Raunak et al. / Tetrahedron 61 (2005) 5687–5697
5695
(1H, d, JZ7.7 Hz, C-7H), 6.92–6.98 (4H, m, C-200H,
C-300H, C-500H a0n0 d C-600H), 7.12–7.23 (6H, m, C-4H,
C-5H, C-6H, C-4 H, C-2000H and C-6000H), 7.44 (1H, br s,
NH) and 7.58 (2H, d, JZ8.0 Hz, C-3000H and C-5000H); 13C
NMR (75.5 MHz; CDCl3): d 13.7 (COOCH2CH3), 21.5
(C6H4CH3), 61.4 (COOCH2CH3), 64.9 (C-40), 71.7 (C-30),
83.1 (C-50), 110.4 (C-400), 117.6 (C-200 and C-600), 123.3
(C-7), 1020 3.6 (C-5), 126.2 (C-9)0,00 126.7 (C-6),0010 28.2 (C-300
and C-5 ), 128.8 (C-2000 and C-6 ), 130.0 (C-3 an0d0 C-5000),
130.9 (C-4), 135.5 (C-1000), 138.5 (C-8), 141.5 (C-1 ), 150.1
(C-4000), 167.9 (CONH) and 175.5 (COOC2H5); HRMS
Calcd for C26H24N2O4: 428.1736. Found: 428.1721.
(NH), 1739 (COOC2H5), 1618 (CONH), 1469, 1231,
1
1073, 753 and 694 cmK1; H NMR (300 MHz; CDCl3): d
0.80 (3H, t, JZ7.0 Hz, COOCH2CH3), 3.80–3.98 (2H, m,
COOCH2CH3), 5.24 (1H, s, C-30H), 5.32 (1H, s, C-50H),
6.69 (1H, d0,0 JZ7.7 Hz, C-0700H), 6.91–7.12 (6H, m, C-200H,
C-300H, C-5 H, C-600H, C-2 H and C-6000H), 7.19–7.23 (2H,
m, C-400H and C-5000H), 7.25–7.30 (0200H, m, C-5H and C-6H)
7.47–7.51 (2H, m, C-4H and C-4 H) and 7.89(1H, br s,
NH); 13C NMR (75.5 MHz; CDCl3): d 13.5 (COOCH2CH3),
61.4 (COOCH2CH3), 66.5 (C-40), 77.6 (C-30), 82.2 (C-50),
109.4 (C-400), 115.5 (C-200 and C-600), 122.5 (C-7), 123.1
(C-5), 1020 4.7 (C-9), 125.1 (C-6), 127.0 (C-4), 129.0 (C-300
and C-5 ), 129.3 (C-6000), 129.6 (C-5000), 129.8 (C-4000), 131.2
(C-2000), 137.9 (C-8 and C-1000), 140.1 (C-100), 150.9 (C-3000),
165.5 (CONH) and 173.8 (COOC2H5); HRMS Calcd for
C25H21N2 79BrO4: 492.0685. Found: 492.0696.
5.4.11.
30-(3-Chlorophenyl)-50-ethoxycarbonyl-20-
phenylspiro[indoline-3,40-isoxazolidine]-2-one (5f).
Obtained as a light yellow solid (177 mg, 21%), mp 158–
159 8C, (from petroleum ether–ethyl acetate), Rf: 0.35
(petroleum ether–ethyl acetate, 3:2); IR (KBr): 3317
(NH), 1741 (COOC2H5), 1619 (CONH), 1595, 1399,
5.4.14.
30-(3-Bromophenyl)-40-ethoxycarbonyl-20-
phenylspiro[indoline-3,50-isoxazolidine]-2-one (6g).
