Novel Phenanthroline-Containing Helicates
J . Org. Chem., Vol. 64, No. 26, 1999 9363
on the ARX 500 NMR spectrometer as described previuosly.21c-f
Chemical shifts are reported in ppm relative to the peak of
(1): Butyllithium (1.6 M, 2.5 mL, 4 mmol) was added, using a
syringe through a septum, to a solution of 5 (0.87 g, 3.8 mmol)
dissolved in dry THF (200 mL) and cooled to -70 °C, under
an argon atmosphere. After 30 min a solution of 6 (0.5 g, 1.4
mmol) in dry THF (30 mL) was added and the mixture was
refluxed for 20 h. After evaporation, the crude solid was
recrystallized from hot methanol, yielding 0.25 g of 1 (27%
the residual protonated solvents (δ DMSO-d
6
2.53, δ CDCl
.26). C NMR chemical shifts are also reported in ppm
relative to the solvent resonance (δ DMSO-d 39.5, δ CDCl
7.0), and the spin-spin couplings are reported in hertz. Fast
3
1
3
7
6
3
7
atomic bombardment mass spectra (FAB-MS) were recorded
on a VG-AutoSpec M250 mass spectrometer (Manchester,
U.K.) in m-nitrobenzyl alcohol (NBA) matrix. Melting points
were all measured on a IA9100 melting point apparatus
1
yield): mp 173 °C. H NMR (500 MHz, CDCl ): 8.29 (d, 8.2,
3
H-11, 2H) 8.34 (d, 7.7, H-19, 2H), 8.15 (d, 8.1, H-4, 2H), 7.98
(d, 8.2, H-12, 2H), 7.83 (t, 7.7, H-18, 2H), 7.75 (s, H-7, H-8,
(Electrothermal, U.K.), and the values are not corrected.
4
4
H), 7.59 (d, 7.5, H-17, 2H), 7.51 (d, 8.1, H-3, 2H), 5.28 (s, H-14,
H), 4.95 (s, H-15, 4H), 2.94 (s, H-1, 6H). C NMR (500 MHz,
The following compounds were prepared according to the
13
1
6b
literature. 1,10-Phenanthroline-2,9-dicarboxyaldehyde (12):
DMSO-d
6
): 159.9, 159.3, 157.7, 155.5, 145.3, 145.1, 137.5 (C-
1
6b
1
mp 237 °C (lit. mp 231-232 °C ). H NMR (200 MHz,
CDCl ): 10.57 (s, 2H), 8.52 (d, 8.0, 2H), 8.39 (d, 8.0, 2H), 8.05
s, 2H). 2,9-Bis(hydroxymethyl)-1,10-phenanthroline (13):
1
8), 136.9 (C-11), 136.5 (C-4), 128.0, 126.9, 126.1 (C-8), 125.5
3
(C-7), 123.7 (C-3), 121.4 (C-17), 120.7 (C-12), 119.9 (C-19), 74.5
1
6b
(
(
6
C-14), 74.2 (C-15), 29.7 (C-1). FAB-MS (DMSO, NBA): m/z
51.2 (1Na , 100%), 635 (1Li , 100%), 629.2 (1H , 10%).
1
6b
1
mp 197 °C (lit. mp 197-198 °C ). H NMR (200 MHz, DMSO-
): 8.50 (d, 8.0, 2H), 7.95 (s, 2H), 7.90 (d, 8.0, 2H), 5.73 (t,
.0, 2H), 4.9 (d, 8.0, 4H). We found that by continuing the
+
+
+
d
6
2
,9-Bis[(2-m e t h yl-1,10-p h e n a n t h r olin -9-yl)m e t h yl-
8
en oxym eth ylen yl]-1,10-p h en a n th r olin e (2). Sodium hy-
dride (143 mg, 3.3 mmol) was added to a stirred solution of 5
reflux for 4 h instead of 2 h the yield increases the 80%-90%.
1
6b
2
,9-Bis(bromomethyl)-1,10-phenanthroline (7): mp 108-
16b 1
(785.5 mg, 3.3 mmol) in dry THF (50 mL) at room temperature
1
d
4
10 °C (lit. mp 110-111 °C ). H NMR (200 MHz, DMSO-
): 8.53 (d, 8.0, 2H), 8.01 (s, 2H), 7.94 (d, 8.0, 2H), 5.01 (s,
H). 6,6′-Bis(bromomethyl)-2,2′-bipyridine (6): mp 182 °C (lit.
under an argon atmosphere. After 1 h of stirring at this
temperature, the mixture was warmed to 45 °C and 7 (600
mg, 1.65 mmol) dissolved in dry THF (20 mL) was added
dropwise. Warming and stirring were continued for an ad-
ditional 20 h, and the mixture was evaporated. The crude solid
was eluted with a 1:1 chloroform:methanol solution through
an LH-20 column. Trituration in hot tert-butyl ether gave 100
6
8
a
8
a
1
mp 180-181 °C ). H NMR (200 MHz, CDCl
H), 7.82 (t, 8.0, 2H), 7.47 (d, 6.0, 2H), 4.62 (s, 4H).
