1502
J. Audoux, S. Achelle, A. Turck, F. Marsais, N. Plé
Vol 43
Anal. Calcd. for C12H8N2O (196.21): C, 73.46; H, 4.11, N,
14.28.. Found: C, 73.49; H, 3.98; N, 14.33.
2853, 1657, 1607, 1567, 1551, 1500, 1455, 1391, 1241, 1152,
1035, 1023, 896, 829, 751, 702, 688, 653 cm-1.
Anal. Calcd. for C19H14N2O2 (302.33): C, 75.48; H, 4.67; N,
9.27.. Found: C, 75.48; H, 4.81; N, 9.13.
2-(Pivaloylaminophenyl)nicotinic ethyl ester (12).
After purification by column chromatography (silica gel,
eluent dichloromethane:diethylether (95:5)) 1.65g (47%) of (12)
8-Phenylsulfanylbenzo[c][2,5]naphthyridin-1(2H)-one (15).
1
as a brown solid, mp 81-83 °; H nmr (deuteriochloroform): ꢀ
Metallation of (11) according to the procedure B followed by
reaction with diphenyl disulfide (9 equiv., 0.501 g) in solution
with anhydrous tetrahydrofurane (15 mL) gave after purification
by column chromatography (silica gel, eluent ethyl acetate:
dichloromethane (1:3)) 0.067g (87%) of (15) as a colorless solid,
mp > 250°; 1H nmr (DMSO-d6) : ꢀ 6.63 (d, J = 5.3 Hz, 1H, H3),
7.34 (t, J = 7.9 Hz, 1H, Hbenz), 7.43 (d, J = 7.9 Hz, 1H, Hbenz),
7.67 (m, 6H, HPh et Hbenz), 8.64 (m, 2H, H2 et Hbenz), 12.00 (s,
1H, NH); 13C nmr (DMSO-d6) : ꢀ 115.9 (CH), 117.1 (Carom),
119.0 (Carom), 119.0 (CH), 122.7 (CH), 125.2 (CH), 130.6 (CH),
130.7 (Carom), 130.8 (2CHPh), 131.8 (CH), 136.1 (2CHPh), 137.9
(Carom), 152.1 (Carom), 152.1 (CH), 155.9 (Carom), 161.8 (Carom). ir
(potassium bromide): 3169, 3015, 2981, 2901, 2854, 1662,
1602, 1541, 1454, 1435, 1373, 1361, 1157, 877, 823, 789, 753,
695, 654, 533, 463 cm-1.
0.90 (t, J = 7.1 Hz, 3H, Me), 1.10 (s, 9H, tert-butyl), 4.01 (q, J =
7.1 Hz, 2H, OCH2), 6.98 (t, J = 7.2 Hz, 1H, HPh), 7.09 (d, J = 6.4
Hz, 1H, HPh), 7.29 (m, 2H, H5py et HPh), 8.08 (dd, JH4-H5 = 7.5 Hz
et JH4-H6 = 1.5 Hz, 1H, H4py), 8.34 (d, J = 8.3 Hz, 1H, HPh), 8.65
(dd, JH6-H5 = 4.5 Hz et JH6-H4 = 1.5 Hz, 1H, H6py), 9.93 (s, 1H,
NH); 13C nmr 13.9 (CH3), 27.7 (3 x CH3ter-butyl), 40.2, 62.1 (CH2),
122.3 (CH), 122.4 (CH), 123.4 (CH), 128.4 (Carom), 129.4
(Carom), 130.1 (CH), 130.5 (CH), 136.6 (Carom), 139.3 (CH),
150.2 (CH), 157.4 (Carom), 168.1 (C=O), 177.0 (C=O). Ir
(potassium bromide): 3271, 2980, 1716, 1583, 1515, 1453,
1422, 1365, 1296, 1166, 1140, 1056, 1017, 923, 863, 752, 623,
548 cm-1.
Anal. Calcd. for C19H22N2O3 (326,39): C, 69.92; H, 6.79; N,
8.58.. Found: C, 69.63; H, 6.86; N, 8.49
Anal. Calcd. for C18H12N2O2S (304.37): C, 71.03; H, 3.97; N,
9.20; S, 10.54.. Found: C, 71.04; H, 4.17; N, 9.42; S, 10.32.
8-(1-Hydroxyethyl)benzo[c][2,5]naphthyridin-1(2H)-one (13).
Metallation of (11) according to the procedure A followed by
reaction with acetaldehyde (10 equiv., 0.15 mL) in solution with
anhydrous tetrahydrofurane (5 mL) gave after purification by
8-Chlorobenzo[c][2,5]naphthyridin-1(2H)-one (16).
Metallation of (11) according to the procedure B followed by
reaction with hexachloroethane (8 equiv., 0.483 g) in solution
with anhydrous THF (5 mL) gave after purification by column
chromatography (silica gel, eluent ethyl acetate: dichloro-
methane (1:1)) 0.049g (85%) of (16) as a colorless solid, mp >
250°; 1H nmr (DMSO-d6): ꢀ 7.37 (m, 2H, Hbenz), 7.66 (t, J = 8.3
Hz, 1H, Hbenz), 7.78 (d, J = 5.3 Hz, 1H, H3), 8.66 (d, 1H, Hbenz),
8.95 (d, 1H, H2), 11.93 (s, 1H, NH); 13C nmr (DMSO-d6): ꢀ
115.7 (Carom), 118.3 (CH), 118.6 (CH), 122.7 (Carom), 125.3
(Carom), 126.2 (Carom), 132.2 (Carom), 138.2 (CH), 145.2 (CH),
153.6 (Carom), 153.7 (CH), 159.4 (CH). ir (potassium bromide):
2922, 2854, 1681, 1605, 1563, 1453, 1375, 1260, 1063, 868,
838, 795, 753, 655, 602, 528, 455 cm-1.
