Chemistry Reference
In-Depth Information
Fig. 16
Structure of
benzo[
c
]phenanthrene [
61
]
112
A
D
B
C
66
1. PCl
5
2. AlCl
3
1. LiAlH
4
2. S
8
,heat
OH
OH
O
O
O
O
2
,19%
67
68
, 62%
Scheme 15
Synthesis of 1,12-dimethylbenzo[
c
]phenanthrene [
9
]
1
12
1 2
O
HO
HO
2
C
CO
2
H
71
5
8
69
70
NO
2
NO
2
O
2
N
NO
2
H
2
N
NH
2
NC
CN
72
73
Fig. 17
Structures of 1,12-dimethylbenzo[
c
]phenanthrenes
Several 5,8-disubstituted 1,12-dimethylbenzo[
c
]phenanthrenes, including diacid
70
[
63
,
64
], diacetylene
71
[
65
], diamine
72
[
66
], and the tetranitro derivative
73
[
66
], have also been synthesized and resolved. The charge transfer complex
between (
M
)-
73
and electron-rich (
M
)-
72
was found to be more stable than the
complex between (
M
)-
73
and (
P
)-
72
.
A series of optically active macrocyclic amides, such as
74
(Fig.
18
), consisting
of one or more units of
70
, have been prepared [
63
]. A modest level of asymmetric
induction using
74
as the catalyst for the addition reaction between aromatic
aldehydes and diethylzinc was observed.
Trimer (
n ¼
9) of
75
(Fig.
19
) containing
m
-phenylene spacers
form thermally stable helix-dimers in non-polar solvents [
67
]. In hydrogen-bond
breaking solvents, such as DMSO and THF,
3) to nonamer (
n ¼
they dissociate into random-coil
monomers.
Cyclic alkyne (
M
,
M
,
M
)-
76
(Fig.
20
) was constructed from three units of (
M
)-
71
and three units of a
m
-phenylene derivative by the Sonogashira reactions [
65
]. The
enantiomer (
P
,
P
,
P
)-
76
and its diastereomers (
M
,
P
,
M
)-
76
and (
P
,
M
,
P
)-
76
were
likewise synthesized. Self-aggregation of (
M
,
M
,
M
)-
76
to form a dimer occurs in
