Y.-L. Wu et al. / Tetrahedron 56 (2000) 6209±6217
6215
4-(2,4-Dichlorobenzoyl)-1-ethyl-6-methyl-2(1H)-quino-
linone 20b. Yellow crystals; mp 149±1508C; IR (CHCl3)
12.6(q), 14.1(q), 37.6(t), 61.9(t), 114.3(d), 117.7(s),
122.4(d), 124.1(d), 127.3(d), 131.0(d), 138.8(s), 139.3(s),
160.9(s), 165.4(s); Anal. Calcd for C14H15NO3: C, 68.56;
H, 6.16; N, 5.71. Found: C, 68.47; H, 6.15; N, 5.78.
3000, 2930, 1645, 1580, 1465, 1375 cm21 1H NMR
;
(400 MHz, CDCl3) d 1.38 (t, J7.1 Hz, 3H, CH3), 2.42 (s,
3H, CH3), 4.38 (q, J7.1 Hz, 2H, NCH2), 6.61 (s, 1H, CH),
7.37 (d, J8.7 Hz, 1H, ArH), 7.38 (dd, J8.2, 2.1 Hz, 1H,
ArH), 7.43±7.52 (m, 2H, ArH), 7.57 (d, J8.2 Hz, 1H,
ArH), 7.83 (d, J2.1 Hz, 1H, ArH); 13C NMR
(100.6 MHz, CDCl3) d 12.7(q), 20.8(q), 37.7(t), 114.5(d),
117.5(s), 122.9(d), 126.9(d), 127.5(d), 130.7(d), 132.0(d),
132.4(s), 132.7(d), 133.9(s), 135.5(s), 137.6(s), 138.9(s),
6-Bromo-4-ethoxycarbonyl-1-ethyl-2(1H)-quinolinone
20g. Yellow needles; mp 142±1438C; IR (CHCl3) 2990,
1730, 1655, 1585, 1430, 1325, 1250 cm21 1H NMR
;
(400 MHz, CDCl3) d 1.36 (t, J7.1 Hz, 3H, CH3), 1.43 (t,
J7.1 Hz, 3H, CH3), 4.35 (q, J7.1 Hz, 2H, NCH2), 4.45
(q, J7.1 Hz, 2H, OCH2), 7.25 (s, 1H, CH), 7.30 (d,
J9.1 Hz, 1H, ArH), 7.68 (dd, J9.1, 2.1 Hz, 1H, ArH),
8.59 (d, J2.1 Hz, 1H, ArH); 13C NMR (100.6 MHz,
CDCl3) d 12.6(q), 14.1(q), 37.8(t), 62.2(t), 115.7(s),
115.9(d), 119.2(s), 125.6(d), 129.8(d), 133.8(d), 137.3(s),
138.3(s), 160.5(s), 164.8(s); Anal. Calcd for C14H14BrNO3:
C, 51.87; H, 4.35; N, 4.32. Found: C, 51.82; H, 4.35; N,
4.32.
145.5(s),
160.6(s),
194.1(s);
Anal.
Calcd
for
C19H15Cl2NO2: C, 63.35; H, 4.20; N, 3.89. Found: C,
63.37; H, 4.21; N, 3.93.
4-Benzoyl-6-bromo-1-ethyl-2(1H)-quinolinone 20c. Yellow
needles; mp 119±1208C; IR (CHCl3) 3005, 2930, 1660,
1
1585, 1550, 1450 cm21; H NMR (400 MHz, CDCl3) d
1.41 (t, J7.1 Hz, 3H, CH3), 4.40 (q, J7.1 Hz, 2H,
NCH2), 6.73 (s, 1H, CH), 7.35 (d, J9.1 Hz, 1H, ArH),
7.52 (t, J7.8 Hz, 2H, ArH), 7.63±7.79 (m, 3H, ArH),
7.90±8.01(m, 2H, ArH); 13C NMR (100.6 MHz, CDCl3) d
12.6(q), 37.8(t), 115.5(s), 116.2(d), 119.8(s), 121.9(d),
128.9(d), 129.5(d), 130.3(d), 134.2(d), 134.7(d), 135.5(s),
138.4(s), 145.7(s), 160.3(s), 194.1(s); Anal. Calcd for
C18H14BrNO2: C, 60.69; H, 3.96; N, 3.93. Found: C,
60.63; H, 3.92; N, 3.95.
4,6-Bis(ethoxycarbonyl)-1-ethyl-2(1H)-quinolinone 20h.
Yellow needles; mp 81±828C; IR (CHCl3) 2990, 2940,
;
1715, 1660, 1620, 1590 cm21 1H NMR (400 MHz,
CDCl3) d 1.38 (t, J7.2 Hz, 3H, CH3), 1.43 (t, J7.1 Hz,
3H, CH3), 1.46 (t, J7.1 Hz, 3H, CH3), 4.35±4.46 (m, 4H,
CH2), 4.49 (q, J7.1 Hz, 2H, OCH2), 7.24 (s, 1H, CH), 7.46
(d, J9.0 Hz, 1H, ArH), 8.25 (dd, J9.0, 1.8 Hz, 1H, ArH),
9.05 (d, J1.8 Hz, 1H, ArH); 13C NMR (100.6 MHz,
CDCl3) d 12.6(q), 14.1(q), 14.3(q), 38.0(t), 61.2(t),
62.2(t), 114.3(d), 117.2(s), 124.5(s), 124.8(d), 129.5(d),
131.7(d), 139.0(s), 142.1(s), 160.9(s), 164.9(s), 165.7(s);
Anal. Calcd for C17H19NO5: C, 64.35; H, 6.03; N, 4.41.