Syn th esis. 2,9-Dim eth yl-1,10-p h en a n th r olin e N-Oxid e
3
): 8.38 (d, 8.0,
2
1
5
(
8). Compound 8 was prepared as described with the follow-
ing modifications: 2,9-dimethyl-1,10-phenanthroline (7) (5 g,
1
mg of 2 (10% yield): mp 215-220 °C (dec). H NMR (500 MHz,
0
7
.024 mol) was dissolved in acetic acid (28 mL) and heated to
5 °C. Then 30% hydrogen peroxide (4.36 mL, 0.04 mol) was
6
DMSO-d ): 8.63 (d, 8.0, H-18, 2H), 8.38 (t, 8.5, H-7, H-8, 4H),
8
2
.08 (s, H-21, 2H), 8.04 (d, 8, H-17, 2H), 7.92 (d, 8.5, H-11,
H), 7.87 (d, 8.5, H-4, 2H), 7.72 (d, 8, H-12, 2H), 7.66 (d, 8.5,
added. After 3.5 h of reflux, the mixture was cooled and added
to a sodium carbonate solution (30 g in 270 mL of water). The
resulting mixture was stirred for 30 min and then extracted
with chloroform, dried, and evaporated, yielding 5.15 g of 8
H-3, 2H), 5.15 (s, H-15, 4H), 4.895 (s, H-14, 4H), 2.66 (s, H-1,
H). 13C NMR (500 MHz, DMSO-d
): 158.6, 158.6, 158.4,
157.8, 144.5, 144.1, 137.4 (C-18), 136.9 (C-7), 136.5 (C-8), 127.9,
6
6
1
5
1
(
(
7
3
∼100% yield): mp 135 °C (lit. mp 131-132 °C ). H NMR
200 MHz, CDCl ): 8.13 (d, 8.0, 1H), 7.71 (s, 1H), 7.69 (s, 1H)
.67 (d, 8.0, 1H), 7.63 (d, 8.0, 1H), 7.52 (d, 8.0, 1H), 2.94 (s,
H), 2.78 (s, 3H).
-(Acetoxym eth yl)-9-m eth yl-1,10-p h en a n th r olin e (9).
1
3
27.5, 126.6, 126.4 (C-21), 126.2 (C-11), 125.4 (C-4), 123.6 (C-
3
), 121.5, 120.6 (C-12), 73.3 (C-15), 72.9 (C-14), 24.9 (C-1). FAB-
+
MS (DMSO, NBA): m/z 675.3 (2Na , 100%).
2
6′′,6′′′-Bis[(6-m eth yl-2,2′-bip yr id in -6′-yl)m eth ylen oxy-
1
5
8a
Compound 9 was prepared as decribed with the only modi-
fication being that the crude was eluted after evaporation
without any workup through a short alummina column with
m eth yl-yl]-2′′,2′′′-bip yr id in e (3). Compound 3, known as
BP , was prepared according to the literature, yielding the
3
1
expected H NMR spectrum: mp 232-233 °C (lit. mp 227-
8
a
1
dichloromethane. The eluent was evaporated, yielding 3.8 g
2 2
229 °C ). H NMR (500 MHz, CD Cl ): 8.32 (d, 7.7, H-8, 4H),
1
of 9 as a brown oil (59% yield). H NMR (200 MHz, CDCl
3
):
8.19 (d, 7.7, H-5, 2H), 7.83 (t, 7.7, H-9, 4H), 7.68 (t, 7.7, H-4,
2H), 7.54 (d, 7.7, H-10 or H-15, 2H), 7.52 (d, 7.7, H-10 or H-15,
2H), 7.16 (d, 7.7, H-3, 2H), 4.85 (s, H-12 and H-13, 8H), 2.58
8
1
.30 (d, 8.0, 1H), 8.24 (d, 8.0, 1H), 7.79 (s, 2H), 7.72 (d, 8.0,
H), 7.58 (d, 8.0, 2H), 5.64 (s, 2H), 2.99 (s, 3H), 2.2 (s, 3H).
-(Hyd r oxym eth yl)-9-m eth yl-1,10-p h en a n th r olin e (5).
2
(s, H-1, 6H).
