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Chapter 8
Chapter 8
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
(.) (-)
(+) (.)
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
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
35
HALOGENATIONS OF ALKYL
SUBSTITUENTS
NOT Lewis acid
37
NUCLEOPHILIC AROMATIC
SUBSTITUTION REACTIONS