106
J. Momoda et al. / Dyes and Pigments 119 (2015) 95e107
4.4.4. Synthesis of 6-(4-morpholinyl)-3,3-diphenylspiro[benzo[3,4]
fluoreno[2,1-b]pyran-13(3H),40-[4H]cyclopenta[def]phenanthrene]
5
(5-benzyloxy-3,9-dimethoxy-7-(4-phenanthryl)-7H-benzo[c]fluo-
ren-7-ol) as a pink solid (1.9 g, 3.3 mmol) in 43% yield.
The phenanthrene adduct (1.0 g, 1.7 mmol) thus obtained was
added to the mixture of 5% Pd/C (0.8 g, 50 wt% water contained),
ammonium formate (0.8 g, 12.7 mmol) and THF (30 mL), and the
resulting mixture was stirred for 2 h. Pd/C was filtered off and the
solvent removed in vacuo. The residue was dissolved in a mixute of
THF (100 mL) and toluene (100 mL), which was washed with sat. aq.
sodium chloride two times. The solvent was removed in vacuo to
give 3,9-dimethoxy-7-(4-phenanthryl)-7H-benzo[c]fluorene-5,7-
diol 15e8 as a yellow solid (1.45 g, 3.0 mmol) in 40% yield.
15e8: Mp 219e221 ꢂC.
To the solution of 16e5 (120 mg, 0.24 mmol) in toluene (120 ml)
were added 1,1-diphenylpropyn-1-ol (77 mg, 0.37 mmol) and cat-
alytic amount of p-TsOH, and the resulting mixture was heated at
80 ꢂC for 18 h. The reaction mixture was washed with sat. aq. so-
dium chloride three times, and the solvent removed in vacuo. The
residue was purified by silica gel column chromatography (100 g,
90/10 CHCl3/ethyl acetate as eluent) two times, and by HPLC (col-
umn: Intersil ODS-3 (GL Science), elution: 90/10 CH3CN/H2O) to
give 6-(4-morpholinyl)-3,3-diphenylspiro[benzo[3,4]fluoreno[2,1-
b]pyran-13(3H),40-[4H]cyclopenta[def]phenanthrene] 5 as a brown
solid (32 mg, 0.047 mmol) in 20% yield.
1H NMR (CDCl3)
d/ppm 3.53 (3H,s), 3.89 (3H, s), 6.31 (1H, t,
J ¼ 7.6 Hz), 6.60 (2H, d, J ¼ 11.6 Hz), 6.86 (1H, d, J ¼ 6.4 Hz), 6.99 (1H,
t, J ¼ 7.9 Hz), 7.32 (1H, d, J ¼ 9.2 Hz), 7.43 (1H, d, J ¼ 8.0 Hz), 7.54 (3H,
m), 7.70 (1H, d, J ¼ 8.8 Hz), 7.80 (1H, t, J ¼ 9.6 Hz), 7.93 (1H, d,
J ¼ 7.2 Hz), 8.16 (1H, d, J ¼ 8.4 Hz), 8.64 (1H, d, J ¼ 9.2 Hz), 9.00 (1H,
d, J ¼ 7.6 Hz)
5: Mp 171e178 ꢂC.
1H NMR (DMSO-d6)
d
/ppm 3.36 (4H, t, J ¼ 4.0 Hz), 3.87 (4H, t,
J ¼ 4.0 Hz), 4.99 (1H, d, J ¼ 10.0 Hz), 5.72 (1H, d, J ¼ 10.0 Hz), 6.28
(1H, d, J ¼ 6.8 Hz), 6.90 (2H, d, J ¼ 6.8 Hz), 7.00 (1H, t, J ¼ 3.8 Hz),
7.23 (11H, m), 7.37 (1H, t, J ¼ 3.9 Hz), 7.60 (3H, m), 8.03 (2H, d,
J ¼ 8.4 Hz), 8.09 (2H, s), 8.42 (1H, d, J ¼ 8.4 Hz), 8.77 (1H, d,
J ¼ 10.0 Hz).
LC-MS Observed 485.1892 (Mþ1) (Calculated exact mass for
C
33H25O4 (Mþ1) 485.1747).
FT-IR (KBr)
1215.
n
/cmꢀ1 3346,1594,1524,1483,1423,1383,1361,1267,
LC-MS Observed 682.2541(Mþ1) (Calculated exact mass for
C
50H36NO2 (Mþ1) 682.2741).
FT-IR (KBr)
n
/cmꢀ1 3049, 2923, 2853, 1615, 1584, 1557, 1515,
4.4.7. Synthesis of 3,9-dimethoxyspiro[7H-benzo[c]fluorine-7,40
[4H]cyclopenta[def]phenanthren]-5-ol 16e8
1462, 1443, 1401, 1260.
To the toluene (50 mL) solution of 15e8 (1.0 g, 1.7 mmol) was
added a small amount of p-TsOH, and the resulting solution was
refluxed for 10 h. After it was cooled down to room temperature,
the reaction mixture washed with sat. aq. sodium chloride, and the
solvent removed in vacuo. The residue was dispersed in chloroform
(20 ml) and stirred for a while, then filtered to give 3,9-
dimethoxyspiro[7H-benzo[c]fluorene-7,40[4H]cyclopenta[def]phe-
nanthren]-5-ol 16e8 as a gray solid (650 mg, 1.4 mmol) in 82%
yield.
