Inorg. Chem., 1998, 37(26), 6874-6883, DOI:10.1021/ic980837j
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Copyright © 1998 American Chemical Society
0
1998
American
Chemical
Society,
Inorg.
Chem.,
Terbrueggen
ic980837j
Supporting
Info
Page
1
Supplementary
Information
Functionalized
Rhodium
Intercalators
for
DNA
Recognition
Robert
H.
Terbrueggen,
Timothy
W.
Johann
and
Jacqueline
K.
Barton*
Division
of
Chemistry
and
Chemical
Engineering,
California
Institute
of
Technology
Pasadena,
CA
91125
Synthesis
of
Ligands.
4-carboxaldehyde-1,10-phenanthroline
(1).
This
compound
was
prepared
using
a
variation
of
the
procedure
described
in
reference
28
such
that
4-methyl-
1,10-phenanthroline
(8.2
g,
42.2
mmole)
was
used
as
a
starting
material.
The
product
was
isolated
by
filtering
the
hot
reaction
through
celite.
The
celite
was
washed
with
100
mL
of
absolute
ethanol,
and
the
ethanol
wash
was
combined
with
the
filtrate.
This
solvent
was
removed
by
rotary
evaporation.
The
residue
was
dissolved
in
water,
and
after
adjusting
the
pH
to
7
with
aqueous
Na
2
COz,
the
solution
was
extracted
with
chloroform.
The
chloroform
was
dried
over
anhydrous
sodium
sulfate
and
after
filtering,
the
solvent
was
removed
by
rotary
evaporation
to
yield
a
yellow
solid.
Yield
=
70%,
1
H NMR
(CDCl
3
,
ppm)
7.80
(111,
dd),
8.10
(2H,
m),
8.40
(1H,
d),
9.1
(lH,
d),
9.3
(1H,
d),
9.55
(1H,
d),
10.65
(1H,
s)
4-carboaldoxime-1,10-phenanthroline
(2)
This
compound
was
prepared
using
a
variation
of
the
procedure
described
in
reference
28
such
that
compound
1
was
used
as
a
starting
material.
The
desired
product
was
isolated
by
collecting
the
precipitate
that
is
formed
during
the
reaction.
The
precipitate
is
dissolved
in
100
mL
H
2
0.
The
solution
is
filtered
and
then
the
solvent
is
removed
by
rotary
evaporation
to
yield
a
white
solid.
Yield
=
65%.
1
H
NMR
(DMSO-d
6
,
ppm)
8.20
(1H,
dd),
8.40
(2H,
m),
8.85
(1H,
d),
9.05
(1H,
d),
9.15
(1H,
s),
9.20
(1H,
d),
9.30
(1H,
d),
12.75
(1H,
s);
13
C
NMR
(D
2
0,
ppm)
122.7,
124.0,
125.2,
125.8,
126.7,
128.6,
135.6,
137.0,
139.7,
143.6,
145.6,
145.9,
147.8.
,A?
M
D
1998
American
Chemical
Society,
Inorg.
Chem.,
Terbrueggen
ic980837j
Supporting
Info
Page
2
4-(aminomethyl)-1,10-phenanthroline
(3)
This
compound
was
prepared
using
a
variation
of
the
procedure
described
in
reference
28
such
that
compound
2
(3.0
g,
13.5
mmole)
was
used
as
a
starting
material.
Yield
=
71
%.
1H
NMR:
(D
2
0(pH
3),
ppm)
4.75
(2H,
s),
8.8
(1H,
d),
7.95
(1H,
d),
8.1
(2H,
m),
8.8
(1H,
d),
9.0
(lH,
d),
9.1
(1H,
d);
13
C
NMR
(D
2
0,
ppm):
40.0,
124,
124.5,
125,
126,
126.5,
129,
135,
137,
142,
144,
147,
151.
4-guanidylmethyl-1,10-phenanthroline
(4).
3
(0.5
g,
2.1
mmole)
was
dissolved
in
100
mL
of
water.
ZnCl
2
(285
mg,
2.1
mmol)
was
added,
and
the
pH
of
the
reaction
mixture
was
raised
to
pH
6.0
by
addition
of
aqueous
Na
2
CO
3
(1.0
M).
2-methyl-2-
thiopseudourea
hydrogen
sulfate
(1.15
g,
4.14
mmole)
was
added
and
the
reaction
mixture
was
heated
to
reflux
for
5
days
under
nitrogen.
The
reaction
was
purified
by
column
chromatography
(silica;
88%
CHC1
3
/10%
ethanol/2%
conc.
HCl).
Yield
=
63%.
1H
NMR
(D
2
0,
ppm)
4.5
(2H,
s),
8.5
(2H,
m),
8.0
(1H,
d),
7.65
(1H,
d),
7.5
(1H,
m),
7.35
(1H,
d),
7.15
(1lH,
d);
1
3
C
NMR
(D
2
0,
ppm)
41.0,
121.6,
122.1,
125.8,
126.3,
127.7,
128.4,
135.2,
136.2,
140.4,
145.4,
148.2,
154.1,
161.4
C14H14N5
calc.