Obtained as a light yellow solid (402 mg, 44%) mp 145–
146 8C (from petroleum ether–ethyl acetate), Rf: 0.38
(petroleum ether–ethyl acetate, 3:2); IR (KBr): 3206
(NH), 1730 (COOC2H5), 1620 (CONH), 1474, 1338,
1
1230, 1075 and 750 cmK1; H NMR (300 MHz; CDCl3):
d 0.81 (3H, t, JZ7.0 Hz, COOCH2CH3), 3.80–3.98 (2H, m,
COOCH2CH3), 5.24 (1H, s, C-30H), 5.32 (1H, s, C-50H),
6.68 (1H, d, JZ7.7 Hz,00C-7H), 060 .91–6.96 (1H, m, C-5000H),
7.01–7.17 (7H, m, C-2 H, C-3 H, C-400H, C-500H, C-600H,
1
1192, 1027 and 834 cmK1; H NMR (300 MHz; CDCl3):
000
C-2 H and C-6000H), 7.25–7.31 (3H, m, C-5H, C-6H and
d 0.70 (3H, t, JZ7.0 Hz, COOCH2CH3), 3.67–3.84 (2H, m,
COOCH2CH3), 4.20 (1H, d, JZ9.5 Hz, C-40H), 5.25 (1H, d,
JZ9.5 Hz, C-30H), 6.90–7.00 (5H, m, C-7H, C-200H,
000
C-4 H), 7.51 (1H, d, JZ7.4 Hz, C-4H) and 7.62 (1H, br s,
NH); 13C NMR (75.5 MHz; CDCl3): d 15.94 (COOCH2-
CH3), 63.8 (COOCH2CH3), 68.8 (C-40), 80.0 (C-30), 84.5
(C-50), 111.75 (C-400), 117.9 (C-200 and C-600), 125.0 (C-7),
125.5 (C-5), 127.0 (C-6), 127.2 0(0C-9), 129.0 (C-5000), 129.4
(C-6000), 130.7 (C-4), 131.400(0C-3 and C-500), 131.7 (C-4000),
131.9 (C-2000), 136.7 (C-1 ), 140.0 (C-8), 142.4 (C-100),
153.3 (C-3000), 167.9 (CONH) and 176.0 (COOC2H5); HRMS
Calcd for C25H21N2 35ClO4: 448.1190. Found: 448.1182.
00
C-3 H, C-500H and C-600H), 7.04 (1H, d, JZ7.2 Hz,
000
C-6 H), 7.15–7.20 (2H, m, C-400H and C-5000H), 7.23–7.29
(2H, m, C-5H and C-6H), 7.44–7.47 (1H, m, C-4000H), 7.65
(1H, d, JZ7.7 Hz, C-4H), 7.89–7.90 (1H, m, C-2000H) and
8.47 (1H, br s, NH); 13C NMR (300 MHz; CDCl3): d 13.7
(COOCH2CH3), 61.7 (COOCH2CH3), 64.8 (C-40), 71.1
(C-30), 83.6 (C-50), 110.9 (C-400), 117.2 (C-200 and C-600),
123.4 (C-7), 123.7 (C-5), 125.9 (C-9), 126.6 (C-6), 126.9
(C-4), 129.0 (C-300 and C-500), 130.9 (C-6000), 131.1 (C-5000),
131.1 (C-4000), 132.0 (C-2000), 141.2 (C-8 and C-1000), 141.7
(C-100), 149.9 (C-3000), 167.6 (CONH) and 175.6
(COOC2H5); HRMS Calcd for C25H21N2 79BrO4:
492.0685. Found: 492.0704.
5.4.12.
30-(3-Chlorophenyl)-40-ethoxycarbonyl-20-
phenylspiro[indoline-3,50-isoxazolidine]-2-one (6f).