A solution of 1 N NaOH (14 mL) was added to a stirred solution
of 9 (3.78 g, 0.0135mole) in ethanol (15 mL) at room temper-
ature. The solution was stirred overnight, and then water was
added. The ethanol was evaporated, and the water layer was
extracted with dichloromethane (4 × 30 mL). The organic
phase was dried with magnesium sulfate and evaporated,
yielding 2.17 g of 5 as a brown powder (67% yield): mp 149-
2
,9-Bis[(6-m e t h yl-2,2′-b ip yr id in -6′-yl)m e t h yle n oxy-
14
m eth yl-yl]-1,10-p h en a n th r olin e (4). Compound 4 was
prepared as previously described by us and gave the expected
1
14
1
H NMR spectrum: mp 141 °C (lit. 141-142 °C ). H NMR
500 MHz, DMSO-d ): 8.56 (d, 8.5, H-16, 2H), 8.33 (d, 7.6, H-8,
H), 8.2 (d, 7.7, H-5, 2H), 8.02, 8.01, 8.00 (s, t, d, 7.5, 8.5, H-19,
H-9, H-15, 6H), 7.82 (t, 7.7, H-4, 2H), 7.7 (d, 7.6, H-10, 2H),
.32 (d, 7.7, H-3, 2H), 5.12 (s, H-13, 4H), 4.92 (s, H-12, 4H),
.59 (s, H-1, 6H).
(
2
6
1
5
1
1
8
1
3
52 °C (lit. mp 153-158 °C ). H NMR (200 MHz, CDCl ):
7
2
.23 (d, 8.0, 1H), 8.16 (d, 8.0, 1H), 7.76 (s, 2H), 7.58 (d, 8.0,
H), 7.52 (d, 8.0, 1H), 5.11 (s, 2H), 2.92 (s, 3H).
Com p lex P r ep a r a tion . [(1)
(CH CN) PF (48.3 mg, 0.13 mmol) in acetonitrile (2 mL) was
added to a solution of 1 (50 mg, 0.076 mmol) in dichlo-
romethane (2 mL). The red solution obtained was stirred for
2 3 6 3
Cu (P F ) ]. A solution of Cu-
6
,6′-Dim eth yl-2,2′-bip yr id in e (11). This compound was
1
6a
prepared as described with the following modifications: 1.4
M methyllithium (110 mL, 0.154 mol) was added to a stirred
solution of 2,2′-bipyridine 10 (6 g, 0.038 mol) in dry THF (250
mL) cooled to -40 °C. The solution was stirred at this
temperature for 1 h and then warmed to 0 °C. After 2 h at
this temperature, the mixture was refluxed for 4 h. Then the
reaction mixture was cooled and ice water (50 mL) was added.
Following evaporation and extracteion with dichloromethane
3
4
6
1
h and then evaporated. The crude product was triturated
with a diethyl ether:dichloromethane (9:1) solution, followed
by a solution of diethyl ether:acetonitrile (95:5). Finally, the
product was dried (50 °C, 25mbar), yielding 40 mg of the
complex as a red powder (53% yield): mp 240 °C (dec). H NMR
6
(500 MHz, DMSO-d ): 8.82 (d, 8.0, H-4, 4H), 8.43 (d, 8.1, H-11,
4H), 8.36 (d, 8.9, H-8, 4H), 8.29 (d, 8.5, H-7, 4H), 8.27 (d, 9.2,
H-19, 4H), 8.00 (d, 8.0, H-3, 4H), 7.61 (t, 7.7, H-18, 4H), 7.13
(d, 8.1, H-12, 4H), 6.44 (d, 7.42, H-17, 4H), 3.8 (AB, 13.3, H-15,
1
(
3
4 × 60 mL), MnO
2
(100 g, Merck 805958) was added. After
0 min the mixture was dried with magnesium sulfate and
filtered over Celite. The solvent was evaporated yielding 3.65
g of 11 as an orange powder (52% yield): mp 89-90 °C (lit.
1
6c
1
13
mp 89.5 °C ). H NMR (200 MHz, CDCl
3
): 8.16 (d, 8.0, 2H),
8H), 3.79 (AB, 17.4, H-14, 8H), 2.45 (s, H-1, 12H). C NMR
7
.68 (t, 8.0, 2H), 7.15 (d, 8.0, 2H), 2.62 (s, 6H).
Liga n d P r ep a r a tion . 6,6′-Bis[(2-m eth yl-1,10-p h en a n -
t h r olin e-9-yl)m et h ylen eoxym et h ylen yl]-2,2′-bip yr id in e
6
(500 MHz, DMSO-d ): 157.7, 154.9, 154.23, 149.6, 141.9, 141.7,
137.9 (C-18), 137.52 (C-12), 137.36 (C-4), 127.92, 127.0 (C-7),
126.74 (C-8), 125.8, 125.8 (C-3), 122.8 (C-17), 122.6 (C-11),