Job/Unit: O20721
/KAP1
Date: 21-08-12 17:20:31
Pages: 10
F.-X. Felpin et al.
FULL PAPER
3-(Benzo[d][1,3]dioxol-5-yl)-2,4-bis(benzyloxy)-5-phenylpyridine
(12e): Purification by recrystallisation from petroleum ether/EtOAc
gave 12e (78.9 mg, 81%) as a white solid, m.p. 139–140 °C. IR
1
IR (ZnSe): ν = 3064, 3032, 2949, 1723, 1610, 1572 cm–1. H NMR
˜
(300 MHz, CDCl3): δ = 8.28 (d, J = 8.5 Hz, 2 H), 8.21 (d, J =
8.2 Hz, 1 H), 8.05 (d, J = 8.1 Hz, 1 H), 7.79 (d, J = 8.5 Hz, 2 H),
(ZnSe):
ν =
˜
3063, 3031, 2941, 2884, 1580 cm–1. 1H NMR 7.74 (t, J = 8.5 Hz, 1 H), 7.53–7.32 (m, 9 H), 7.29–7.20 (m, 2 H),
(300 MHz, CDCl3): δ = 8.15 (s, 1 H), 7.56 (d, J = 8.1 Hz, 2 H),
7.48–7.29 (m, 8 H), 7.21–7.12 (m, 3 H), 7.02–6.97 (m, 2 H), 6.99–
6.85 (m, 1 H), 6.74 (d, J = 6.6 Hz, 2 H), 6.02 (s, 2 H), 5.49 (s, 2
H), 4.32 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 162.3,
161.6, 147.4, 147.0, 146.7, 137.8, 136.1, 135.6, 129.5, 128.5, 128.4,
128.2, 127.5, 127.3, 126.4, 126.1, 124.6, 117.8, 111.5, 108.1, 101.1,
74.7, 67.8 ppm. HRMS (ESI): calcd. for C32H26NO4 [M + H]+
488.1862; found 488.1801.
5.71 (s, 2 H), 4.73 (s, 2 H), 4.05 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 167.1, 161.2, 160.1, 146.9, 138.2, 137.5, 136.3, 131.3,
130.3, 129.4, 128.6, 128.4, 128.4, 128.4, 128.3, 127.6, 127.6, 127.4,
124.3, 122.9, 121.6, 115.9, 75.9, 68.0, 52.2 ppm. HRMS (ESI): m/z
calcd. for C31H26NO4 [M + H]+ 476.1862; found 476.1871.
2,4-Bis(benzyloxy)-3-(4-nitrophenyl)-5-phenylpyridine (12h): Purifi-
cation by flash chromatography (50% CH2Cl2-petroleum ether)
gave 12h (69.3 mg, 71%) as a yellow solid, m.p. 159–160 °C. IR
3-(Benzo[d][1,3]dioxol-5-yl)-2,4-bis(benzyloxy)quinoline (13e): Puri-
fication by recrystallisation from petroleum ether/toluene gave 13e
(ZnSe): ν = 3063, 3031, 2939, 1600, 1580, 1519 cm–1. 1H NMR
˜
(300 MHz, CDCl3): δ = 8.25 (s, 1 H), 8.23 (d, J = 9.9 Hz, 2 H),
7.63–7.58 (m, 4 H), 7.52–7.43 (m, 3 H), 7.35–7.30 (m, 5 H), 7.23–
7.18 (m, 1 H), 7.14–7.08 (m, 2 H), 6.64 (d, J = 7.2 Hz, 2 H), 5.47
(s, 2 H), 4.29 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 162.1,
(76.5 mg, 83%) as a white solid, m.p. 120–121 °C. IR (ZnSe): ν =
˜
3064, 3031, 2884, 1596, 1571 cm–1. 1H NMR (300 MHz, CDCl3):
δ = 8.11 (d, J = 8.2 Hz, 1 H), 8.34 (d, J = 8.3 Hz, 1 H), 7.67 (t, J
= 7.6 Hz, 1 H), 7.51–7.22 (m, 11 H), 7.14–7.06 (m, 2 H), 6.97 (dd, 160.9, 148.4, 147.0, 140.0, 137.1, 135.3, 135.2, 132.1, 129.3, 128.8,
J = 8.4, J = 1.5 Hz, 1 H), 6.06 (s, 2 H), 5.64 (s, 2 H), 4.74 (s, 2 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 160.9, 160.6, 147.5, 147.1,
146.3, 137.8, 136.6, 129.8, 128.5, 128.3, 128.2, 128.2, 127.5, 127.4,
127.1, 126.3, 124.7, 124.0, 122.7, 121.8, 116.1, 111.5, 108.2, 101.1,
75.3, 67.7 ppm. HRMS (ESI): calcd. for C30H24NO4 [M + H]+
462.1697; found 462.1705.
