Synthesis of 3-Pyrrolylquinolines
2785
4
3
2
.27 (dt, J ¼ 8.2, 5.8, 1H), 4.23–4.18 (m, 2H), 3.29 (dd, J ¼ 8.1, 6.4, 1H),
.22 (dd, J ¼ 8.1, 7.3, 1H), 3.12 (dd, J ¼ 8.2, 7.2, 1H), 2.94–2.86 (m, 2H),
1
3
.69 (s, 3H), 2.64 (s, 3H), 2.46 (s, 3H), 1.25 (t, J ¼ 7.2, 3H). C NMR (d
ppm): 173.6 (CO), 149.4 (C), 146.0 (C), 134.3 (C), 134.0 (C), 133.1 (CH),
31.9 (C), 129.8 (CH), 127.2 (CH), 126.8 (C), 62.9 (CH ), 61.0 (CH ), 59.5
1
2
2
(
CH ), 50.8 (CH), 44.3 (CH), 41.8 (CH ), 18.6 (CH ), 17.7 (CH ), 14.2 (CH ).
2 3 3 3 3
Methyl 4-(2-chloro-7-methoxyquinolin-3-yl)-1-methylpyrrolidine-3-carboxy-
1
late 4d: R ¼ 0.6, oil. IR (n , KBr) ¼ 1735 (C 55 O, ester). H NMR (d ppm,
f
max
J Hz): 8.14 (s, 1H), 7.63 (d, J ¼ 8.8, 1H), 7.24 (d, J ¼ 2.5, 1H), 7.12
(
dd, J ¼ 8.8, 2.5, 1H), 4.20 (dd, J ¼ 8.1, 5.2, 1H), 3.86 (s, 3H), 3.66
(
s, 3H), 3.22–3.14 (m, 2H), 2.99 (dd, J ¼ 9.5, 8.2, 1H), 2.85 (dd, J ¼ 9.7,
1
3
.1, 1H), 2.81–2.73 (m, 1H), 2.40 (s, 3H). C NMR (d ppm): 174.0 (CO),
5
1
61.1 (C), 151.0 (C), 148.1 (C), 135.9 (CH), 132.8 (CH), 128.3 (C), 122.6
(
(
C), 120.1 (CH), 106.1 (CH), 62.8 (CH ), 59.5 (CH ), 55.4 (CH ), 52.1
2 2 3
þ.
CO CH ), 50.7 (CH), 43.8 (CH), 41.7 (CH ). HRMS (E.I) [M] calcd. for
2
3
3
C H C1N O ¼ 334.10842; found 334.1070.
1
7
19
2 3
Methyl
4-(2-chloro-7-methylquinolin-3-yl)-1-methylpyrrolidine-3-carbo-
xylate 4e: R ¼ 0.35, mp 65–668C. IR (n , KBr) ¼ 1719 (C 55 O, ester).
f
max
1
H NMR (d ppm, J Hz): 8.25 (s, 1H), 7.75 (d, J ¼ 8.4, 1H), 7.48 (s, 1H),
7
.40 (d, J ¼ 8.4, 1H), 4.23 (dd, J ¼ 8.1, 5.0, 1H), 3.71 (s, 3H), 3.26–3.18
(
(
(
m, 2H), 3.03 (dd, J ¼ 9.5, 8.1, 1H), 2.89 (dd, J ¼ 9.5, 5.0, 1H), 2.83–2.75
1
3
m, H), 2.54 (s, 3H), 2.48 (s, 3H). C NMR (d ppm): 173.9 (CO), 150.7
C), 146.5 (C), 140.6 (CH), 134.2 (CH), 131.9 (CH), 128.6 (CH), 127.0 (C),
25.5 (C), 124.8 (C), 62.7 (CH ), 59.4 (CH ), 52.2 (CH ), 50.6 (CH), 43.9
2 2 3
1
þ.
(
CH), 41.8 (CH3), 21.9 (CH3). HRMS (E.I) [M]
cacld. for
C H C1N O ¼ 304.09786; found 304.0975.
1
6
17
2 2
Methyl 4-(2-chloro-6,7-dimethylquinolin-3-yl)-1-methylpyrrolidine-3-carbox-
1
ylate 4f: R ¼ 0.40, oil. IR (n , KBr) ¼ 1742 (C 55 O, ester). H NMR
f
max
(
d ppm, J Hz): 8.20 (s, 1H), 7.73 (s, 1H), 7.56 (s, 1H), 4.24 (dd, J ¼ 8.2, 5.5
1
H), 3.70 (s, 3H), 3.34–3.24 (m, 2H), 3.11 (d, J ¼ 9.6, 8.3, 1H), 3.01
(
(
d, J ¼ 9.5, 5.4, 1H), 2.97–2.85 (m, 2H), 2.51 (s, 3H), 2.44 (s, 3H), 2.44
1
3
s, 3H). C NMR (d ppm): 173.9 (CO), 149.7 (C), 145.5 (C), 140.5 (C),
37.0 (C), 135.2 (C), 134.0 (CH), 127.3 (C), 126.5 (CH), 126.0 (CH), 62.6
1
(
CH ), 59.4 (CH ), 52.1 (CH ), 50.6 (CH), 43.9 (CH), 41.7 (CH ), 20.4 (CH ),
2
2
3
3
3
1
9.9 (CH3).
Ethyl
3
4-(2-chloro-6,7-deoxymethylquinolin-3-yl)-1-methylpyrrolidine-
-carboxylate 4g: R ¼ 0.62, yellow crystals, mp 224–2258C. IR (nmax,
f
1
KBr) ¼ 1735 (C 55 O, ester). H NMR (d ppm, J Hz): 8.35 (s, 1H), 7.28
(
s, 1H), 7.13 (s, 1H), 6.14 (s, 2H), 4.35–4.14 (m, 3H), 3.57–3.31 (m, 2H),
.25 (dd, J ¼ 9.4, 8.2, 1H), 2.97 (dd, J ¼ 9.4, 5.1, 1H), 2.84–2.75 (m, 1H),
3
1
3
2
.52 (s, 3H). 1.35 (t, J ¼ 7.1, 3H). C NMR (d ppm): 172.4 (CO), 151.4
(
C), 148.3 (C), 148.1 (C), 144.9 (C), 134.4 (CH), 131.7 (C), 124.9 (C),