ORGANIC CHEMISTRY

Dr Nam T. S. Phan
Faculty of Chemical Engineering
HCMC University of Technology
Office: room 211, B2 Building
Phone: 38647256 ext. 5681
Email: ptsnam@hcmut.edu.vn
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 π cloud
above & below the plane of the molecule
• The π cloud must contain (4n + 2) π electrons (n
= 0, 1, 2…)

un-interrupted
cyclic π cloud 6πe=4x1+2

3
Aromatic:

(+)
(-) (+)

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

(.) (-)

(+) (.)

4πe 5πe 7πe 8πe

Interrupted
cyclic π
cloud

5
 NOMENCLATURE OF
MONOSUBSTITUTED BENZENES
Name of substituent + benzene

6
Names have to be memorized:

7
 NOMENCLATURE OF DI- &
POLYSUBSTITUTED BENZENES

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

8
 1 of the substituents can be incorporated into a name:

Names
incorporating
2 substituents

9
Alphabetical Lowest possible
order numbers

10
PREPARATION OF BENZENE

Petroleum Bezene

11
 REACTIONS OF BENZENE
Halogenations of benzene

12
Reaction mechanism: electrophilic substitution

Catalyst regeneration 13
Nitration of benzene

14
Sulfonation of benzene

Reversible reaction
15
Reaction mechanism: electrophilic substitution

16
Friedel-Crafts Alkylations of benzene
R càng dài thì
càng khó thế, và
giảng hiệu xuất

17
18
Carbocation
rearrangement

19
20
Friedel-Crafts Acylations of benzene

21
Reaction mechanism: electrophilic substitution

22
Rearrangement

23
REACTIONS OF SUBSTITUTED
BENZENES
Relative rates of electrophilic substitutions:

Electron- Electron-
donating withdrawing
24
 +I,
+C, - I,
Relative reactivity -C,
+H

Electron-donating Eelectron-withdrawing

Activating Deactivating

ortho/para-directing meta-direcring
25
26
27
 EFFECTS OF SUBSTITUENTS
ON ORIENTATION
E/D
group

Only for
halogen
group

28
E/W
group

29
E/D
group

30
E/W
group

31
 THE ORTHO-PARA RATIO

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

32
 ADDITIONAL CONSIDERATIONS
More deactivating than halogen, the ring is too unreactive for
(only) Friedel-Crafts alkylations & acylations

33
 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 34
SYNTHESIS OF TRISUBSTITUTED BENZENES
More activating substituent controls the regioselectivity

35
 HALOGENATIONS OF ALKYL
SUBSTITUENTS
NOT Lewis acid

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

36
OXIDATIONS OF ALKYL SUBSTITUENTS

37
 NUCLEOPHILIC AROMATIC
SUBSTITUTION REACTIONS

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

38
The greater the number of E/W substituents, the easier it is
to carry out the reaction
39
40