4.4.5. Synthesis of 5-benzyloxy-3,9-dimethoxy-7H-benzo[c]fluoren-
7-one 14e8
To the dry DMF (150 mL) solution of 5-hydroxy-3,9-dimethoxy-
7H-benzo[c]fluoren-7-one 12e8 (7.6 g, 25 mmol) were added
benzyl chloride (6.40 g, 50 mmol) and K2CO3 (9.66 g, 70 mmol), and
the resulting mixture was kept at 60 ꢂC for 3 h. The solution was
cooled down to room temperature, then water (150 mL), tetrahy-
drofuran (300 mL) and toluene (300 mL) were added and the
mixture was stirred well. The organic layer was separated, washed
with sat. aq. sodium chloride two times, and the solvent removed in
vacuo. To the resulting residue was added methanol (100 mL) and
the mixture was stirred for 1 h. The solid material precipitated was
collected by filtration. After drying in vacuo, 5-benzyloxy-3,9-
dimethoxy-7H-benzo[c]fluoren-7-one 14e8 was obtained as a red
solid (7.9 g, 20 mmol) in 80% yield.
16e8: Mp 186e188 ꢂC.
1H NMR (CDCl3)
d/ppm 3.56 (3H, s), 3.94 (3H, s), 5.91 (1H, s), 6.18
(1H, d, J ¼ 2.8 Hz), 6.99 (2H, d, J ¼ 7.2 Hz), 7.03 (1H, d, J ¼ 8.8 Hz),
7.44 (1H, d, J ¼ 8.0 Hz), 7.54 (2H, t, J ¼ 7.6 Hz), 7.64 (1H, d, J ¼ 2.4 Hz),
7.92 (2H, d, J ¼ 8.0 Hz), 8.03 (2H, s), 8.33 (1H, d, J ¼ 8.8 Hz), 8.77 (1H,
d, J ¼ 9.2 Hz).
LC-MS Observed 467.1823 (Mþ1) (Calculated exact mass for
C
33H23O3 (Mþ1) 467.1642).
14e8: Mp 185e187 ꢂC.
FT-IR (KBr) n
/cmꢀ1 3382, 3012, 2936, 1692, 1594, 1580, 1523,
1H NMR (CDCl3)
d/ppm 3.86 (3H, s), 3.94 (3H, s), 6.89 (1H, d,
1478, 1433, 1416, 1270, 1218.
J ¼ 11.2 Hz), 7.18 (1H, d, J ¼ 2.4 Hz), 7.25 (3H, m), 7.36 (1H, m), 7.43
(2H, t, J ¼ 8.0 Hz), 7.52 (2H, d, J ¼ 7.2 Hz), 7.63 (1H, d, J ¼ 2.8 Hz), 7.69
(1H, d, J ¼ 8.0 Hz), 8.24 (1H, d, J ¼ 8.0 Hz).
4.4.8. Synthesis of 6,11-dimethoxy-3,3-bis(4-methoxyphenyl)spiro
[benzo[3,4]fluoreno[2,1-b]pyran-13(3H),40-[4H]cyclopenta[def]
phenanthrene] 8
LC-MS Observed 397.1489 (Mþ1) (Calculated exact mass for
C
26H21O4 (Mþ1) 397.1434).
To the solution of 16e8 (466 mg, 1.0 mmol) in toluene (120 ml)
were added 1,1-bis(4-methoxyphenyl)propyn-1-ol (376 mg,
1.40 mmol) and catalytic amount of p-TsOH, and the resulting
mixture was heated at 80 ꢂC for 30 min. The reaction mixture was
washed with sat. aq. sodium chloride three times, and the solvent
removed in vacuo. The residue was purified by silica gel column
chromatography (100 g, 90/10 CHCl3/ethyl acetate as eluent) two
times and recrystallization from a mixture of toluene and ethyl
acetate to give 6,11-dimethoxy-3,3-bis(4-methoxyphenyl)spiro
[benzo[3,4]fluoreno[2,1-b]pyran-13(3H),40-[4H]cyclopenta[def]
phenanthrene] 8 as a pale yellow solid (315 mg, 0.44 mmol) in 44%
yield.
FT-IR (KBr)
1218.
n
/cmꢀ11699, 1606, 1574, 1481, 1462, 1430, 1367, 1265,
4.4.6. Synthesis of 3,9-dimethoxy-7-(4-phenanthryl)-7H-benzo[c]
fluorene-5,7-diol 15e8
To the dry THF solution (100 mL) of 4-bromophenꢀa3nthrene
(2.88 g, 11.3 mmol) at ꢀ78 ꢂC was added 1.6 mol dm butyl-
lithium in hexane (5.6 mL,
9 mmol) gradually to give 4-
lithiophenanthrene. It was gradually added to 14e8
(3.0 g,7.6 mmol) dissolved in dry THF (300 ml) cooled to ꢀ78 ꢂC,
and the solution was stirred for 1 h, then water (150 mL) and
toluene (400 mL) were added and the mixture stirred well. The
organic layer was separated, washed with sat. aq. sodium chloride
two times, and the solvent removed in vacuo. The residue was
purified by silica gel column chromatography (300 g, 90/10 CHCl3/
ethyl acetate as eluent) two times to give the phenanthrene adduct
8: Mp 252e254 ꢂC.
1H NMR (CDCl3)
d/ppm 3.53 (3H, s), 3.72 (6H, s), 3.97 (3H, s), 5.02
(1H, d, J ¼ 10.0 Hz), 5.23 (1H, d, J ¼ 9.6 Hz), 5.98 (1H, d, J ¼ 2.0 Hz),
6.68 (2H, d, J ¼ 1.6 Hz), 6.70 (2H, d, J ¼ 1.6 Hz), 6.90 (1H, d,
J ¼ 11.0 Hz), 6.99 (2H, d, J ¼ 7.2 Hz), 7.09 (4H, m), 7.31 (1H, d,