Introduction of Subunits by Friedla¨nder Methodology
J . Org. Chem., Vol. 61, No. 9, 1996 3021
g (45%) of 8d as a yellow solid: mp 201-204 °C; 1H NMR
(CDCl3) δ 9.22 (dd, 1H, J ) 4.32 Hz), 8.32 (d, 2H, J ) 8.9 Hz),
8.22 (overlapping m, 2H), 8.04 (d, 1H, J ) 8.5 Hz), 7.72 (AB
quartet, 2H), 7.61 (dd, 1H), 6.85 (d, 2H), 3.05 (s, 6H); 13C NMR
(CDCl3) δ 169.8, 158.2, 152.2, 149.9, 146.8, 146.6, 137.3, 136.2,
134.6, 133.7, 133.6, 130.0, 128.5, 127.3, 126.0, 124.2, 120.1,
112.6, 40.3. Anal. Calcd for C20H17N3-0.25 H2O: C, 79.07; H,
5.76; N, 13.83. Found: C, 79.53, H, 5.65, N, 13.38.
to separate the unreacted amino aldehyde and then with CH2-
Cl2/EtOH (9:1), to give 0.24 g (60%) of 10b: mp > 300 °C; H
1
NMR (CDCl3) δ 9.24 (d, 2H, J ) 4.0 Hz), 9.15 (s, 1H), 8.54 (d,
2H, J ) 8.0 Hz), 8.34 (m, 4H), 8.26 (d, 2H, J ) 8.0 Hz), 7.81
(AB quartet, 2H), 7.76 (m, 3H), 7.64 (dd, 2H), 2.48 (broad s,
H2O); 13C NMR (CDCl3) δ 157.5, 150.3, 146.4, 146.0, 140.1,
136.8, 136.2, 129.5, 129.3, 129.1, 127.7, 127.0, 126.5, 126.2,
122.9, 121.1. Anal. Calcd for C30H18N4-0.5 H2O: C, 81.26; H,
4.18; N, 12.64. Found: C, 80.97; H, 4.13; N, 12.29.
2-(â-Na p h th yl)-1,10-p h en a n th r olin e (8e). To a mixture
of 1a (0.17 g, 1.0 mmol) and 2-acetylnaphthalene (0.17 g, 1.0
mmol) in EtOH (7 mL) under Ar was added saturated
ethanolic KOH (0.5 mL), and the mixture was refluxed for 18
h. After cooling, water was added and the mixture was
extracted with CHCl3 (3 × 30 mL). The combined organic
layers were washed with water and dried (MgSO4). Evapora-
tion of the solvent gave a crude material which was recrystal-
lized from CH2Cl2/cyclohexane to provide 0.14 g (48%) of 8e
as a yellow solid: mp 157-159 °C; 1H NMR (CDCl3) δ 9.38 (d,
1H, J ) 3.3 Hz), 8.95 (s, 1H), 8.59 (d, 1H, J ) 8.6 Hz), 8.40-
8.30 (overlapping m, 3H), 8.09 (m, 1H), 8.03 (d, 1H), 7.91(m,
1H), 7.86 (AB quartet, 2H), 7.72 (q, 1H), 7.53 (overlapping m,
2H); 13C NMR (CDCl3) δ 157.4, 150.1, 145.9, 145.8, 136.8,
136.7, 136.5, 133.9, 133.5, 132.1, 129.1, 129.0, 128.5, 127.6,
127.5, 126.7, 126.5, 126.2, 125,8, 125.4, 122.9, 120.9. Anal.
Calcd for C22H14N2: C, 86.27; H, 4.58; N, 9.15. Found: C,
86.00; H, 4.65; N, 9.55.
2,6-Di(ben zo[h ]qu in olin -2-yl)p yr id in e (10c). To a solu-
tion of 2,6-diacetylpyridine (0.20 g, 1.16 mmol) and 1b (0.40
g, 2.34 mmol) in absolute EtOH (50 mL) was added saturated
ethanolic KOH (2 mL). The solution was refluxed under Ar
for 18 h, cooled, and filtered to yield 0.43 g (86%) of 10c: mp
1
> 300 °C; H NMR (nitrobenzene-d5 at 100 °C) δ 9.58 (d, 2H,
J ) 8.1 Hz), 9.06 (m, 4H), 8.42 (d, 2H, J ) 7.9 Hz), 8.24 (t,
1H), 7.95 (d, 2H, J ) 7.8 Hz), 7.80 (m, 8H); 13C NMR could
not be obtained due to poor solubility. Anal. Calcd for
C31H19N3: C, 85.91; H, 4.39; N, 9.70. Found: C, 86.21; H, 4.43;
N, 9.62.
