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Matteo Staderini et al.
121.5, 119.2, 112.8, 111.1 ppm; IR (NaCl): n=1583, 1498,
1431, 1370, 1257, 1136, 1041, 916 cmÀ1; elemental analysis
calcd. (%) for C13H10Cl2N2: C 58.89, H 3.80, N 10.57; found:
C 58.49, H 4.10, N 10.48.
(63 MHz, CDCl3): d=169.7, 161.5, 151.7, 149.4, 146.5, 138.6,
135.2, 129.4 (2C), 128.9, 128.7, 128.0, 127.8, 127.5, 127.3
(2C), 125.4, 92.2, 59.5, 47.7, 17.3, 14.7; IR (NaCl): n=3237,
2977, 2923, 1651, 1607, 1260, 1230 cmÀ1; elemental analysis
calcd. (%) for C22H21ClN2O2: C 69.38, H 5.56, N 7.36;
found: C 69.01, H 5.34, N 7.24.
(Z)-Ethyl 2-(7-chloroquinolin-4-yl)-3-(methylamino)but-2-
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enoate (6): pale brown solid; mp 998C; H NMR (250 MHz,
CDCl3): d=9.60 (br s, 1H), 8.78 (d, J=4.4 Hz, 1H), 8.03 (d,
J=2.1 Hz, 1H), 7.73 (d, J=8.9 Hz, 1H), 7.35 (dd, J=9.0,
2.1 Hz, 1H), 7.11 (d, J=4.4 Hz, 1H), 3.95–3.81 (m, 2H),
2.94 (d, J=5.2 Hz, 3H), 1.56 (s, 3H), 0.88 (t, J=7.1 Hz,
3H); 13C NMR (63 MHz, CDCl3): d=169.7, 162.5, 151.7,
149.4, 146.7, 135.1, 128.9, 128.8, 127.9, 127.4, 125.5, 91.1,
59.4, 30.5, 17.0, 14.8; IR (NaCl): n=3263, 2974, 2930, 1647,
1597, 1265, 1231, 1061 cmÀ1; Eelemental analysis calcd. (%)
for C16H17ClN2O2: C 63.05, H 5.62, N 9.19; found: C 62.95,
H 5.44, N 9.03.
(Z)-Ethyl 3-(butylamino)-2-(7-chloroquinolin-4-yl)but-2-
enoate (7): pale brown solid; mp 1028C; 1H NMR
(250 MHz, CDCl3): d=9.75 (br t, J=5.0 Hz, 1H), 8.88 (d,
J=4.4 Hz, 1H), 8.12 (d, J=2.1 Hz, 1H), 7.83 (d, J=8.9 Hz,
1H), 7.44 (dd, J=8.9, 2.1 Hz, 1H), 7.21 (d, J=4.4 Hz, 1H),
4.07–3.89 (m, 2H), 3.37–3.29 (m, 2H), 1.78–1.66 (m, 2H),
1.65 (s, 3H), 1.58–1.43 (m, 2H), 1.04–0.94 (m, 6H);
13C NMR (63 MHz, CDCl3): d=169.6, 161.6, 151.7, 149.5,
146.8, 135.1, 128.9, 128.8, 128.0, 127.4, 125.5, 90.8, 59.3, 43.7,
32.6, 20.6, 17.2, 14.8, 14.3; IR (NaCl): n=3251, 2970, 2932,
1645, 1594, 1264, 1228, 877 cmÀ1; elemental analysis calcd.
(%) for C19H23ClN2O2: C 65.79, H 6.68, N 8.08; found: C
65.29, H 6.55, N 8.12.
6-Chloro-9-(1H-indol-3-yl)-2-methoxyacridinium chloride
(11): yellow solid; mp 2238C; H NMR (250 MHz, CDCl3):
1
d=8.79 (br s, 1H), 8.28 (d, J=1.8 Hz, 1H), 8.19 (d, J=
9.4 Hz, 1H), 7.89 (d, J=9.3 Hz, 1H), 7.63 (d, J=8.2 Hz,
1H), 7.51 (dd, J=7.7, 2.4 Hz, 2H), 7.39–7.31 (m, 2H), 7.23–
7.12 (m, 3H), 3.69 (s, 3H); 13C NMR (63 MHz, CDCl3): d=
157.5, 147.6, 146.9, 139.5, 136.5, 135.3, 131.3, 128.9, 128.2,
128.2, 127.6, 127.1, 126.1, 125.7, 125.3, 123.4, 121.1, 120.7,
112.0, 111.4, 103.2, 55.8; IR (NaCl): n=1628, 1563, 1535,
1466, 1419, 1209, 701 cmÀ1; elemental analysis calcd- (%) for
C22H16Cl2N2O: C 66.85, H 4.08, N 7.09; found: C 66.72, H
4.15, N 7.24.
