H4), 7.37 (d, J = 8.5 Hz, H8/H9), 7.20 (dd, J = 7.4 Hz, 4.6 Hz, H3),
6.79 (d, J = 8.5 Hz, H9/H8), 2.95-2.96 (m, 2H), 3.02-3.05 (m, 2H).
13C NMR (62.5 MHz, CDCl3) δ 192.8, 151.1, 150.6, 149.4, 148.6,
138.2, 135.06, 135.03, 134.2, 131.5, 131.4, 124.2, 113.1, 112.2,
28.1, 27.6. The latter fractions eluting with EtOAc:CH3OH (9:1)
afforded the compound 12 (Rf = 0.1) as a yellow solid (119 mg,
was chromatographed on alumina (Al2O3) eluting with CH2Cl2 (Rf
= 0.7) to afford the desired compound 17 as a white crystalline
solid (227.0 mg, 81%): mp > 200 oC. 1H NMR (250 MHz, CDCl3)
δ 9.27 (dd, J = 8.0, 1.8 Hz, 2H, H3 and H8), 8.96 (d, J = 8.5 Hz, 2H,
H3 of pyridine), 8.43 (d, J = 8.3 Hz, 2H, H5 of pyridine), 8.14-8.11
(m, 4H, H4, H6, H4 of pyridine), 7.89 (s, 2H, H5 and H6), 2.90 (s,
6H, CH3). 13C NMR (62.5 MHz, CDCl3) δ 200.5, 155.6, 155.4,
153.2, 145.8, 138.2, 137.5, 129.6, 127.2, 125.5, 122.3, 120.85,
26.1. MS (ESI) m/z 418.14 [M+, 100%], 419.15 [M + H+, 28.1%].
1
o
83%): mp >200 °C. H NMR (250 MHz, CDCl3, 25 C) δ 8.15 (s,
2H, H7 & H10), 7.96 (br. s, 2H, H2 & H15), 7.88 (s, 2H, H8 & H9),
7.38 (d, 2H, H4 & H9), 6.84 (dd, 2H, H3 & H14), 3.18 (t, 4H, J = 5.8
Hz), 2.96 (t, 4H, J = 5.8 Hz). 1H NMR (250 MHz, CDCl3, 50 oC) δ
8.84 (d, 2H, J = 4.8 Hz, H2 & H15), 7.98 (s, 2H, H7 & H10), 7.88 (s,
2H, H8 & H9), 7.38 (dd, 2H, J = 7.8, 1.8 Hz, H4 & H13), 7.20 (dd, J
= 7.8, 4.8 Hz, H3 & H14), 3.24 (t, 4H, J = 6.8 Hz), 3.08 (t, 4H, J =
1,3(2,9)-Diphenanthrolina-2,4(2,6)-dipyridinacyclobutapha
ne (18)
To a solution of 2,3-diaminoterephthalaldehyde (110 mg, 0.67
mmol) and 2,9-di(6-acetylpyridin-2-yl)-1,10-phenanthroline (280
mg, 0.67 mmol) in EtOH (30 mL) was added 2 drops (0.8 mL) of
saturated KOH in EtOH. Resulting reaction mixture was refluxed
for 12 h and filtered while hot. The filter cake was washed with
CH2Cl2, CH3OH, and CH3CN to afford the compound 18 as a
o
6.8 Hz). 13C NMR (62.5 MHz, CDCl3, 25 C) δ 152.0, 151.5,
148.8, 145.9, 136.1, 135.2, 134.5, 133.8, 129.0, 126.9, 124.1, 28.0,
27.6. MS (ESI) m/z 386.15 [M+, 100%], 387.16 [M + H+, 28.1%].
12-(Pyridin-2-yl)-5,6-dihydroquinolino[8,7-b][1,10]phenant
hroline (13).
o
1
brown solid (321 mg, 94%): mp >200 C. H NMR (250 MHz,
DMSO-d6) 8.68 (d, J = 8.0 Hz, 4H, H4 and H7 of phen), 8.49 (d, J
= 8.0 Hz, 4H, H3 and H8 of phen), 8.35 (d, J = 7.8 Hz, 4H, H3 and
H5 of pyridine), 8.23 (t, J =7.8 Hz, 2H, H4 of pyridine), 8.01 (AB
quartet, 4H, H5 and H6 of phen). Not soluble enough to give 13C
NMR spectrum. MS (ESI) m/z 510.16 [M+, 100%], 511.16 [M +
H+, 36.8%]. HRFAB m/z 511.1668 Calcd for [C34H19N6]+:
511.1666. Anal. Calcd for C34H18N6-2H2O: C, 74.71; H, 4.06; N,
15.38; O, 5.85. Found C, 74.82; H, 4.05; N, 15.34.