2,6-Di(1,10-p h en a n th r olin -2-yl)p yr id in e (10d ). To a
solution of 2,6-diacetylpyridine (0.20 g, 1.16 mmol) and 1a
(0.40 g, 2.34 mmol) in absolute EtOH (50 mL) was added
saturated ethanolic KOH (2 mL). The solution was refluxed
under Ar for 24 h, cooled, and poured into H2O (100 mL). The
aqueous solution was extracted with CH2Cl2 (3 × 100 mL),
and the combined organic layers were dried (MgSO4). Evapo-
ration of the solvent yielded a residue which was recrystallized
from CH2Cl2 to give 0.30 g (59%) of 10d : mp > 300 °C; 1H
NMR (CDCl3) δ 9.27 (d, 2H, J ) 4.3 Hz), 9.08 (m, 4H), 8.40 (d,
2H, J ) 8.3 Hz), 8.26 (d, 2H, J ) 8.1 Hz), 8.16 (t, 1H), 7.82
(AB quartet, 4H), 7.66 (dd, 2H), 1.95 (s, H2O); 13C NMR (CDCl3)
δ 156.4, 155.3, 150.5, 147.0, 146.0, 138.1, 136.8, 136.1, 129.0,
128.8, 126.7, 126.5, 123.3, 122.9, 121.0. Anal. Calcd for
C29H17N5-0.25 H2O: C, 79.18; H, 3.98; N, 15.93. Found: C,
79.26; H, 3.79; N, 15.75.
2-(1′-An th r a cen yl)-1,10-p h en a n th r olin e (8f). To a mix-
ture of 1a (0.17 g, 1.0 mmol) and 1-acetylanthracene (0.22 g,
1.0 mmol) in absolute EtOH (7 mL) under Ar was added
saturated ethanolic KOH solution (0.5 mL) dropwise, and the
mixture was refluxed for 36 h. After cooling, the solvent was
evaporated and the crude product was purified by chromatog-
raphy on Al2O3 (20 g), eluting with CH2Cl2, to give 0.14 g (41%)
of 8f: mp 113-117 °C; 1H NMR (CDCl3) δ 9.21 (d, 1H, J ) 4.1
Hz), 8.68 (s, 1H), 8.52 (s, 1H), 8.42 (d, 1H, J ) 8.2 Hz), 8.31
(d, 1H, J ) 8.0 Hz), 8.13 (d, 1H), 8.04 (d, 2H), 7.92 (AB quartet,
2H), 7.88 (m, 2H), 7.62 (q, 1H), 7.59 (m, 1H), 7.42 (overlapping
m, 2H), 1.56 (H2O); 13C NMR (CDCl3) δ 150.5, 146.5, 139.0,
136.0, 135.9, 132.2, 132.0, 131.4, 130.0, 129.8, 129.3, 129.0,
128.9, 128.7, 128.0, 127.9, 127.6, 126.6, 126.5, 126.3, 125.5,
125.2, 125.1, 124.9, 124.7, 122.9. Anal. Calcd for C26H16N2-
0.5 H2O: C, 85.48; H, 4.66; N, 7.67. Found: C, 86.01; H, 4.41;
N, 7.36.
3,4,6,7-Tetr a h yd r obis(2,3-ben zo[h ]qu in olin o)[c,l]a cr i-
d in e (12). A mixture of 1,2,3,4,5,6,7,8-octahydroacridine-2,8-
dione (11, 0.06 g, 0.28 mmol) and 1b (0.10 g, 0.58 mmol) in
absolute EtOH (10 mL) containing 1 pellet of KOH was
refluxed under Ar for 5 h. The product precipitated and was
filtered to yield 0.07 g of 12. The filtrate was evaporated, and
the residue was chromatographed on SiO2 (10 g), eluting with
CH2Cl2/EtOAc (4:1) and then CH2Cl2/EtOH, to give an ad-
2-(1′-P yr en yl)-1,10-p h en a n th r olin e (8g). To a mixture
of 1a (0.37 g, 0.15 mmol) and 1-acetylpyrene (0.26 g, 0.15
mmol) in EtOH (8 mL) under Ar was added saturated
ethanolic KOH (0.5 mL), and the mixture was refluxed for 24
h. After cooling, the solvent was evaporated. Purification by
chromatography on Al2O3 (15 g), eluting with CHCl3, provided
1
ditional 0.01 g (57% combined yield) of 12: mp > 300 °C; H
NMR (CDCl3) δ 9.93 (d, 2H), 7.96 (s, 2H), 7.89 (m, 4H), 7.79
(d, 2H), 7.73 (m, 2H), 7.62 (d, 2H), 7.56 (s, 1H), 3.22 (m, 4H),
3.17 (m, 4H), 2.38 (broad s, H2O). 13C NMR could not be
obtained due to poor solubility. Anal. Calcd for
C35H23N3‚2.0H2O: C, 80.61; H, 4.46; N, 7.83. Found: C, 80.12;
H, 4.46; N, 7.83.