252.3;
Found
FABMS
m/z
253
(M+)
4-(2-Hydroxyethyl)-4'-methyl-2,2'-bipyridine
(5).
This
compound
was
prepared
using
a
variation
of
the
procedure
described
in
reference
18
such
that
paraformaldehyde
was
added
a
solution
of
lithiated
4,4'-dimethyl-2,2'-bipyridine.
The
paraformaldehyde
(3.0
g,
99
mmole)
was
dried
under
vacuum
for
3
hours
and
added
to
the
lithiated
bipyridine
against
a
strong
flow
of
argon.
After
one
hour,
the
low-temperature
bath
was
removed
and
the
reaction
was
stirred
overnight
under
a
slow
flow
of
argon.
The
reaction
turned
bright
yellow.
A
solution
of
saturated
NaCl
(120
mL)
was
added
and
the
reaction
was
extracted
with
CH
2
C1
2
(2
x150
mL).
The
solution
was
dried
over
anhydrous
Na
2
SO
4
and
the
solvent
was
removed
to
yield
an
oily
mixture,
which
was
purified
by
column
chromatography
(silica;
19:1
CH2
C1
2
:Methanol).
The
product
was
recovered
as
a
yellow
oil.
Yield
=
42.5%.
1
H
NMR
(CDCl
3
,
ppm)
2.45
(1H,
s),
2.96
(211,
t),
3.98
(2H,
t),
7.13
II
D
1998
American
Chemical
Society,
Inorg.
Chem.,
Terbrueggen
ic980837j
Supporting
Info
Page
3
(lH,
d),
7.19
(lH,
d),
8.20
(1H,
s),
8.23
(1H,
s),
8.49
(1H,
d),
8.56
(1H,
d);
1
3
C
NMR
(CDC1
3
,
ppm)
21.60,
39.02
,
62.55,
122.18,
122.65,
124.98,
125.15,
148.80,
149.13,
149.45,
149.70,
156.20,
156.40.
4-(2-Bromoethyl)-4'-methyl-2,2'-bipyridine-
2HBr
(6).
This
compound
was
prepared
using
a
variation
of
the
procedure
described
in
reference
18
such
that
5
(4.5
g,
21.3
mmole)
was
refluxed
in
48%
HBr
(60
mL)
for
8
hours.
The
solvent
was
removed
under
vacuum
and
the
resulting
dark
brown
powder
was
dissolved
in
200
mL
ethanol
with
warming.
The
product
was
precipitated
by
addition
of
ether
(500
mL).
The
brown
sticky
solid
was
filtered
and
washed
with
ether.
Yield
=
69.5
%.
1
H
NMR
(D
2
0,
ppm)
2.4
(3H,
s),
3.2
(2H,
t),
3.65
(2H,
t),
7.45
(1H,
d),
7.6
(lH,
d),
8.0
(1H,
s),
8.15
(1H,
s),
8.45
(1H,
d),
8.55
(1H,
d);
13
C
NMR
(D
2
0,
ppm)
22,
32,
37,
123,
125,
127,
127.2,
143,
145,
145.1,
147,
154,
159
4-(2-Phthalimidoethyl)-4'-methyl-2,2'-bipyridine
(7).
This
compound
was
prepared
using
a
variation
of
the
procedure
described
in
reference
18
such
that
6
(4.5
g,
10.4
mmole)
was
dissolved
in
0.2
M
NaOH
(350
mL).
The
solution
was
extracted
with
CHCl
3
(2
x
350
mL).
The
extracts
were
washed
with
water
(350
mL)
and
dried
over
anhydrous
Na
2
SO
4
.
The
volume
of
the
solution
was
reduced
to
25
mL
on
a
rotary
evaporator.
Evaporation
to
dryness
has
to
be
avoided
because
of
product
decomposition.
DMF
(110
mL)
and
potassium
phthalimide
(3.2
g,
17.2
mmole)
were
added.
The
mixture
was
heated
at
50
oC
for
12
hours,
colled
to
room
temperature,
and
400
mL
of
water
were
added.
The
solution
was
extracted
with
CHCl
3
(2
x
400
mL).he
combined
organic
layers
were
washed
with
0.2
M
NaOH
(400
mL),
water
(400
mL),
and
dried
over
anhydrous
Na2SO4.
The
mixture
was
purified
by
column
chromatography
on
silica.
The
first
product
which
was
eluted
off
with
9:1
toluene:
ethyl
acetate
(Rf
=
0.47)
was
an
elimination
product;
4-vinyl-4'-methyl-2,2'-bipyridine
(Yield
=
40%,
Rf
=
0.47)
1
H
NMR
(CDCl
3
)
2.5
(3H,s),
5.55
(1H,
d),
6.05
(lH,
d),
6.8
(1H,
dd),
7.15
(1H,
d),
7.3
(1H,
d),
8.25
(1H,
s),
8.4
(1H,
s),
8.55
(1H,
d),
8.65
(lH,
d)
13
C
NMR
(CDCl
3
,
ppm)
21.6,
34