Sun et al.
FULL PAPER
boxylate (2c) White solid, yield 80%, m.p. 242—244
℃; H NMR (600 MHz, DMSO-d6) δ: 10.30 (s, 1H,
129.2, 128.5, 125.9, 123.9, 118.3, 114.1, 110.7, 101.9,
59.1, 52.4, 51.7, 50.1, 20.8; IR (KBr) ν: 3453, 3316,
3219, 2962, 2190, 1736, 1709, 1652, 1566, 1510, 1478,
1427, 1330, 1287, 1232, 1196, 1137, 1109, 1049, 987,
941, 877, 817, 780 cm ; MS (m/z) (%): 477.27 ([M-
1]+, 100). Anal. calcd for C24H19ClN4O5: C 60.19, H
4.00, N 11.70; found C 60.35, H 4.16, N 11.43.
1
NH), 7.59 (d, J=8.4 Hz, 2H, ArH), 7.44 (d, J=8.4 Hz,
2H, ArH), 7.07 (brs, 1H, ArH), 7.00 (d, J=7.8 Hz, 1H,
ArH), 6.71 (d, J=7.8 Hz, 1H, ArH), 5.87 (s, 2H, NH),
3.38 (s, 3H, OCH3), 3.32 (s, 3H, OCH3), 2.29 (s, 3H,
CH3); 13C NMR (150 MHz, DMSO-d6) δ: 178.7, 164.1,
162.5, 151.2, 143.2, 138.9, 135.7, 134.9, 134.3, 132.2,
130.9, 129.7, 129.0, 124.3, 118.4, 109.1, 103.7, 60.3,
52.5, 51.7, 49.8, 20.7; IR (KBr) ν: 3501, 3407, 3176,
3066, 2945, 2179, 1745, 1709, 1636, 1556, 1486, 1412,
1331, 1279, 1223, 1093, 1012, 981, 946, 915, 873, 804,
-
1
Dimethyl 6'-amino-5'-cyano-5-chloro-1'-p-chloro-
phenylspiro[indoline-3,4'-pyridine]-2',3'-dicarboxy-
1
late (2g) Yellow solid, yield 83%, m.p.>250 ℃; H
NMR (600 MHz, DMSO-d6) δ: 10.55 (s, 1H, NH), 7.58
(d, J=9.0 Hz, 2H, ArH), 7.49 (d, J=8.4 Hz, 2H, ArH),
7.41 (d, J=7.8 Hz, 1H, ArH), 7.25 (d, J=7.8 Hz, 1H,
ArH), 6.83 (d, J=8.4 Hz, 1H, ArH), 5.97 (s, 2H, NH),
3.38 (s, 3H, OCH3), 3.36 (s, 3H, OCH3); 13C NMR (150
MHz, DMSO-d6) δ: 178.6, 163.9, 162.3, 151.2, 143.8,
140.3, 137.7, 135.0, 134.0, 132.4, 129.6, 128.5, 126.0,
124.0, 118.3, 110.7, 102.2, 59.1, 56.0, 52.5, 51.8, 50.1;
IR (KBr) ν: 3454, 3318, 3222, 2964, 2193, 1736, 1708,
1654, 1570, 1481, 1427, 1337, 1288, 1233, 1197, 1138,
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+
1
768 cm ; MS (m/z) (%): 477.40 ([M-1] , 100). Anal.
calcd for C24H19ClN4O5: C 60.19, H 4.00, N 11.70;
found C 59.87, H 4.25, N 11.56.
Dimethyl 6'-amino-5'-cyano-5-methyl-1'-p-nitro-
phenylspiro[indoline-3,4'-pyridine]-2',3'-dicarboxyl-
1
ate (2d) Yellow solid, yield 87%, m.p.>250 ℃; H
NMR (600 MHz, DMSO-d6) δ: 10.34 (s, 1H, NH), 8.36
(d, J=9.0 Hz, 2H, ArH), 7.73 (d, J=9.0 Hz, 2H, ArH),
7.11 (brs, 1H, ArH), 7.01 (d, J=7.8 Hz, 1H, ArH), 6.72
(d, J=7.8 Hz, 1H, ArH), 6.00 (s, 2H, NH), 3.39 (s, 3H,
OCH3), 3.34 (s, 3H, OCH3), 2.30 (s, 3H, CH3); 13C
NMR (150 MHz, DMSO-d6) δ: 178.6, 164.0, 162.4,
150.9, 148.1, 142.5. 141.4, 138.9, 135.4, 132.1, 130.9,
129.0, 124.8, 124.4, 118.2, 109.1, 104.6, 60.6, 52.7,
51.8, 49.8, 20.6; IR (KBr) ν: 3506, 3412, 3174, 3075,
2955, 2179, 1712, 1639, 1602, 1559, 1489, 1416, 1340,
1280, 1225, 1143, 1010, 1034, 982, 948, 916, 855, 807,
-
1
1108, 1048, 941, 877, 818, 779 cm ; MS (m/z) (%):
497.21 ([M-1]+, 100). Anal. calcd for C23H16Cl2N4O5:
C 55.33, H 3.23, N 11.22; found C 55.20, H 3.61, N
10.78.
