The Journal of Organic Chemistry
Page 16 of 24
(
ppm) = 8.20 (d, J = 7.2 Hz, 2H), 7.56 (t, J = 6.9 Hz, 1H), 7.46 (t, J = 7.2 Hz, 2H), 7.27-7.33 (m, 6H),
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
7
4
1
1
4
.14 (s, 1H), 7.03 (d, J = 7.2 Hz, 1H), 6.62 (d, J = 7.8 Hz, 1H), 5.08 (d, J = 15.6 Hz, 1H), 4.78 (s, 1H),
1
3
.71 (d, J = 15.6 Hz, 1H), 2.24 (s, 3H), 1.05 (s, 9H); C NMR (150 MHz, CDCl ) δ (ppm) = 186.6,
3
75.7, 165.4, 146.7, 140.2, 136.5, 135.0, 132.9, 132.6, 130.8, 129.9, 128.8, 128.1, 127.8, 127.2, 126.6,
+
25.8, 109.2, 82.1, 71.9, 60.5, 44.2, 27.3, 20.8; HRMS (ESI) m/z [M+H] calcd for C H N O
3
0
30
3
4
-1
96.2231, found 496.2226; IR (KBr, cm ) υ 3447, 2981, 1730, 1712, 1647, 1232.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
tert-butyl
5'-benzoyl-1-benzyl-5,7-dimethyl-2-oxo-2',4'-dihydrospiro[indoline-3,3'-pyrazole]-4'-
carboxylate (4m): colorless solid; yield 224 mg (88%); mp 174.8-176.4 °C; dr > 20:1; 1H NMR (600
MHz, CDCl ) δ (ppm) = 8.20 (d, J = 7.8 Hz, 2H), 7.56 (t, J = 7.2 Hz, 1H), 7.47 (t, J = 7.2 Hz, 2H), 7.33
3
(t, J = 7.2 Hz, 2H), 7.27 (t, J = 7.2 Hz, 2H), 7.20 (d, J = 7.2 Hz, 2H), 7.03 (s, 1H), 6.82 (s, 1H), 5.33 (d,
1
J = 16.8 Hz, 1H), 4.99 (d, J = 16.8 Hz, 1H), 4.78 (s, 1H), 2.22 (s, 3H), 2.20 (s, 3H), 1.14 (s, 9H); C
3
NMR (150 MHz, CDCl ) δ (ppm) = 186.6, 176.9, 165.5, 146.6, 138.2, 136.8, 136.6, 134.9, 132.9,
3
132.6, 129.9, 128.9, 128.1, 127.3, 126.6, 125.5, 124.5, 120.0, 82.2, 71.3, 60.8, 45.4, 27.5, 20.5, 18.5;
+
-1
HRMS (ESI) m/z [M+H] calcd for C H N O 510.2387, found 510.2393; IR (KBr, cm ) υ 3440,
3
1
32
3
4
3057, 2932, 1728, 1708, 1632, 1575, 1236.
tert-butyl 5'-benzoyl-1-benzyl-6-chloro-2-oxo-2',4'-dihydrospiro[indoline-3,3'-pyrazole] -4'-carboxylate
1
(4n): colorless solid; yield 219 mg (85%); mp 135.8-136.4 °C; dr > 20:1; H NMR (400 MHz, CDCl ) δ
3
(ppm) = 8.13 (d, J = 8.0 Hz, 2H), 7.52 (t, J = 6.8 Hz, 1H), 7.41 (t, J = 7.2 Hz, 2H), 7.20-7.31 (m, 6H),
6.95 (d, J = 8.0 Hz, 1H), 6.68-6.72 (m, 2H), 5.05 (d, J = 15.6 Hz, 1H), 4.71 (s, 1H), 4.61 (d, J = 15.6 Hz,
13
1
H), 1.06 (s, 9H); C NMR (100 MHz, CDCl ) δ (ppm) = 186.0, 175.5, 165.0, 146.4, 143.7, 136.3,
3
136.2, 134.3, 132.5, 129.8, 128.8, 127.9, 127.1, 127.0, 126.8, 124.0, 122.9, 109.9, 82.5, 71.4, 60.8, 44.4,
-
-1
2
3
7.6; HRMS (ESI) m/z [M-H] calcd for C H N O Cl 514.1539, found 514.1551; IR (KBr, cm ) υ
2
9
25
3
4
330, 3033, 2931, 1717, 1651, 1608, 1488, 1214.
tert-butyl 5'-benzoyl-1-benzyl-6-bromo-2-oxo-2',4'-dihydrospiro[indoline-3,3'-pyrazole] -4'-carboxylate
1
(4o): colorless solid; yield 229 mg (82%); mp 103.6-105.1 °C; dr > 20:1; H NMR (400 MHz, CDCl ) δ
3
(ppm) = 8.13 (d, J = 7.2 Hz, 2H), 7.52 (t, J = 7.4 Hz, 1H), 7.41 (t, J = 7.6 Hz, 2H), 7.25-7.29 (m, 4H),
7
.11-7.15 (m, 3H), 6.84 (s, 1H), 6.79 (s, 1H), 5.04 (d, J = 15.4 Hz, 1H), 4.70 (s, 1H), 4.59 (d, J = 15.4
1
3
Hz, 1H), 1.06 (s, 9H); C NMR (100 MHz, CDCl ) δ (ppm) = 186.0, 175.4, 165.0, 146.4, 143.8, 136.2,
3
1
2
3
34.3, 132.5, 129.8, 128.9, 127.9, 127.1, 127.0, 125.9, 124.6, 124.2, 122.7, 112.6, 82.5, 71.4, 60.8, 44.4,
-
-1
7.6; HRMS (ESI) m/z [M-H] calcd for C H N O Br 558.1034, found 558.1040; IR (KBr, cm ) υ
2
9
25
3
4
442, 2980, 1722, 1604, 1546, 1256.
Methyl 5'-benzoyl-1-benzyl-2-oxo-2',4'-dihydrospiro[indoline-3,3'-pyrazole] -4'-carboxylate (4p):
1
colorless solid; yield 193 mg (88%); mp 83.5-84.7 °C; dr > 20:1; H NMR (400 MHz, CDCl ) δ (ppm)
3
= 8.21 (d, J = 7.6 Hz, 2H), 7.55 (t, J = 7.3 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 7.20-7.32 (m, 7H), 7.00 (t, J
=
7.4 Hz, 1H), 6.71 (d, J = 7.6 Hz, 1H), 6.64 (s, 1H), 5.11 (d, J = 15.6 Hz, 1H), 4.86 (s, 1H), 4.73 (d, J =
1
3
15.6 Hz, 1H), 3.30 (s, 3H); C NMR (100 MHz, CDCl ) δ (ppm) = 185.7, 175.1, 166.5, 145.0, 142.0,
3
1
36.0, 134.6, 132.5, 130.4, 129.7, 128.5, 127.8, 127.5, 126.7, 125.1, 124.7, 122.9, 109.4, 71.8, 59.5,
16
ACS Paragon Plus Environment