
the size of the o/p ratio
substituents

42
 ADDITIONAL CONSIDERATIONS
More deactivating than halogen, the ring is too unreactive
for (only) Friedel-Crafts alkylations & acylations, so be
careful in designing the synthesis of a substituted benzene

43
 Aniline & N-substituted anilines do NOT undergo Friedel-
Crafts reactions:

More
deactivating
than
halogen

Also can NOT undergo nitration –

primary amines are easily oxidized

Phenol & anisole do undergo Friedel-Crafts reactions,

orienting ortho & para – oxygen does “NOT” complex
with the Lewis acid 44
SYNTHESIS OF TRISUBSTITUTED BENZENES
More activating substituent controls the regioselectivity

45
SYNTHESIS OF TRISUBSTITUTED BENZENES
Consider electronic effects first and then steric effects

46
Exercise
Complete following reactions:

47
48
Exercise
Complete following reactions:

49
50
Exercise
From which acyl chlorides/anhydrides and arenes were
the following compounds prepared?

51
52
 HALOGENATIONS OF ALKYL
SUBSTITUENTS
NOT Lewis acid

Can undergo E1 & E2, SN1 & SN2 reactions as usual

53
OXIDATIONS OF ALKYL SUBSTITUENTS

54
55
Exercise
From benzene and other chemicals,
prepare following compounds:

56
57
58
 NUCLEOPHILIC AROMATIC
SUBSTITUTION REACTIONS

E/W groups must be positioned ortho / para to the halogen

59
The greater the number of E/W substituents, the easier it is
to carry out the reaction
60
61
Exercise
Complete following reactions:

62
63
Exercise

From benzene, Cl2, FeCl3, HNO3, H2SO4, Na, CH3OH,

H2O, NH3, and NaI, prepare following compounds:

64
65