Dimethyl 6'-amino-5'-cyano-5-chloro-1'-p-nitro-
phenylspiro[indoline-3,4'-pyridine]-2',3'-dicarboxy-
1
late (2h) Yellow solid, yield 87%, m.p.>250 ℃; H
NMR (600 MHz, DMSO-d6) δ: 10.58 (s, 1H, NH), 8.36
(d, J=7.8 Hz, 2H, ArH), 7.79 (d, J=8.4 Hz, 2H, ArH),
7.47 (brs, 1H, ArH), 7.26 (d, J=7.2 Hz, 1H, ArH), 6.85
(d, J=7.8 Hz, 1H, ArH), 6.09 (s, 2H, NH), 3.38 (d, J=
6.6 Hz, 6H, OCH3); 13C NMR (150 MHz, DMSO-d6) δ:
178.5, 163.9, 162.3, 150.9, 148.2, 143.2, 141.0, 140.3,
137.5, 132.3, 128.6, 126.0, 124.7, 124.2, 118.1, 110.7,
102.8, 59.4, 52.7, 51.9, 50.1; IR (KBr) ν: 3456, 3315,
3221, 3107, 2962, 2197, 1742, 1709, 1656, 1577, 1529,
1478, 1427, 1345, 1288, 1229, 1138, 1108, 1047, 990,
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+
1
764 cm ; MS (m/z) (%): 488.36 ([M-1] , 100). Anal.
calcd for C24H19N5O7: C 58.90, H 3.91, N 14.31; found
C 58.73, H 4.28, N 14.27.
Diethyl 6'-amino-5'-cyano-5-methyl-1'-p-
methoxy-phenylspiro[indoline-3,4'-pyridine]-2',3'-
dicarboxylate (2e) Yellow solid, yield 72%, m.p.
1
178—180 ℃; H NMR (600 MHz, DMSO-d6) δ: 10.26
(s, 1H, NH), 7.33 (d, J=8.4 Hz, 2H, ArH), 7.06—7.04
(m, 3H, ArH), 7.00 (d, J=7.8 Hz, 1H, ArH), 6.69 (d,
J=7.8 Hz, 1H, ArH), 5.63 (s, 2H, NH), 3.80—3.74 (m,
7H, OCH2, OCH3), 2.29 (s, 3H, CH3), 0.90 (t, J=7.2 Hz,
3H, CH3), 0.82 (t, J=7.2 Hz, 3H, CH3); 13C NMR (150
MHz, DMSO-d6) δ: 179.0, 163.7, 162.0, 160.1, 151.5,
143.9, 139.0, 136.1, 131.7, 130.7, 128.7, 127.4, 124.2,
118.6, 114.6, 108.9, 102.7, 61.5, 60.3, 55.5, 49.7, 20.6,
13.2, 13.0; IR (KBr) ν: 3445, 3344, 2979, 2189, 1713,
1646, 1565, 1499, 1417, 1371, 1319, 1253, 1218, 1101,
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1
940, 912, 880, 856, 832, 779, 753 cm ; MS (m/z) (%):
508.17 ([M-1]+, 100). Anal. calcd for C23H16ClN5O7:
C 54.18, H 3.16, N 13.74; found C 53.85, H 3.47, N
13.51.
Diethyl 6'-amino-5'-cyano-5-chloro-1'-p-
methoxyphenylspiro[indoline-3,4'-pyridine]-2',3'-
dicarboxylate (2i) White solid, yield 71%, m.p.>250
1
℃; H NMR (600 MHz, DMSO-d6) δ: 10.52 (s, 1H,
NH), 7.38—7.36 (m, 3H, ArH), 7.26 (d, J=8.4 Hz, 1H,
ArH), 7.05 (d, J=9.0 Hz, 2H, ArH), 6.83 (d, J=8.4 Hz,
1H, ArH), 5.74 (s, 2H, NH), 3.80—3.76 (m, 7H, OCH2,
OCH3), 0.90 (t, J=7.2 Hz, 3H, CH3), 0.84 (t, J=7.2 Hz,
3H, CH3); 13C NMR (150 MHz, DMSO-d6) δ: 178.9,
163.5, 161.8, 160.2, 151.6, 144.6, 140.4, 138.1, 131.9,
128.4, 127.1, 125.9, 123.9, 118.5, 114.6, 110.6, 101.3,
61.6, 60.5, 58.9, 55.5, 50.1, 13.2, 13.0; IR (KBr) ν: 3447,
3369, 3318, 3218, 2975, 2187, 1736, 1703, 1649, 1566,
1510, 1473, 1431, 1372, 1328, 1252, 1221, 1189, 1137,
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+
1
1027, 815 cm ; MS (m/z) (%): 503.43 ([M+1] , 100).
Anal. calcd for C27H26N4O6: C 64.53, H 5.22, N 11.15;
found C 64.49, H 5.517, N 10.76.
Dimethyl 6'-amino-5'-cyano-5-chloro-1'-p-
methylphenylspiro[indoline-3,4'-pyridine]-2',3'-
dicarboxylate (2f) Yellow solid, yield 79%, m.p.
1
229—231 ℃; H NMR (600 MHz, DMSO-d6) δ: 10.55
(s, 1H, NH), 7.35—7.32 (m, 5H, ArH), 7.25 (d, J=8.4
Hz, 1H, ArH), 6.84 (d, J=8.4 Hz, 1H, ArH), 5.75 (s,
2H, NH), 3.34 (d, J=5.4 Hz, 6H, OCH3), 2.37 (s, 3H,
CH3); 13C NMR (150 MHz, DMSO-d6) δ: 178.7, 164.0,
162.3, 151.3, 144.2, 140.3, 139.9, 137.8, 132.3, 130.0,
-
1
1107, 1061, 1027, 990, 851, 818, 776 cm ; MS (m/z)
(%): 523.36 ([M+1]+, 100). Anal. calcd for C26H23Cl-
N4O6: C 59.72, H 4.43, N 10.71; found C 59.60, H 4.87,
4
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, XX, 1—7