Obtained as a light yellow solid (272 mg, 33%), mp 159–
160 8C (from petroleum ether–ethyl acetate), Rf: 0.38
(petroleum ether–ethyl acetate, 3:2); IR (KBr): 3205
(NH), 1729 (COOC2H5), 1620 (CONH), 1472, 1339,
1292, 1033, 1097 and 841 cmK1 1H NMR (300 MHz;
;
5.4.15. 50-Ethoxycarbonyl-30-(3-nitrophenyl)-20-phenyl-
spiro[indoline-3,40-isoxazolidine]-2-one (5h). Obtained
as a light yellow solid (123 mg, 12%), mp 165–166 8C
(from petroleum ether–ethyl acetate), Rf: 0.28 (petroleum
ether–ethyl acetate, 3:2); IR (KBr): 3310 (NH), 1741
(COOC2H5), 1619 (CONH), 1474, 1348, 1231, 1076 and
830 cmK1; 1H NMR (300 MHz; CDCl3): d 0.81 (3H, t, JZ
7.0 Hz, COOCH2CH3), 3.81–3.99 (2H, m, COOCH2CH3),
5.28 (1H, s, C-30H), 5.45 (1H, s, C-50H), 6.68 (1H, d, JZ
7.7 Hz,00C-7H), 6.87–6.93 (1H, m, C-5000H), 7.03–7.10 (4H,
m, C-2 H, C-300H, C-500H and C-600H),7.29–7.35 (3H, m,
C-5H, C-6H and C-400H), 7.49 (1H, d, JZ7.3 Hz, C-4H),
7.63–7.67 (2H, m, C-2000H and C-6000H), 7.95–7.98 (1H, m,
C-4000H) and 8.16 (1H, br s, NH); 13C NMR (75.5 MHz;
CDCl3): d 13.9 (COOCH2CH3), 61.9 (COOCH2CH3), 66.9
(C-40), 77.9 (C-30), 82.7 (C-50), 109.9 (C-400), 116.0 (C-200
and C-600), 121.9 (C-7), 123.2 (C-5), 123.5 (C-6), 123.9
(C-6000), 124.7 (C-9), 127.200(0 C-5000), 129.5 (C-300 and C-500),
129.8 (C-4000), 129.9 (C-2 ), 132.9 00(0 C-4), 138.5 (C-1000),
140.4 (C-8), 148.5 (C-100), 150.9 (C-3 ), 165.7 (CONH) and
173.8 (COOC2H5); HRMS Calcd for C25H21N3O6:
459.1430. Found: 459.1438.
CDCl3): d 0.70 (3H, t, JZ7.1 Hz, COOCH2CH3), 3.69–3.82
(2H, m, COOCH2CH3), 4.17 (1H, d, JZ9.5 Hz, C-40H),
5.23 (1H, d0,0 JZ9.5 Hz, C-30H), 6.89–6.99 (5H, m, C-7H,
00
C-2 H, C-3 H, C-500H and C-600H), 7.05 (1H, d, JZ7.4 Hz,
000
C-6 H) 7.15–7.20 (2H, m, C-400H and C-5000H), 7.23–7.33
(3H, m, C-5H, C-6H and C-4000H), 7.60–7.62 (1H, m, C-4H),
7.73 (1H, br s, C-2000H) and 8.13 (1H, br s, NH); 13C NMR
(75.5 MHz; CDCl3):
d
13.3 (COOCH2CH3), 610.3
(COOCH2CH3), 64.4 (C-40), 70.6 (C-30), 82.9 (C-5 ),
110.1 (C-400), 116.8 (C-200 and C-600), 120300.0 (C-7), 123.3
000
(C-5), 125.4 (C-9), 125.9 (C-6), 126.3 (C-5 ), 127.8 (C-6 ),
128.6 (C-4, C-300 and C-500), 130.2 (C-4 ), 130.6 (C-2 ),
000
000
000
134.8 (C-1000), 140.5 (C-8), 141.0 (C-1 ), 149.4 (C-3 ),
167.2 (CONH) and 174.6 (COOC2H5); HRMS Calcd for
C25H21N2 35ClO4: 448.1190. Found: 448.1183.
00
5.4.13.
30-(3-Bromophenyl)-50-ethoxycarbonyl-20-
phenylspiro[indoline-3,40-isoxazolidine]-2-one (5g).
Obtained as a light yellow solid (83 mg, 9%), mp 160–
161 8C (from petroleum ether–ethyl acetate), Rf: 0.36
(petroleum ether–ethyl acetate, 3:2); IR (KBr): 3284