To a solution of 8-amino-2-(pyridine-2-yl)quinoline-7-carb-
aldehyde (10, 60.0 mg, 0.24 mmol) and 2-acetylpyridine (35.4 mg,
0.2 mmol) in EtOH (30 mL), was added 2 drops (0.8 mL) of
saturated KOH in EtOH solution. The resulting reaction mixture
was refluxed for 10 h. Evaporation of the solvent and the residue
was chromatographed on silica gel eluting with ethyl acetate to
afford compound 13 (86.7 mg, 79%, Rf = 0.1) as a yellow solid:
o
mp > 200 C. 1H NMR (500 MHz, CDCl3) δ 9.15 (d, 1H, J = 8.0
Hz, 1.0 Hz, H3 of pyridine), 8.85 (dd, 1H, J = 4.8, 1.5 Hz, H2),
8.80 (d, J = 8.5 Hz, H11), 8.72 (ddd, 59 (d, 1H, J = 4.8, 1.8, 0.8 Hz,
H6 of pyridine), 8.35 (d, J = 8.5 Hz, H10), 8.09 (s, 1H, H7), 7.97 (dt,
J = 8.0, 1.0 Hz, H4 of pyridine), 7.82 (d, 1H, J = 8.8 Hz, H8/H9),
7.76 (d, H, J = 8.8 Hz, H9/H8), 7.63 (dd, 1H, J = 7.8, 1.5 Hz, H5),
7.36 (ddd, 1H, J = 7.8, 4.8, 1.5 Hz, H5 of pyridine), 7.31 (dd, J =
7.8, 4.8 Hz, H3), 3.32-3.20 (m, 2H), 3.12-3.05 (m, 2H). 13C NMR
(62.5 MHz, CDCl3) δ 156.7, 155.9, 151.9, 151.8, 149.0, 148.9,
146.2, 145.7, 137.2, 137.1, 136.1, 134.93, 134.87, 133.6, 129.2,
128.8, 127.1, 126.2, 124.13, 124.09, 123.4, 121.1, 28.0, 27.7. MS
(ESI) m/z 360.14 [M+, 100%], 361.14 [M + H+, 26.0%]. Anal.
Calcd for C24H16N4: C, 79.98; H, 4.47; N, 15.55. Found C, 81.08;
H, 4.56; N, 14.36.
Supporting Information
The supporting information for this article is available on the
Acknowledgement
Financial support from Yeungnam University (#2016A380213)
is gratefully appreciated.
References
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2003, 125, 4732.
2-(6-Acetylpyridin-2-yl)-8-aminoquinoline-7-carbaldehyde
(15)
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o
1
compound 16 as a brown solid (61 mg, 23%): mp > 200 C. H
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= 7.8 Hz, H3), 8.97 (d, 2H, J = 8.5 Hz, H3 and H5 of pyridine), 8.45
(dm, 1H, J = 8.6 Hz, H4 of pyridine, overlapped with NH2), 8.40 (d,
2H, J = 7.7 Hz, H4), 7.71 (d, 2H, J = 8.6 Hz, H5), 7.17 (d, 1H, J =
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= 0.1) as a yellow solid (90 mg, 51%): mp > 250 oC. 1H NMR (250
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H2 of pyridine), 8.73 (d, 1H, J = 8.0 Hz, H3), 8.20 (d, 1H, J = 8.0
Hz, H5 of pyridine), 8.09 (dd, 1H, J = 8.0, 1.3 Hz, H5 of pyridine),
8.01 (t, 1H, J = 7.8 Hz, H4 of pyridine), 7.54 (d, 1H, J = 8.5 Hz,
H5), 7.04 (d, 1H, J = 8.5 Hz, H5), 2.85 (s, 3H, CH3). MS (ESI) m/z
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2,9-Di(6-acetylpyridin-2-yl)-1,10-phenanthroline (17)
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