Professional Documents
Culture Documents
1. Provide valid syntheses for the following compounds starting from either toluene or
benzene:
(a) 2-Bromo-4-nitrobenzoic acid
start with toluene
1. HNO3/H2SO4
2. Br2/FeBr3
3. KMnO4 or chromic acid
(b) 4-chloro-1-nitro-2-propylbenzene
start with benzene
1. CH3CH2COCl/AlCl3
2. Cl2/FeCl3
3. H2/Pd-C
4. HNO3/H2SO4
(c) 2-chloro-4-methylphenol
CH3
COOH
KMnO4
HNO3
OH
H2SO4
(g) 1,2-Diphenylethane
COOH
Br2
O2N
FeBr3
O2N
Br
O O
ClCCCl
Zn(Hg)
HCl
AlCl3
(h) 3-Ethylnitrobenzene
O
CH3COCl
HNO3
AlCl3
H2SO4
(i) 3-Bromonitrobenzene
Start with benzene
1. HNO3/H2SO4
2. Br2/FeBr3
(j) 3-Bromo-4-methylaniline
Start with toluene
1. HNO3/H2SO4
2. Br2/FeBr3
3. SnCl2/HCl
Zn(Hg)
HCl
NO2
NO2
2. (a) Provide a mechanism for the following reaction using the curved arrow
formalism.
H3O+
H
O
H3O+
OH
OH
OH
OH2
(b) Provide a mechanism for the following reaction using the curved arrow formalism.
OH
tBu
H3 O+
H3 C
tBu
CH3
SH
This group is ____ortho/para___ directing
ortho/para or meta
Benzene thiol
or
Thiophenol
(b) Explain, using resonance forms. Be sure to indicate why the thiol group is both
ortho/para or meta directing and activating or deactivating.
SH
SH
+
SH
H
E
SH
SH
SH
H
E
ortho
attack
major
esp stable
(PARA ATTACK SIMILAR)
SH
SH
SH
SH
SH
+
meta
attack
minor
The lone pairs on the sulfur atom stabilize the cationic charge in the intermediate leading to ortho and
para isomers. This indicates ortho/para directing ability. Since the intermediates for the favorable
electrophilic aromatic substitution of thiophenol are more stable than those for the EAS of benzene, the
thiol group must be activating.
4. Outline a sequence of reactions that is suitable for the preparation of the indicated
compound below from benzene or toluene and any needed organic or inorganic
reagents containing six carbons or less. Your synthesis will require more than one step.
You must show the structures of intermediate compounds in your synthesis. Do
not provide just a list reagents or you will lose points!
OH
O2N
???
benzene
or
toluene
Br
O
CH3COCl
HNO3
AlCl3
H2SO4
O2N
O
Br2
O2N
OH
NaBH4 O2N
FeBr3
Br
Br
5. Provide a mechanism for the following reaction using the curved arrow
formalism. [McMurray 16.64]
O
O
CH2Cl
H3C
H3C
Cl3Al Cl
O
H3C
CH3
AlCl3
O
H
CH2
H3C
Cl3Al Cl
O
H3C
CH3
CH3
H2
Pt-C
AlCl3
Br2
FeBr3
HNO3
H2SO4
Br
Br
NO2
HNO3
HCl
NO2
FeBr3
H2SO4
SnCl2
Br
Br2
Br
NH2
1. NaNO2
2. CuCl/Cl
Br
Cl
7. Outline a sequence of reactions that is suitable for the preparation of each of the
following compounds from the indicated starting material and any organic or
inorganic reagents containing six carbons or less. The syntheses will require more
than one step. Do not just provide reagents; you must provide the nature of the
synthetic intermediates.
(a) 2-Chloro-4-methylphenol from benzene or toluene [McMurray 16.49d]
CH3
CH3
CH3
CH3
SO3
KOH
Cl2
H2SO4
FeCl3
SO3H
Cl
OH
OH
O
O
O
Cl
Cl2
FeCl3
AlCl3
NO2
H2
HNO3
Pt-C
H2SO4
Cl
Cl
Cl