the solution was concentrated in vacuo to give a white solid
(0.82 g). The solid was added to a 100 ml round-bottom flask,
and 4-butoxybenzoyl chloride (0.64 g, 3.03 mmol), 4-(N,N-
dimethylamino)pyridine (0.30 g, 2.46 mmol), and THF (50 ml)
were added. The mixture was stirred at room temperature for
20 h. To the solution was added ethyl acetate (30 ml), and the
solution was washed with an aqueous solution of NaHCO3
(100 ml) and dried over MgSO4. The solvent was evaporated
under reduced pressure, and a white solid was obtained as the
residue. The crude product was purified by silica gel
chromatography (chloroform) to give 2a as a white solid
(0.69 g, 58.7%)
2a: yield 58.7%; white solid (methanol–ethyl acetate); n/cm21
(KBr) 2920, 2854, 1648, 1600, 1511, 1474, 1273, 1171, 762; dH
(500 MHz, CDCl3, TMS) 0.98 (t, 3H, J ~ 7.6 Hz), 1.00 (t, 3H,
J ~ 7.3 Hz), 1.46–1.54 (m, 4H), 1.77 (t, 2H, J ~ 8.0 Hz), 1.81
(t, 2H, J ~ 8.0 Hz), 3.97 (t, 2H, J ~ 6.6 Hz), 4.06 (t, 2H, J ~
6.4 Hz), 6.90 (d, 2H, J ~ 9.2 Hz), 6.98 (d, 2H, J ~ 9.2 Hz), 7.31
(d, 2H, J ~ 8.6 Hz), 7.38 (d, 2H, J ~ 8.9 Hz), 7.52 (d, 2H, J ~
8.9 Hz), 7.75 (s, 1H), 7.91 (d, 2H, J ~ 8.6 Hz), 8.14 (d, 2H, J ~
9.2 Hz), 8.28 (d, 2H, J ~ 9.2 Hz); dC (125.65 MHz, CDCl3,
TMS) 13.82, 13.87, 19.21, 19.25, 31.13, 31.35, 68.04, 68.08,
113.54, 114.43, 114.94, 121.06, 122.10, 122.22, 128.46, 130.76,
132.42, 132.55, 134.46, 138.54, 139.08, 153.76, 156.33, 163.83,
164.58, 164.85, 171.52; Elemental analysis found: C% 72.16,
H% 6.32, N% 2.56, calcd for C35H35NO7: C% 72.27, H% 6.06,
N% 2.41.
4. Experimental
Typical examples of the procedures and spectral data of these
compounds are described below. The spectral data of the other
compounds are described in the Electronic Supplementary
Information.{
An example for preparation of 5, 7, 9 and 11
To a 300 ml round-bottom flask were added 4-benzyloxyben-
zoyl chloride (7.36 g, 29.9 mmol), 4-butoxyaniline (4.40 g,
19.9 mmol), triethylamine (16.6 ml, 119.4 mmol), and toluene
(100 ml). The mixture was then stirred at reflux for 1.5 h. After
cooling, the solution was washed with 1 N HCl(200 ml), and an
aqueous solution of NaHCO3 (300 ml), and dried over MgSO4.
The solvent was evaporated under reduced pressure, and a
yellow solid was obtained as the residue. The crude product
was purified by silica gel chromatography eluting with
chloroform to give 7a as a white solid (5.59 g, 65.1%).