1
0.45 g (60%) of 8g: mp 190-193 °C; H NMR (CDCl3) δ 9.22
(d, 1H, J ) 2.9 Hz), 8.38 (m, 3H), 8.25 (m, 3H), 8.13 (m, 3H),
8.05 (m, 3H), 7.80 (q, 2H), 7.64 (q, 1H), 1.56 (H2O); 13C NMR
(CDCl3) δ 114.4, 115.8, 122.6, 124.8, 124.9, 125.4, 125.7, 125.8,
125.9, 126.0, 126.1, 126.2, 126.3, 126.4, 127.2, 127.5, 128.2,
129.0, 130.2, 130.7, 131.2, 133.2, 134.6, 135.9, 138.8, 140.4,
144.8, 147.8. Anal. Calcd for C28H16N2-0.5 H2O: C, 86.38; H,
4.37; N, 6.81. Found: C, 86.42; H, 4.14; N, 6.81.
1,4-Di(1,10-p h en a n th r olin -2-yl)ben zen e (13). A mixture
of 1a (0.12 g, 0.71 mmol), 1,4-diacetylbenzene (0.06 g, 0.35
mmol), and saturated ethanolic KOH (0.25 mL) in absolute
ethanol (5 mL) was heated at 50 °C for 3 h and then at 90 °C
for 18 h. The solvent was evaporated, and the residue was
purified by chromatography on Al2O3, eluting with EtOAc/CH2-
Cl2 (2:3), to provide 0.10 g (68%) of 13: mp > 300 °C; 1H NMR
(CDCl3) δ 9.28 (dd, 2 H, J ) 4.4, 1.5 Hz), 8.56 (s, 4 H), 8.37 (d,
2 H, J ) 8.4 Hz), 8.29 (dd, 2 H, J ) 8.1, 1.5 Hz), 8.24 (d, 2 H,
J ) 8.4 Hz), 7.83 (AB quartet, 4 H), 7.67 (dd, 2 H, J ) 8.1, 4.4
Hz), 1.56 (H2O); 13C NMR could not be obtained due to poor
solubility. Anal. Calcd for C30H18N4-0.75 H2O: C, 80.44; H,
4.36, N, 12.51. Found: C, 80.37, H, 4.12, N, 12.51.
1,3-Di(ben zo[h ]qu in olin -2-yl)ben zen e (10a ). To a solu-
tion of 1,3-diacetylbenzene (0.15 g, 0.93 mmol) and 1b (0.32
g, 1.85 mmol) in absolute EtOH (25 mL) was added saturated
ethanolic KOH (1 mL). The solution was refluxed under Ar
for 31 h. The mixture was cooled and filtered to yield 0.23 g
(58%) of 10a : mp > 300 °C; 1H NMR (CDCl3) δ 9.62 (d, 2H, J
) 8.1 Hz), 9.37 (s, 1H), 8.46 (d, 2H, J ) 7.6 Hz), 8.31 (d, 2H,
J ) 8.3 Hz), 8.18 (d, 2H, J ) 8.4 Hz), 7.94 (d, 2H, J ) 7.7 Hz),
7.78 (overlapping m, 9H), 1.58 (s, H2O); 13C NMR (CDCl3) δ
155.4, 146.3, 140.3, 136.6, 134.0, 131.4, 129.3, 128.3, 128.2,
127.8, 127.5, 126.9, 126.6, 125.3, 125.1, 124.8, 119.0. Anal.
Calcd for C32H20N2-3.25 H2O: C, 86.20; H, 4.83; N, 6.29.
Found: C, 86.30; H, 4.46; N, 6.13.
4,4′-Di(1,10-ph en an th r olin -2-yl)biph en yl (14). To a mix-
ture of 1a (0.17 g, 1.0 mmol) and 4,4′-diacetylbiphenyl (0.12
g, 1.0 mmol) in absolute EtOH (35 mL) under Ar was added
saturated ethanolic KOH (0.5 mL), and the mixture was
refluxed for 23 h. After cooling, the mixture was stored at 0
°C overnight. The precipitate was collected and washed
several times with EtOH to provide 0.20 g (39%) of 14 as a
1
1,3-Di(1,10-p h en a n t h r olin -2-yl)b en zen e (10b ). To a
solution of 1,3-diacetylbenzene (0.16 g, 0.99 mmol) and 1a (0.34
g, 1.98 mmol) in absolute EtOH (50 mL) was added saturated
ethanolic KOH (2 mL). The solution was refluxed under Ar
for 17 h. After cooling, filtration yielded crude material which
was chromatographed on SiO2 (40 g), eluting first with CH2Cl2
brown solid: mp > 300 °C; H NMR (CDCl3) δ 9.27 (d, 2H, J
) 3.1 Hz), 8.50 (d, 4H, J ) 8.1 Hz), 8.37 (d, 2H, J ) 8.3 Hz),
8.28 (d, 2H, J ) 7.5 Hz), 8.20 (d, 2H), 7.91 (d, 4H), 7.82 (AB
quartet, 4H), 7.66 (q, 2H); 13C NMR (CDCl3) δ 157.0, 155.6,
150.3, 146.1, 141.4, 138.6, 136.7, 136.0, 131.0, 129.0, 128.3,
127.4, 126.3, 123.2, 122.8, 120.4.