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
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 Chapter 8: ARENES

Benzene

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 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

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Aromatic:

(+)
(-) (+)

N O S
H 4

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NOT aromatic: NOT (4n + 2) π e

(.) (-)

(+) (.)

4πe 5πe 7πe 8πe

Interrupted
cyclic π
cloud

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 NOMENCLATURE OF
MONOSUBSTITUTED BENZENES
Name of substituent + benzene

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Names have to be memorized:

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 NOMENCLATURE OF DI- &
POLYSUBSTITUTED BENZENES

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

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 1 of the substituents can be incorporated into a name:

Names
incorporating
2 substituents

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Alphabetical Lowest possible
order numbers

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PREPARATION OF BENZENE

Petroleum Bezene

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 REACTIONS OF BENZENE
Halogenations of benzene

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Reaction mechanism: electrophilic substitution

Catalyst regeneration 13

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Nitration of benzene

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Sulfonation of benzene

Reversible reaction
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Reaction mechanism: electrophilic substitution

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Friedel-Crafts Alkylations of benzene

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Carbocation
rearrangement

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Friedel-Crafts Acylations of benzene

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Reaction mechanism: electrophilic substitution

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 Rearrangement

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REACTIONS OF SUBSTITUTED
BENZENES
Relative rates of electrophilic substitutions:

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

Electron-donating Eelectron-withdrawing

Activating Deactivating

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

Only for
halogen
group

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E/W
group

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E/D
group

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E/W
group

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 THE ORTHO-PARA RATIO

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

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

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 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

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SYNTHESIS OF TRISUBSTITUTED BENZENES
More activating substituent controls the regioselectivity

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 HALOGENATIONS OF ALKYL
SUBSTITUENTS
NOT Lewis acid

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

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OXIDATIONS OF ALKYL SUBSTITUENTS

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 NUCLEOPHILIC AROMATIC
SUBSTITUTION REACTIONS

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

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