6-Chloro-2-methoxy-9-(1H-pyrrol-2-yl)acridinium chloride
1
(12): Yellow solid; mp 2368C; H NMR (250 MHz, CDCl3):
d=9.40 (br s, 1H), 8.06 (d, J=2.0 Hz, 1H), 7.94 (d, J=
9.4 Hz, 1H), 7.82 (d, J=9.4 Hz, 1H), 7.35–7.27 (m, 3H),
7.05 (d, J=2.1 Hz, 1H), 6.60–6.57 (m, 2H), 3.84 (s, 3H);
13C NMR (63 MHz, acetone-d6): d=158.7, 148.6, 148.1,
138.7, 135.3, 132.6, 130.1, 129.1, 127.9, 127.8, 126.7, 125.6,
121.6, 121.4, 113.5, 110.3, 103.8, 56.2; IR (NaCl): n=1630,
1473, 1232, 807 cmÀ1; elemental analysis calcd. (%) for
C18H14Cl2N2O: C 62.62, H 4.09, N 8.11; found: C 62.23, H
4.25, N 8.21.
(Z)-Ethyl 3-(sec-butylamino)-2-(7-chloroquinolin-4-yl)but-
2-enoate (8): white solid; mp 1158C; 1H NMR (250 MHz,
CDCl3): d=9.66 (br d, J=8.9 Hz, 1H), 8.78 (d, J=4.4 Hz,
1H), 8.02 (d, J=2.1 Hz, 1H), 7.73 (dd, J=8.9, 4.9 Hz, 1H),
7.35 (dd, J=8.9, 2.1 Hz, 1H), 7.13 (dd, J=4.4, 1.5 Hz, 1H),
3.95–3.81 (m, 2H), 3.55–3.39 (m, 1H), 1.59–1.52 (m, 2H),
1.56 (s, 3H), 1.20 (dd, J=6.4, 2.0 Hz, 3H), 0.98–0.84 (m,
6H); 13C NMR (63 MHz, CDCl3): d=169.6, 160.8, 151.8,
149.5, 146.9, 135.1, 128.9, 128.0, 127.9, 127.4, 125.6, 90.5,
59.3, 50.9, 31.4, 22.2, 17.2, 14.8, 11.0; IR (NaCl): n=3250,
2971, 2927, 1645, 1594, 1561, 1536, 1335, 1241, 710 cmÀ1; ele-
mental analysis calcd. (%) for C19H23ClN2O2: C 65.79, H
6.68, N 8.08; found: C 65.73; H 6.58; N 8.13.
6-Chloro-9-(4-hydroxy-2-oxo-2H-chromen-3-yl)-2-meth-
oxyacridinium chloride (13): orange solid; mp >3008C;
1H NMR (250 MHz, DMSO): d=8.43 (d, J=2.0 Hz, 1H),
8.34 (d, J=9.4 Hz, 1H), 8.14 (d, J=9.3 Hz, 1H), 8.08 (dd,
J=7.9, 1.4 Hz, 1H), 7.85–7.76 (m, 2H), 7.67 (dd, J=9.3,
2.1 Hz, 1H), 7.58 (dd, J=8.3, 0.7 Hz, 1H), 7.51–7.44 (m,
1H), 7.28 (d, J=2.6 Hz, 1H), 3.85 (s, 3H); 13C NMR
(63 MHz, DMSO): d=164.2, 161.2, 158.2, 154.0, 139.4,
137.0, 133.5, 129.3, 129.1, 129.0, 128.3, 128.1, 127.3, 127.3,
125.2, 124.6, 124.5, 123.9, 117.0, 116.9, 103.0, 98.5, 56.4; IR
(KBr disk): n=1696, 1606, 1228, 1043, 951, 761 cmÀ1; ele-
mental analysis calcd. (%) for C23H15Cl2NO4: C 62.74, H
3.43, N 3.18; found: C 62.31, H 3.39, N 3.45.