128.5, 128.4, 128.3, 127.9, 127.8, 127.4, 126.1, 122.9, 116.3, 75.2,
68.1 ppm. HRMS (ESI): calcd. for C31H25N2O4 [M
489.1814; found 489.1904.
+
H]+
2,4-Bis(benzyloxy)-3-(4-nitrophenyl)quinoline (13h): Purification by
flash chromatography (50% CH2Cl2-petroleum ether) gave 13h
(67.5 mg, 73%) as a yellow solid, m.p. 136–137 °C. IR (ZnSe): ν =
˜
4-[2,4-Bis(benzyloxy)-5-phenylpyridin-3-yl]benzoic Acid (12f): Puri-
fication by recrystallisation from petroleum ether/EtOAc gave 12f
(69.2 mg, 71%) as a light yellow solid, m.p. 197–198 °C. IR (ZnSe):
3065, 3033, 2945, 1602, 1571 cm–1. 1H NMR (300 MHz, CDCl3):
δ = 8.42–8.25 (m, 2 H), 8.14 (d, J = 8.2 Hz, 1 H), 7.99 (d, J =
8.2 Hz, 1 H), 7.82–7.70 (m, 3 H), 7.62–7.24 (m, 9 H), 7.22–7.10 (m,
2 H), 5.64 (s, 2 H), 4.75 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
ν = 3062, 3031, 2947, 2877, 2547, 1610, 1582 cm–1. 1H NMR
˜
(300 MHz, CD3OD): δ = 8.13 (s, 1 H), 8.04 (d, J = 8.3 Hz, 2 H), δ = 161.4, 159.5, 147.1, 147.1, 144.9, 140.2, 137.2, 135.8, 132.1,
7.56 (d, J = 6.5 Hz, 2 H), 7.56–7.37 (m, 5 H), 7.34–7.11 (m, 6 H), 130.7, 128.6, 128.5, 128.3, 128.2, 127.8, 127.7, 127.4, 123.1, 122.4,
7.06 (t, J = 7.3 Hz, 2 H), 6.62 (d, J = 7.0 Hz, 2 H), 5.40 (s, 2 H), 121.3, 115.1, 76.4, 68.1 ppm. HRMS (ESI): calcd. for C29H23N2O4
4.27 (s, 2 H) ppm. 13C NMR (75 MHz, CD3OD): δ = 171.7, 162.1, [M + H]+ 463.1658; found 463.2123.
161.1, 147.0, 137.3, 135.7, 135.3, 130.7, 129.0, 129.0, 128.8, 128.2,
4-[2,4-Bis(benzyloxy)-5-phenylpyridin-3-yl]phenyl
enesulfonate (12i): Purification by flash column chromatography
(20% EtOAc/petroleum ether) gave 12i (69.9 mg, 57%) as a white
4-Methylbenz-
128.2, 128.0, 127.9, 127.7, 127.7, 127.3, 127.2, 127.0, 126.3, 117.6,
74.4, 67.6 ppm. HRMS (ESI): calcd. for C32H26NO4 [M + H]+
488.1862; found 488.1873.
solid, m.p. 161–162 °C. IR (ZnSe): ν = 2921, 2851, 1652, 1635,
˜
1
4-[2,4-Bis(benzyloxy)quinolin-3-yl]benzoic Acid (13f): Purification
by recrystallisation from petroleum ether/EtOAc gave 13f (61.8 mg,
1577, 1558 cm–1. H NMR (300 MHz, CDCl3): δ = 8.20 (s, 1 H),
7.75 (d, J = 8.3 Hz, 2 H), 7.59 (d, J = 6.5 Hz, 2 H), 7.52–7.12 (m,
15 H), 7.07 (d, J = 8.8 Hz, 2 H), 6.67 (d, J = 7.8 Hz, 2 H), 5.46 (s,
2 H), 4.24 (s, 2 H), 2.43 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 161.0, 161.2, 148.9, 147.3, 145.3, 137.4, 135.6, 135.3, 132.5,
132.2, 131.7, 129.8, 129.7, 129.3, 128.6, 128.4, 128.3, 128.2, 128.2,
127.6, 127.5, 127.1, 126.1, 121.9, 117.0, 74.7, 67.8, 21.7 ppm.