column
chromatography
(silica
gel,
eluent
ethyl
acetate:dichloromethane (1:1)) 58 mg (96%) of (13) as a
colorless solid, mp 224-226°; 1H nmr (DMSO-d6): ꢀ 1.43 (d, J
= 6.4 Hz, 3H, Me), 5.50 (d, J = 4.5 Hz, 1H, OH), 6.22 (quint, J =
4.9 Hz, 1H, CHOH), 7.34 (t, J = 7.2 Hz, 1H, Hbenz), 7.42 (d, J =
7.5 H, 1H, Hbenz), 7.63 (t, J = 8.2 Hz, 1H, Hbenz), 7.97 (d, J = 5.3
Hz, 1H, H3), 8.72 (d, J = 7.2 Hz, 1H, Hbenz), 9.04 (d, J = 4.9 Hz,
1H, H2), 11.81 (s, 1H, NH); 13C nmr (DMSO-d6) : ꢀ 25.9 (Me),
65.0 (CHOH), 115.6 (CH), 117.7 (Carom), 119.3 (Carom), 120.3
(CH), 122.5 (CH), 125.0 (CH), 131.4 (CH), 137.9 (Carom), 151.7
(Carom), 153.7 (CH), 161.2 (Carom), 161.7 (C=O). ir (potassium
bromide): 3171, 3114, 3031, 2983, 2923, 2867, 1658, 1605,
1557, 1498, 1459, 1434, 1387, 1356, 1262, 1110, 805, 757, 669
cm-1.
Anal. Calcd. for C12H7N2OCl (230.65): C, 62.49; H, 3.06; N,
12.15.. Found: C, 62.55; H, 2.99; N, 12.11.
8-Bis(tri-n-butylstannyl)benzo[c][2,5]naphthyridin-1(2H)-one
(17).
Anal. Calcd. for C14H12N2O2 (240.26): C, 69.99; H, 5.03; N,
11.66.. Found: C, 70.11; H, 5.22; N, 11.71.
Metallation of (11) according to the procedure B followed by
reaction with tributyltin chloride (9 equiv., 0.63 mL) in solution
with anhydrous THF (5 mL) gave after purification by column
chromatography (silica gel, eluent dichloromethane) 0.107 g
8-(Hydroxyphenylmethyl)benzo[c][2,5]naphthyridin-1(2H)-one
(14).
Metallation of (11) according to the procedure B followed by
reaction with benzaldehyde (9 equiv., 0.23 ml) in solution with
anhydrous tetrahydrofurane (15 mL) gave after purification by
column chromatography (silica gel, eluent ethyl acetate:
dichloromethane (1:1)) 0.063g (82%) of (14) as a colorless solid,
1
(88%), of (17) and as a colorless solid, mp 150-151°; H nmr
(deuteriochloroform): ꢀ 0.78 (m, 18H, Me), 1.08 (m, 24H, CH2),
1.51 (m, 12H, SnCH2), 7.32 (m, 2H, Hbenz), 7.48 (t, J = 7.2 Hz,
1H, Hbenz), 7.69 (td, JH3-H2 = 4.5 Hz et JH3-Sn = 19.2 Hz, 1H, H3),
1
mp 226-228°; H nmr (deuteriochloroform): ꢀ 6.08 (d, J = 7.2
8.75 (d, J = 7.9 Hz, 1H, Hbenz), 8.84 (q, JH3-H2 = 4.5 Hz et JH3-Sn
=
10.2 Hz, 1H, H2), 11.20 (s, 1H, NH); 13C nmr
(deuteriochloroform) : ꢀ 10.7 (CH2), 12.59 (Me), 12.6 (Me),
16.4 (CH2), 25.8 (CH2), 26.4 (CH2), 26.8 (CH2), 28.2 (CH2),
114.8 (CH), 119.8 (Carom), 122.3 (CH), 124.1 (CH), 125.1
(Carom), 129.6 (CH), 130.8 (CH), 135.5 (Carom), 149.7 (Carom),
150.7 (CH), 157.1 (Carom), 163.7 (Carom). ir (potassium bromide):
3177, 3114, 3022, 2922, 1660, 1602, 1540, 1505, 1455, 1363,
1258, 1149, 1073, 1018, 961, 873, 841, 818, 754, 670, 642, 599,
523 cm-1.
Hz, 1H, OH), 6.53 (d, J = 7.2 Hz, 1H, CHOH), 7.01 (d, J = 7.9
Hz, 1H, Hbenz), 7.27 (m, 7H, HPh, H3 et Hbenz), 7.46 (t, J = 8.3 Hz,
1H, Hbenz), 8.72 (dd, J = 7.9 et 1.14 Hz, 1H, Hbenz), 8.87 (d, J =
4.5 Hz, 1H, H2), 11.57 (s, 1H, NH); 13C nmr
(deuteriochloroform): ꢀ 74.7 (CHOH), 116.0 (CH), 118.9
(Carom), 120.5 (Carom), 124.0 (CH), 124.1 (CH), 124.2 (CH),
125.9 (CH), 127.1 (2CHPh), 127.9 (CH), 128.7 (2CHPh), 131.9
(CH), 136.6 (Carom), 142.2 (Carom), 153.9 (Carom), 154.5 (CH),
155.2 (Carom), 164.4 (C=O). ir (potassium bromide): 3315, 2922,