(Z)-Ethyl 2-(7-chloroquinolin-4-yl)-3-(furan-2-ylmethyl-
amino)but-2-enoate (9): yellow oil; 1H NMR (250 MHz,
CDCl3): d=10.03 (br t, J=5.6 Hz, 1H), 8.89 (d, J=4.6 Hz,
1H), 8.23 (d, J=2.0 Hz, 1H), 7.85 (d, J=9.0 Hz, 1H), 7.49
(dd, J=9.0, 2.1 Hz, 1H), 7.44 (dd, J=1.8, 0.8 Hz, 1H), 7.28
(d, J=4.6 Hz, 1H), 6.40 (dd, J=3.2, 1.9 Hz, 1H), 6.31 (dd,
J=3.2, 0.8 Hz, 1H), 4.52 (d, J=5.9 Hz, 2H), 4.04–3.94 (m,
2H), 1.75 (s, 3H), 0.97 (t, J=7.1 Hz, 3H); 13C NMR
(63 MHz, CDCl3): d=167.9, 159.6, 150.1, 149.2, 146.8, 146.4,
141.6, 134.5, 127.3, 126.6, 126.5 (2H), 123.9, 109.5, 106.4,
91.0, 58.2, 39.5, 15.8, 13.3; IR (NaCl): n=3255, 2980, 2930,
1651, 1583, 1444, 1262, 1231, 1095, 1071, 1016 cmÀ1; elemen-
tal analysis calcd. (%) for C20H19ClN2O3: C 64.78, H 5.16, N
7.55; found: C 64.55, H 4.99, N 7.23.
(Z)-Ethyl 3-(benzylamino)-2-(7-chloroquinolin-4-yl)but-2-
enoate (10): yellow oil; 1H NMR (250 MHz, CDCl3): d=
10.13 (br t, J=5.9 Hz, 1H), 8.88 (d, J=4.4 Hz, 1H), 8.13 (d,
J=2.1 Hz, 1H), 7.84 (d, J=8.9 Hz, 1H), 7.48–7.34 (m, 6H),
7.23 (d, J=4.4 Hz, 1H), 4.56 (d, J=6.1 Hz, 2H), 4.07–3.93
(m, 2H), 1.66 (s, 3H), 0.98 (t, J=7.1 Hz, 3H); 13C NMR
6-Chloro-2-methoxy-9-(5-methylfuran-2-yl)acridinium
chloride (14): brown solid; mp 1718C; H NMR (250 MHz,
1
MeOD): d=8.64 (d, J=9.5 Hz, 1H), 8.26–8.21 (m, 2H),
7.99–7.84 (m, 3H), 7.47 (s, 1H), 6.72 (s, 1H), 4.05 (s, 3H),
2.66 (s, 3H); 13C NMR (63 MHz, MeOD): d=159.6, 145.0,
143.4, 142.0, 139.8, 131.8, 130.3, 129.4, 125.6, 125.1, 123.1,
123.1, 122.6, 121.7, 118.8, 110.4, 104.4, 55.6, 13.0; IR (KBr
disk): n=3120, 1626, 1526, 1453, 1240 cmÀ1; elemental analy-
sis calcd. (%) for C19H15Cl2NO2: C 63.35, H 4.20, N 3.89;
found: C 63.01, H 3.97, N 3.63.
(Z)-9-(3-Amino-1-ethoxy-1-oxobut-2-en-2-yl)-6-chloro-2-
1
methoxyacridinium (15): orange solid; mp 2458C; H NMR
(250 MHz, MeOD): d=8.34–8.24 (m, 3H), 7.96 (dd, J=9.5,
2.6 Hz, 1H), 7.83 (d, J=9.5 Hz, 1H), 7.47 (d, J=2.5 Hz,
1H), 4.02 (s, 3H), 4.04–3.94 (m, 2H), 1.58 (s, 3H), 0.88 (t,
J=7.1 Hz, 3H); 13C NMR (63 MHz, DMSO): d=167.8,
161.9, 157.5, 156.4, 135.8, 135.4, 135.1, 132.8, 128.9, 128.4,
127.5, 127.5, 127.4, 125.9, 102.3, 86.5, 58.4, 55.9, 20.4, 14.7;
IR (KBr disk): n=3348, 3240, 3164, 1660, 1628, 1426, 1239,
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ꢃ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
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