67%) as a light yellow solid, m.p. 161 °C (decomp). IR (ZnSe): ν
˜
= 3064, 3031, 2945, 1694, 1598 cm–1. 1H NMR (300 MHz,
CD3OD): δ = 8.08 (d, J = 8.0 Hz, 2 H), 8.02 (d, J = 8.2 Hz, 1 H),
7.82 (d, J = 8.4 Hz, 1 H), 7.61 (t, J = 7.6 Hz, 1 H), 7.53 (d, J =
8.0 Hz, 2 H), 7.42–7.17 (m, 9 H), 7.14–7.03 (m, 2 H), 5.49 (s, 2 H),
4.60 (s, 2 H) ppm. 13C NMR (75 MHz, CD3OD): δ = 173.3, 160.8, HRMS (ESI): calcd. for C38H32NO5S [M + H]+ 614.2001; found
160.3, 146.4, 137.3, 136.3, 135.3, 133.7, 130.3, 129.7, 128.7, 128.0,
127.9, 127.9, 127.1, 127.0, 126.6, 123.8, 122.4, 121.5, 116.3, 108.7,
75.3, 67.5 ppm. HRMS (ESI): calcd. for C30H24NO4 [M + H]+
462.1705; found 462.1700.
614.1989.
4-[2,4-Bis(benzyloxy)quinolin-3-yl]phenyl 4-Methylbenzenesulfonate
(13i): Purification by flash column chromatography (20% EtOAc/
petroleum ether) gave 13i (50.5 mg, 43%) as a white solid, m.p.
Methyl 4-[2,4-Bis(benzyloxy)quinolin-3-yl]benzoate (12g): Purifica-
tion by flash column chromatography (50% CH2Cl2/petroleum
132–134 °C. IR (ZnSe): ν = 3063, 3358, 3062, 2921, 2850, 1657,
˜
1
1596 cm–1. H NMR (300 MHz, CDCl3): δ = 8.08 (d, J = 8.2 Hz,
ether) gave 12g (95.2 mg, 95%) as a white solid, m.p. 153–154 °C.
1 H), 7.91 (d, J = 8.0 Hz, 1 H), 7.73 (d, J = 8.2 Hz, 2 H), 7.66 (d,
J = 6.9 Hz, 1 H), 7.51 (d, J = 8.7 Hz, 2 H), 7.46–6.98 (m, 15 H),
5.58 (s, 2 H), 4.61 (s, 2 H), 2.41 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 160.9, 160.1, 149.1, 146.7, 145.3, 137.4, 136.1, 132.4,
132.3, 132.0, 130.2, 129.7, 128.5, 128.5, 128.4, 128.3, 128.2, 127.5,
127.3, 127.2, 124.2, 122.7, 122.1, 121.5, 115.5, 75.6, 67.7, 21.7 ppm.
HRMS (ESI): calcd. for C36H29NO5S [M + Na]+ 610.1664; found
610.1678.
1
IR (ZnSe): ν = 2949, 2374, 1720, 1579, 1528, 1498 cm–1. H NMR
˜
(300 MHz, CDCl3): δ = 8.24 (s, 1 H), 8.15 (d, J = 8.5 Hz, 2 H),
7.66–7.59 (m, 4 H), 7.55–7.10 (m, 11 H), 6.71–6.63 (m, 2 H), 5.51
(s, 2 H), 4.31 (s, 2 H), 4.01 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 167.1, 162.1, 161.2, 147.6, 137.8, 137.4, 135.6, 135.4,
131.1, 130.2, 129.4, 129.1, 129.1, 128.6, 128.5, 128.4, 128.2, 127.6,
127.6, 127.2, 126.2, 117.3, 74.8, 67.9, 52.2 ppm. HRMS (ESI):
calcd. for C33H28NO4 [M + H]+ 502.2018; found 502.2018.
3-Biphenyl-4-hydroxypyridin-2(1H)-one (14): Pd(OH)2/C (20 mol-
%) was added to a solution of pyridone 4a (184 mg, 0.5 mmol)
in AcOH (5 mL), and the mixture was stirred at 60 °C under an
atmosphere of H2 for 12 h. The mixture was filtered and concen-
Methyl 4-[2,4-Bis(benzyloxy)quinolin-3-yl]benzoate (13g): Purifica-
tion by flash column chromatography (15% EtOAc/petroleum
ether) gave 13g (90.3 mg, 95%) as a white solid, m.p. 133–134 °C.
8
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