Found: C, 64.34; H, 6.10; N, 4.46.
4-Acetyl-1-ethyl-6-methyl-2(1H)-quinolinone 20d. Yellow
crystals; mp 140±1418C; IR (CHCl3) 3000, 2925, 1700,
1
1645, 1580, 1565 cm21; H NMR (400 MHz, CDCl3) d
1.37 (t, J7.1 Hz, 3H, CH3), 2.42 (s, 3H, CH3), 2.64 (s,
3H, CH3), 4.37 (q, J7.1 Hz, 2H, NCH2), 6.92 (s, 1H,
CH), 7.34 (d, J8.7, Hz, 1H, ArH), 7.43 (d, J8.7 Hz,
1H, ArH), 7.79 (s, 1H, ArH); 13C NMR (100.6 MHz,
CDCl3) d 12.6(q), 20.8(q), 30.1(q), 37.6(t), 114.3(d),
116.8(s), 121.3(d), 126.8(d), 132.2(s), 132.5(d), 137.4(s),
146.1(s), 160.9(s), 201.0(s); Anal. Calcd for C14H15NO2:
C, 73.34; H, 6.59; N, 6.11. Found: C, 73.35; H, 6.67; N,
6.11.
6-Chloro-4-ethoxycarbonyl-1-ethyl-2(1H)-quinolinone
20i. Yellow needles; mp 133±1348C; IR (CHCl3) 2990,
1
2925, 1730, 1660, 1590, 1430 cm21; H NMR (400 MHz,
CDCl3) d 1.36 (t, J7.1 Hz, 3H, CH3), 1.43 (t, J7.2 Hz,
3H, CH3), 4.36 (q, J7.1 Hz, 2H, NCH2), 4.45 (q, J
7.2 Hz, 2H, OCH2), 7.27 (s, 1H, CH), 7.36 (d, J9.1 Hz,
1H, ArH), 7.56 (dd, J9.1, 2.4 Hz, 1H, ArH), 8.46 (d,
J2.4 Hz, 1H, ArH); 13C NMR (100.6 MHz, CDCl3) d
12.6(q), 14.1(q), 37.9(t), 62.2(t), 115.7(d), 118.8(s),
125.7(d), 126.8(d), 128.3(s), 131.1(d), 137.4(s), 137.8(s),
160.5(s), 164.8(s); Anal. Calcd for C14H14ClNO3: C,
60.11; H, 5.04; N, 5.01. Found: C, 60.04; H, 5.01; N, 5.04.
4-Ethoxycarbonyl-1-ethyl-6-methyl-2(1H)-quinolinone
20e. Yellow needles; mp 85±868C; IR (CHCl3) 2990, 1730,
1665, 1645, 1585, 1255 cm21; 1H NMR (400 MHz, CDCl3)
d 1.36 (t, J7.1 Hz, 3H, CH3), 1.43 (t, J7.1 Hz, 3H, CH3),
2.44 (s, 3H, CH3), 4.37 (q, J7.1 Hz, 2H, NCH2), 4.45 (q,
J7.1 Hz, 2H, OCH2), 7.16 (s, 1H, CH), 7.33 (d, J8.7 Hz,
1H, ArH), 7.43 (dd, J8.7, 1.5 Hz, 1H, ArH), 8.13 (d,
J1.5 Hz, 1H, ArH); 13C NMR (100.6 MHz, CDCl3) d
12.6(q), 14.1(q), 20.8(q), 37.6(t), 61.9(t), 114.2(d),
117.7(d), 124.0(d), 126.9(d), 132.1(s), 132.3(d), 137.3(s),
138.6(s), 160.8(s), 165.6(s); Anal. Calcd for C15H17NO3:
C, 69.48; H, 6.61; N, 5.40. Found: C, 69.58; H, 6.56; N,
5.34.
Typical experimental procedure for the manganese(III)
acetate mediated reaction of anilide 24
A solution of 156 mg (0.49 mmol) of 24a, 393 mg
(1.47 mmol) of manganese(III) acetate in 5 ml of acetic
acid was heated at 808C for 15 h. The reaction mixture
was diluted with 50 ml of ethyl acetate, washed with
50 ml of aqueous saturated sodium bisul®te, three 50-ml
portions of aqueous saturated sodium bicarbonate, three
25-ml portions of water, dried (Na2SO4) and concentrated
in vacuo. The residue was chromatographed over 20 g of
silica gel (eluted with ethyl acetate±hexane, 1:2.5) to give
147 mg (95%) of 25a as a single product.
4-Ethoxycarbonyl-1-ethyl-2(1H)-quinolinone 20f. Yellow
crystals; mp 92±938C; IR (CHCl3) 3000, 1730, 1655, 1590,
;
1450 cm21 1H NMR (400 MHz, CDCl3) d 1.37 (t,
J7.1 Hz, 3H, CH3), 1.43 (t, J7.1 Hz, 3H, CH3), 4.39
(q, J7.1 Hz, 2H, NCH2), 4.45 (q, J7.1 Hz, 2H, OCH2),
7.19 (s, 1H, CH), 7.28 (t, J7.6 Hz, 1H, ArH), 7.43 (d,
J7.6 Hz, 1H, ArH), 7.61 (t, J7.6 Hz, 1H, ArH), 8.35
(d, J7.6 Hz, 1H, ArH); 13C NMR (100.6 MHz, CDCl3) d
3,3-Bis(methylsulfonyl)-1-ethyl-2-indolinone 25a. White
crystals; mp 211±2128C; IR (CHCl3) 3030, 2930, 1725,
1
1610, 1340 cm21; H NMR (400 MHz, CDCl3) d 1.31 (t,