1. Aromaticity
Compound
N
B
N
H
π electrons
2
aromaticity
Aromatic
6
Non-aromatic
8
Anti-aromatic
4
Anti-aromatic
6
Aromatic
2. Predict the trend in acidity for the following substituted phenols. Rank by increasing
acidity and explain.
Trend: B A D C
OH
OH
OH
OH
NO2
OMe
A
B
NO2
C
D
3. Draw the relative energies for the molecular orbitals of the cyclooctatetraenyl dianion.
Predict the stability of this species:
π∗8
π∗7
π∗6
π5
π4
π2
π3
π1
4. Predict the products:
1. HCOCl, AlCl3
2. Ph3P=CH2
CO2H
CO2H
H2N
H2N
1. H3PO4,
O
O
CO2H
1. FeCl3, Cl2
2. NaOH, H2O,
high pressure, heat
3. H3O+
4. NaOH, H2O; CO2
5. HCl, H2O
6. Ac2O
O
1. Benzene, AlCl3
2. Zn(Hg), HCl, Heat
O
3. SOCl2
4. AlCl3
5. HNO3, H2SO4
O2N
O
O
OH
O
NH2
1. NaNO2, H2SO4
2. H2O, Heat
3. NaOH, H2O
4. O
5. H3O+
NO2
NO2
KOCH3, 70o
EtOH
F
F
F
F
F
OCH3
5. Provide reagents for the transformations:
Cl
Cl
1. Cl2, FeCl3
2. HNO3, H2SO4
3. Cl2, FeCl3
4. Fe, HCl
NH2
H
N
1. HNO3, H2SO4
2. Cl2, FeCl3
3. H2, Pd-C
4. CH3CH2COCl
O
Cl
Cl
1. HNO3, H2SO4
Cl
2. Cl2, FeCl3 (xs)
3. Fe, HCl
4. NaNO2, H2SO4
5. CuCl
Cl
O
Cl
Cl
1. AlCl3
2. FeCl3, Cl2
3. N2H4, KOH, Heat
O
Cl
1. AlCl3
2. Zn(Hg), HCl, heat
Cl
OH
1. HNO3, H2SO4
Br
NO2
2. KOH
3. Br2, FeBr3
Cl
Cl
6. Remembering that AlCl3 is a Lewis Acid, and the byproduct is hydrochloric acid,
propose a reasonable mechanism for the following transformation:
O
O
H
H
Cl
O
AlCl3, heat
AlCl3
H2O
O
H
Cl
O
H
O
H
H
O
H2O
AlCl3
O
H
H
Cl
OH2
O
OH
O
H3O+
H
H
O
O
H
O
OH
H
HCl
O
ClAlCl3
O
H
O
H
OH
HCl
O
H
Cl
AlCl3
O
H
O
HCl
AlCl3
7. Provide Conditions for the following:
A
Cl
+
AlCl3
B
+
AlCl3
Cl
C
+
H3PO4
D
OH
+
H2SO4
8. Mechanisms
Cl
O
NH3
NH2
N
NO2
O
+ NH4+
NH3
NH3
Cl
H3N
O
Cl
H2N
N
O
O
N
O
CH3
CH3
CH3
NH2
KNH2
+
liquid NH3
NH2
H
NH2
Cl
NH2
CH3
CH3
A
NH3
A
CH3
NH2
NH3
Cl-
B
B
NH2
NH3
NH2