7a: yield 65.1%; mp 193.2–193.6 uC; white solid (methanol–
ethyl acetate); n/cm21 (KBr) 2916, 2871, 1643, 1608, 1516,
1476, 1246, 1175, 761; dH (500 MHz, CDCl3, TMS) 0.98 (t, 3H,
J ~ 7.3 Hz), 1.49 (q, 2H, J ~ 7.3 Hz), 1.77 (t, 2H, J ~ 7.0 Hz),
3.96 (t, 2H, J ~ 6.6 Hz), 5.13 (s, 2H), 6.89 (d, 2H, J ~ 8.9 Hz),
7.04 (d, 2H, J ~ 8.9 Hz), 7.35 (d, 1H, J ~ 6.7 Hz), 7.39 (d, 2H,
J ~ 8.0 Hz), 7.43 (d, 2H, J ~ 7.6 Hz), 7.50 (d, 2H, J ~ 8.6 Hz),
7.63 (s, 1H), 7.82 (d, 2H, J ~ 8.9 Hz); dC (125.65 MHz, CDCl3,
TMS) 13.87, 19.25, 31.35, 68.03, 70.16, 114.86, 114.90, 122.03,
127.50, 128.24, 128.71, 128.84, 130.97, 136.32, 156.13, 161.52;
Elemental analysis found: C% 76.70, H% 6.97, N% 3.63, calcd
for C24H25NO3: C% 76.77, H% 6.71, N% 3.73.
Acknowledgements
This work was supported by Tokuyama Science Foundation
and the Ministry of Education, Science, Sports and Culture,
Grant-in-Aid for Scientific Research (B), 2002, 14390012 and
2003, 15350108.
A typical procedure for synthesis of 6, 8, 10 and 12
To a 500 ml flask were added 7a (2.70 g, 7.19 mmol), ethanol
(100 ml), THF (100 ml), and 10% palladium-activated carbon
(1.20 g). The mixture was stirred at room temperature for 1.5 h
under an atmosphere of hydrogen. After filtering off by celite,
the solution was concentrated in vacuo to give a white solid
(2.05 g). The solid was added to a 300 ml round-bottom flask,
and 4-benzyloxybenzoyl chloride (2.66 g, 10.8 mmol), 4-(N,N-
dimethylamino)pyridine (0.50 g, 4.09 mmol), and THF (70 ml)
were added. The mixture was stirred at room temperature for
20 h. To the solution was added ethyl acetate (50 ml), and the
solution was washed with an aqueous solution of NaHCO3
(150 ml) and dried over MgSO4. The solvent was evaporated
under reduced pressure, and a white solid was obtained as the
residue. The crude product was purified by silica gel
chromatography (chloroform) to give 8a as a white solid
(1.64 g, 46.2%)
8a: yield 46.2%; mp 211.7–212.1 uC; white solid (methanol–
ethyl acetate); n/cm21 (KBr) 2925, 2855, 1729, 1650, 1608,
1515, 1474, 1251, 1175, 764; dH (500 MHz, CDCl3, TMS) 0.98
(t, 3H, J ~ 7.4 Hz), 1.50 (q, 2H, J ~ 7.6 Hz), 1.77 (t, 2H, J ~
7.9 Hz), 3.97 (t, 2H, J ~ 6.6 Hz), 5.17 (s, 2H), 6.91 (d, 2H, J ~
9.2 Hz), 7.07 (d, 2H, J ~ 9.2 Hz), 7.33 (d, 2H, J ~ 8.6 Hz), 7.41
(d, 2H, J ~ 7.6 Hz), 7.43 (d, 1H, J ~ 6.8 Hz), 7.45 (d, 2H, J ~
7.3 Hz), 7.52 (d, 2H, J ~ 8.9 Hz), 7.68 (s, 1H), 7.92 (d, 2H, J ~
8.6 Hz) 8.16 (d, 2H, J ~ 8.9 Hz); dC (125.65 MHz, CDCl3,
TMS) 13.86, 19.26, 31.35, 68.05, 70.26, 114.85, 114.96, 121.60,
122.22, 127.51, 128.46, 128.76, 132.46, 132.77, 136.08, 144.14,
156.18, 163.31, 164.46; Elemental analysis found: C% 75.01,
H% 5.95, N% 2.75, calcd for C31H29NO5: C% 75.13, H% 5.90,
N% 2.83.
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J . M a t e r . C h e m . , 2 0 0 4 , 1 4 , 3 4 4 9 – 3 4 5 6
3 4 5 5