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Modules 06710-12-14
Ph
N
H
Br
H3C
N
O
CH3
H3C
N
H
H
N
CH3
OMe
NH
Ph
CH3
H
N
Br
CH3
2-bromoindole
5-methoxyisoquinolin-1-one
2-phenyl-3,4-dihydroquinoline
2,7-dimethylquinolin-4-one
3,8-dimethylisoquinoline
4-phenyl-1,2-dihydroquinoline
7-bromo-2,3-dihydroindole
2,7-dimethylquinoline
A2 Name the following heterocycles
Br
H3C
CH3
N
H
CH3
N
H
H
N
MeO
NH
OMe
CH3
CH3
N
H
N
H
N
Ph
OMe
page 1
Modules 06710-12-14
H3C
NH2
Br
2
H2N
Ph
CH3
3
CH3
H3C
NH2
O
4
Br
?
Ph
NH2
O
5
NH2
Ph
?
CH3
Et
Et
NH2
O
+
Ph
Br
7
H2N
H3C
?
CH2CH3
page 2
Modules 06710-12-14
B2 Formulate the products from the following reactions, all of which are quinoline,
quinolone or isoquinoline syntheses. Identify key pre-cyclisation intermediates in
each case.
MeO
CH3
NH2
H+
+
H3C
MeO
O
2
H+
+
O2N
H
NH2
1. Et3N
2. POCl3, heat
Cl
3
Cl
NH2
+
H3C
O
4
Cl
1. Et3N
2. POCl3, heat
3. Pd-C, heat (no H2)
NH2
H3C
+
1. AcOH, 40 oC,
with azeotropic
removal of H2O
Ph
OEt
NH2
H3C
+
?
2. Ph2O, 250 oC
1. 150 oC,
2. conc. H2SO4
Ph
OEt
NH2
Br
7
H2N
O
NaOH, 0 oC
H3C
?
Ph
CH3
Br
8
NH2
H
H2SO4, heat
page 3
Modules 06710-12-14
B3 Formulate the products from the following reactions, all of which are Fischer
indole syntheses. In each case identify the enamine intermediate prior to the [3,3]sigmatropic rearrangement step.
O
1
NHNH2
H3C
O
2
NHNH2
H3C
CH3
NHNH2
Br
4
CH3CH2
H2NHN
Br
CH2CH3
+
NHNH2
H3C
CH3
O
NHNH2
+
MeO
O
7
NHNH2
H3C
Ph
CH3
O
8
CH3
NHNH2
O
+
NHNH2
page 4
Modules 06710-12-14
B4 From what starting materials could you make these two indoles? In these
examples, could there be any problems with formation of isomeric indole products? If
so what is (are) their structure(s)?
1
H3C
?
CH3
N
H
?
MeO
N
H
.
C:- Effect of substituents on reaction rate
For each of the following pairs of reactions, which will have the faster rate of reaction
and why?
C1
O
MeO
MeO
H
+
reaction A
NH2
CH3
CH3
CH3
CH3
CH3
O
O2N
O2N
H
+
NH2
CH3
reaction B
C2
O
MeO
MeO
H
+
reaction A
NH2
CH3
O
H
+
MeO
NH2
CH3
MeO
reaction B
C3
MeO
MeO
NC
NH2
NC
NC
NC
MeO
MeO
CH2O
NC
NH
NC
reaction B
CH2O
NH2
reaction A
MeO
page 5
MeO
NH
Modules 06710-12-14
Cl
heat
HN
+
N
(1 mole equivalent)
Cl
heat
Na O
(1 mole equivalent)
Cl
Cl
heat
+
N
H2N
Cl
(1 mole equivalent)
CH3
4
heat
HNO3 / H2SO4
Br2
Br2
CH3
N
H
CH3
6
N
H
O
7
N
H
H+ cat
H
O
8
N
H
Br
?
C13H17NO
H+ cat
H
N
H
NaOEt
+
EtO2C
?
heat
Cl
9
CH3I
CO2Et
?
N
Cl
N
H
NH2
page 6