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HETEROCYCLES, Vol. 66, 2005
CH3), 25.6 (s, CH2), 62.1 (s, OCH2CH3), 122.0, 129.0, 129.8, 131.4, 132.8, 135.0, 136.4, 144.2, 150.8 (s,
aromatic C); 166.5 (s, CO), HRMS (FAB) calcd for C14H15NO2Br [M + H]+ 308.0286, found 308.0289.
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Ethyl 6-fluoro-3-ethylquinaldate (3k): pale yellow oil (180 mg, 73 %), H NMR (500 MHz, CDCl3)
δ 1.31 (t, J = 7.5 Hz, 3H, CH3), 1.44 (t, J = 7.1 Hz, 3H, OCH2CH3), 2.99 (q, J = 7.5 Hz, 2H, CH2), 4.50 (q,
J = 7.1 Hz, 2H, OCH2CH3), 7.36 (dd, J = 8.8, 2.7 Hz, 1H, aromatic H), 7.41 – 7.45 (m, 1H, aromatic
13
H), 7.96 (s, 1H, aromatic H), 8.14 (dd, J = 9.2, 5.3 Hz, 1H, aromatic H), C NMR (125 MHz, CDCl3)
δ 14.2 (s, OCH2CH3), 15.0 (s, CH3), 25.6 (s, CH2), 62.0 (s, OCH2CH3), 109.9 (d, JCF = 23 Hz, aromatic
C), 119.7 (d, JCF = 27 Hz, aromatic C), 129.6 (d, JCF = 9.7 Hz, aromatic C), 132.4 (d, JCF = 9.7 Hz,
aromatic C), 135.5 (d, JCF = 5.6 Hz, aromatic C), 136.4, 142.8 (s, aromatic C), 149.8 (d, JCF = 3.2 Hz,
aromatic C), 161.3 (d, JCF = 256 Hz, aromatic C), 166.6 (s, CO); HRMS (FAB) calcd for C14H15NO2F [M
+ H]+ 248.1087, found 248.1080.
Ethyl 6-methoxycarbonyl-3-ethylquinaldate (3l): colorless crystals (from hexane, 152 mg, 53 %), mp
1
84-85 ºC, H NMR (500 MHz, CDCl3) δ 1.32 (t, J = 7.5 Hz, 3H, CH3), 1.44 (t, J = 7.1 Hz, 3H,
OCH2CH3), 2.98 (q, J = 7.5 Hz, 2H, CH2), 3.96 (s, 3H, OCH3), 4.51 (q, J = 7.1 Hz, 2H, OCH2CH3), 8.11
(s, 1H, aromatic H), 8.15 (d, J = 8.8 Hz, 1H, aromatic H), 8.23 (dd, J = 8.8, 1.6 Hz, 1H, aromatic H), 8.53
(d, J = 1.6 Hz, 1H, aromatic H), 13C NMR (125 MHz, CDCl3) δ 14.2 (s, OCH2CH3), 14.9 (s, CH3), 25.5 (s,
CH2), 52.5 (s, OCH3), 62.1 (s, OCH2CH3), 127.9, 128.7, 129.2, 130.0, 130.1, 136.0, 137.3, 147.4, 152.6 (s,
aromatic C); 166.4, 166.5 (s, CO), HRMS (FAB) calcd for C16H18NO4 [M + H]+ 288.1236, found
288.1251, Anal. Calcd for C15H19NO: C, 66.89; H, 5.96; N, 4.88. Found: C, 66.69; H, 5.79; N, 4.89.
Ethyl 6-(ethoxycarbonylmethyl)-3-ethylquinaldate (4): pale yellow oil (47 mg, 15 %, obtained along
with 3g), 1H NMR (500 MHz, CDCl3) δ 1.20 (t, J = 7.1 Hz, 3H, OCH2CH3), 1.29 (t, J = 7.5 Hz, 3H, CH3),
1.42 (t, J = 7.1 Hz, 3H, OCH2CH3), 2.96 (q, J = 7.5 Hz, 2H, CH2CH3), 3.75 (s, 2H, CH2), 4.13 (q, J = 7.1
Hz, 2H, OCH2CH3), 4.48 (q, J = 7.1 Hz, 2H, OCH2CH3), 7.58 (dd, J = 8.8, 1.8 Hz, 1H, aromatic H), 7.65
(d, J = 1.8 Hz, 1H, aromatic H), 7.96 (s, 1H, aromatic H), 8.08 (d, J = 8.8 Hz, 1H, aromatic H), 13C NMR
(125 MHz, CDCl3) δ 14.1, 14.2 (s, OCH2CH3), 15.0 (s, CH3), 25.6 (s, CH2CH3), 52.5 (s, OCH3), 61.0,
61.9 (s, OCH2CH3), 126.9, 128.7, 129.8, 130.9, 134.0, 135.6, 135.9, 144.8, 150.2 (s, aromatic C); 166.7,
171.0 (s, CO), HRMS (FAB) calcd for C18H22NO4 [M + H]+ 316.1549, found 316.1550.
Ethyl 2,2-bis(2-ethoxycarbonyl-3-ethylquinolin-6-yl)acetate (5): pale yellow oil (119 mg, 22 %,
1
obtained along with 3g), H NMR (500 MHz, CDCl3) δ 1.25 (t, J = 7.1 Hz, 3H, OCH2CH3), 1.29 (t, J =
7.5 Hz, 6H, CH3), 1.43 (t, J = 7.1 Hz, 6H, OCH2CH3), 2.96 (q, J = 7.5 Hz, 4H, OCH2CH3), 4.26 (q, J =