Nitration of Methyl Benzoate - University of Illinois Archives Archives/1505050... · Z Electron...
Transcript of Nitration of Methyl Benzoate - University of Illinois Archives Archives/1505050... · Z Electron...
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Nitration of Methyl Benzoate
COOCH3
HNO3, H2SO4
COOCH3
NO2
COOCH3COOHCH3OH
H2SO4
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Multistep Synthesis
A B C50% 50%
Yield = 25%
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(CH3)3COH (CH3)3ClHCl
Nucleophilic Aliphatic Substitution
NO2+
+
H NO2
Electrophilic Aromatic Substitution
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ARENE SUBSTITUTION
H EE+
+ H+
The electrophile REPLACES H+
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H E - Y H E
+
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H E - Y H E
+
H E
+
H E
+
H E
+
E
+ H+
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H E
+
H E
+
H E
+
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Nitration of BenzeneNO2
HNO3
H2SO4
Nitrobenzene
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Nitration Reagent
Nitronium Ion
HONO2 + 2 H2SO4 NO2+ + H3O+ + 2 HSO4
-
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HNO2
+ H NO2
+
NO2
+ H+
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Multiple SubstituentsG
G G
G
Second Group. Where go? How fast?
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Nitration of TolueneCH3
CH3NO2
CH3
NO2
CH3
NO2
HNO3
63% 3% 34%
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CH3NO2
H
CH3NO2
H
CH3NO2
H+
+ +
CH3
NO2
H
CH3
NO2
H
CH3
NO2
H
CH3
NO2H
CH3
NO2H
CH3
NO2H
+
+
+
+ ++
ORTHO
META
PARA
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G
Electron donating groups favorreaction ORTHO and PARA.
Electron Donating
Ortho
Para
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CF3
Nitration of (trifluoromethyl)benzene
HNO3
H2SO4
CF3
NO2
CF3
NO2
CF3
NO2
6% 91% 3%
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CF3
Electron Withdrawing group
+ chargehere bad
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CF3HNO2
CF3H
NO2
CF3H
NO2
CF3
H
NO2
CF3
H
NO2
CF3
H
NO2
CF3
H NO2
CF3
H NO2
CF3
H NO2
Ortho
Meta
Para
++ +
+
+
+
+ ++
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Z
Electron Withdrawing Groups areMeta Directors and DEACTIVATING
ElectronWithdrawingGroup
Meta Product
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COOCH3
HNO3, H2SO4
COOCH3
NO2
Main Reaction
Side Products
meta
COOCH3NO2
NO2
COOCH3 COOCH3
NO2O2N
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Procedure
1. Dissolve methyl benzoate in H2SO4
2. Mix HNO3 and H2SO4 at 0oC
3. Add HNO3 / H2SO4 dropwise to methyl benzoate at 0oC
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4. Let stand at roomtemperature 10minutes
5. Pour onto ice
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Filter
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Wash
Recrystallize frommethanol
Dry
Weigh
m.p.