MIND MAP
BENZENE
&
ITS DERIVATIVE
Prepared by: NFAG, KMPh
CHEMICAL PROPERTIES OF BENZENE
Br
*Mechanism
Halogenation
*Mechanism
Friedel Crafts alkylation Br2 FeBr3
COOH CH3 conc. HNO3 , NO2
conc. H2SO4
KMnO4 , H+ CH3Cl Nitration
heat FeCl3 50-55 oC
*Mechanism
Cl2 uv CH3COCl AlCl3
CH2Cl COCH3
Friedel Crafts acylation
*Mechanism
Prepared by: NFAG, KMPh
MECHANISM OF BENZENE
NITRATION HALOGENATION
conc. HNO3 , NO2 Br2 , FeBr3 Br
conc. H2SO4 + H2O + HBr
50-55ÂșC
STEP 1 .. H .. STEP 1
.. . . + O : + + O:
N O.. ..:- + HSO4-
HO3SO.. H + H .O. N O.. ..:- H .O.
.. .. .. B....r+......-FeBr3 Br+ + FeBr4-
:O : :B..r B..r: + FeBr3 :B..r
H2O + N +
:O:
STEP 2 STEP 2
NO2+ Slow NO2 NO2 + NO2 Br+ Slow Br Br + Br
HH H H
H H
+
+ ++
STEP 3 NO2 + STEP 3 Br
+ FeBr3 + HBr
NO2+ Slow H NO2 + NO2 + Br
H H H FeBr4 -
+
Prepared by: NFAG, KMPh
MECHANISM OF BENZENE
FRIEDEL-CRAFTS ACYLATION FRIEDEL-CRAFTS ALKYLATION
O O Reaction of Benzene Ring with 10 haloalkane
CH3CCl , AlCl3 CCH3
CH3CH2Cl , AlCl3 CH2CH3
+ HCl + HCl
STEP 1 O O H .. H C....l+ -
CH3C C....l+ -AlCl3 CH3C + + AlCl4- C.. l: + AlCl3 CH3C AlCl3
O CH3C
.. H H
CH3C C..l: + AlCl3
STEP 2 O H C....l+
+CCH3 + CH3C
-
H AlCl3
Slow
Slow
O O O CH2CH3 CH2CH3 + CH2CH3
CCH3 + CCH3 H H
CCH3 H H + AlCl4-
H H
++
+ +
STEP 3
O O + CH2CH3 CH2CH3
CCH3 H AlCl4- + AlCl3 + HCl
+ CCH3
H AlCl4- + AlCl3 + HCl
Prepared by: NFAG, KMPh
MECHANISM OF BENZENE
FRIEDEL-CRAFTS ALKYLATION FRIEDEL-CRAFTS ALKYLATION
Rearrangement of 1o Haloalkane to a 3o Haloalkane Reaction of Benzene Ring with 2o / 30 Haloalkane CH3
(CH3)3CCH2Cl, AlCl3 CH2C(CH3)3 CH3CHClCH3 , AlCl3 CHCH3
+ HCl + HCl
STEP 1 .. CH3 H C.... l+ - STEP 1 CH3 C....l+ - CH3
.C. l: + AlCl3 CH3C C AlCl3 CH3C AlCl3 CH3C + + AlCl4-
CH3 H CH3 ..
CH3 H CH3C C.. l: + AlCl3 H
CH3C C
H
CH3 H
1, 2 - methyl shift H
STEP 2 CH3 H STEP 2
CH3 CH3C+ C H+ - CH3
+CCH2CH3 AlCl4 +CHCH3
CH3 CH3
3o carbocation electrophile
Slow
Slow
CH3 CH3 CH3CH3 CH3 CH3 CH3 CH3 CH3
CCH2CH3 + CH2CH3
CCH2CH3 H CHCH3 CHCH3 + CHCH3
H H
H HH
+
++ +
STEP 3CH3 CH3 CH3 CH3 STEP 3 CH3 CH3
CCH2CH3 CHCH3
+ CCH2CH3 + CHCH3
H AlCl4- + AlCl3 + HCl H AlCl4- + AlCl3 + HCl
Fast Fast
Prepared by: NFAG, KMPh
Prepared by: NFAG, KMPh