PAPER
Synthesis of Nitromethyl Derivatives of 1,2-Dihydroisoquinolines
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1H NMR (300 MHz, CDCl3): d = 7.50–7.55 (m, 1 H), 7.39 (d,
J = 13.5 Hz, 1 H), 7.07 (d, J = 7.5 Hz, 1 H), 7.02 (d, J = 7.5 Hz,
1 H), 6.50 (d, J = 8.3 Hz, 1 H), 6.27 (d, J = 8.3 Hz, 1 H), 5.58 (t,
J = 6.7 Hz, 1 H), 5.32 (d, J = 13.5 Hz, 1 H), 4.58 (dd, J = 11.3, 6.0
Hz, 1 H), 4.42 (dd, J = 11.3, 7.5 Hz, 1 H), 4.17 (q, J = 14.3, 6.7 Hz,
2 H), 1.30 (t, J = 6.7 Hz, 3 H).
1H NMR (300 MHz, CDCI3): d = 7.29 (t, J = 7.5 Hz, 1 H), 7.20 (t,
J = 7.5 Hz, 1 H), 7.12 (d, J = 7.5 Hz, 1 H), 7.04 (d, J = 7.5 Hz, 1 H),
6.31 (d, J = 7.5 Hz, 1 H), 6.05 (d, J = 7.5 Hz, 1 H), 5.47 (dd, J = 8.3,
5.2 Hz, 1 H), 5.27 (s, 1 H), 4.36–4.64 (m, 4 H), 4.14 (q, J = 14.3, 7.5
Hz, 2 H), 1.42 (t, J = 7.5 Hz, 3 H), 1.28 (t, J = 7.5 Hz, 3 H).
ESI-MS: m/z = 383 [M + Na], 361, 346, 314, 300.
13C NMR (75 MHz, CDCl3): d = 14.3, 56.8, 59.9, 74.5, 93.6, 106.6,
120.6, 125.4, 127.2, 128.3, 129.4, 129.7, 133.4, 145.5, 167.5.
HRMS: m/z calcd for C18H20N2O6Na: 383.1219; found: 383.1219.
ESI-MS: m/z = 390 [M + Na], 309, 307.
Methyl (E)-3-[2-(Nitromethyl)quinolin-1(2H)-yl]acrylate (4m)
Dark-yellow semi-solid.
HRMS: m/z calcd for C15H15N2O4NaBr: 389.0112; found:
389.0100.
IR (KBr): 2923, 2853, 1697, 1616, 1552, 1493, 1435, 1243, 1162,
1045, 756 cm–1.
Ethyl (E)-3-[3-Methyl-1-(nitromethyl)isoquinolin-2(1H)-
yl]acrylate (4i)
Yellow solid; mp 118–120 °C.
1H NMR (300 MHz, CDCl3): d = 7.87 (d, J = 13.9 Hz, 1 H), 7.23–
7.36 (m, 1 H), 7.01–7.19 (m, 3 H), 6.66 (d, J = 9.5 Hz, 1 H), 5.94
(dd, J = 9.5, 5.8 Hz, 1 H), 5.36 (d, J = 13.9 Hz, 1 H), 5.15–5.30 (m,
1 H), 4.30–4.43 (m, 2 H), 3.72 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 51.1, 52.7, 74.5, 92.1, 117.8, 120.5,
124.1, 127.6, 128.1, 129.4, 129.8, 140.4, 145.8, 168.7.
IR (KBr): 2925, 1700, 1602, 1548, 1489, 1415, 1375, 1314, 1241,
1152, 1045, 969, 804, 756, 669, 473 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.69 (d, J = 13.9 Hz, 1 H), 6.96–
7.33 (m, 4 H), 5.82 (s, 1 H), 5.68 (t, J = 6.6 Hz, 1 H), 5.36 (d,
J = 13.9 Hz, 1 H), 4.33–4.57 (m, 2 H), 4.17 (q, J = 13.9, 6.6 Hz,
2 H), 2.23 (s, 3 H), 1.29 (t, J = 6.6 Hz, 3 H).
ESI-MS: m/z = 297 [M + Na+], 275, 214.
HRMS: m/z calcd for C14H14N2O4Na: 297.0851; found: 297.0857.
13C NMR (75 MHz, CDCl3): d = 14.3, 19.8, 56.0, 59.8, 74.5, 91.9,
107.9, 124.3, 125.3, 125.7, 126.8, 129.3, 130.7, 135.3, 142.7, 168.2.
References
ESI-MS: m/z = 325 [M + Na], 242.
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10653.
HRMS: m/z calcd for C16H19N2O4: 303.1344; found: 303.1340.
(E)-3-[1-(Nitromethyl)isoquinolin-2(1H)-yl]-1-phenylprop-2-
en-1-one (4j)
Dark-yellow solid; mp 159–161 °C.
IR (KBr): 3015, 2951, 1653, 1542, 1374, 1197, 1044, 969, 867, 776,
697, 650 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.93 (d, J = 8.3 Hz, 2 H), 7.67 (d,
J = 13.5 Hz, 1 H), 7.41–7.55 (m, 3 H), 7.19–7.35 (m, 2 H), 7.12 (d,
J = 8.3 Hz, 2 H), 6.54 (d, J = 7.5 Hz, 1 H), 6.50 (d, J = 13.5 Hz,
1 H), 5.99 (d, J = 7.5 Hz, 1 H), 5.80 (t, J = 6.7 Hz, 1 H), 4.67 (dd,
J = 12.0, 6.7 Hz, 1 H), 4.45 (dd, J = 12.0, 6.7 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 57.2, 75.4, 97.5, 109.3, 125.4,
125.8, 126.1, 127.8, 128.3, 129.5, 129.8, 132.0, 138.8, 147.3, 188.8.
ESI-MS: m/z = 343 [M + Na], 321, 260.
HRMS: m/z calcd for C19H16N2O3Na: 343.1058; found: 343.1051.
Dimethyl 2-[1-(Nitromethyl)isoquinolin-2(1H)-yl]maleate (4k)
Yellow solid; mp 132–134 °C.
IR (KBr): 2981, 2926, 2854, 1694, 1612, 1551, 1457, 1428, 1373,
1344, 1262, 1157, 1114, 1043, 967, 943, 812, 774, 645 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.02–7.35 (m, 4 H), 6.29 (d,
J = 7.5 Hz, 1 H), 6.06 (d, J = 7.5 Hz, 1 H), 5.47 (dd, J = 8.3, 5.2 Hz,
1 H), 5.30 (s, 1 H), 4.46–4.64 (m, 2 H), 3.98 (s, 3 H), 3.69 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 51.5, 53.5, 56.4, 75.1, 92.7, 111.1,
124.6, 125.4, 126.3, 128.0, 129.2, 129.6, 148.8, 164.5, 166.7.
ESI-MS: m/z = 355 [M + Na].
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Asymmetry 2002, 13, 2117. (d) Taylor, M. S.; Tokunaga, N.;
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Ed. 2006, 45, 2260.
HRMS: m/z calcd for C16H16N2O6Na: 355.0906; found: 355.0920.
Diethyl 2-[1-(Nitromethyl)isoquinolin-2(1H)-yl]maleate (4l)
Yellow semi-solid.
IR (KBr): 2925, 2851, 2739, 1734, 1684, 1600, 1511, 1460, 1260,
1215, 1160, 1105, 1024, 833, 764, 601 cm–1.
Synthesis 2009, No. 7, 1131–1136 © Thieme Stuttgart · New York