Job/Unit: O31284
/KAP1
Date: 13-11-13 18:45:19
Pages: 9
X.-H. Yang, K. Li, R.-J. Song, J.-H. Li
FULL PAPER
130.1, 127.8, 123.7, 122.7, 121.9, 120.9, 108.3, 26.2 ppm. IR (KBr):
H), 7.91 (d, J = 8.0 Hz, 1 H), 7.85–7.80 (m, 2 H), 7.61 (s, 1 H),
7.52–7.45 (m, 3 H), 7.25 (t, J = 7.5 Hz, 1 H), 7.04 (t, J = 7.5 Hz,
1 H), 6.76 (d, J = 7.5 Hz, 1 H), 3.24 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 166.1, 142.2, 137.0, 134.1, 133.0, 132.9,
131.5, 129.1, 128.8, 128.6, 127.6, 127.5, 127.4, 126.2, 126.0, 124.4,
ν = 1759, 1645, 1536 cm–1. LRMS (EI, 70 eV): m/z (%) = 315 (86)
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[M + 2]+, 313 (86) [M]+, 158 (100), 117 (55).
1-Methyl-3-(4-nitrobenzylidene)indolin-2-one (2j):[12a] (Z/E, 1.6:1).
Data for (Z) isomer: red solid; m.p. 187.6–189.1 °C. 1H NMR
(500 MHz, CDCl3): δ = 8.36 (d, J = 8.5 Hz, 2 H), 8.26 (d, J =
7.0 Hz, 2 H), 7.54 (d, J = 7.5 Hz, 1 H), 7.51 (s, 1 H), 7.35 (t, J =
7.0 Hz, 1 H), 7.09 (t, J = 7.5 Hz, 1 H), 6.83 (d, J = 8.0 Hz, 1 H),
3.27 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 165.6, 147.9,
143.0, 139.8, 133.0, 132.2, 130.2, 129.6, 123.4, 123.3, 122.2, 119.7,
121.8, 118.8, 107.8, 25.9 ppm. IR (KBr): ν = 1749, 1648, 1563 cm–1.
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LRMS (EI, 70 eV): m/z (%) = 285 (100) [M]+, 207 (16), 158 (35),
142 (15). HRMS (ESI): calcd. for C20H16NO [M + H]+ 286.1226;
found 286.1229. Data for (E) isomer: yellow solid; m.p. 178.6–
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181.5 °C. H NMR (500 MHz, CDCl3): δ = 8.12 (s, 1 H), 8.00 (s,
1 H), 7.92–7.85 (m, 3 H), 7.72 (d, J = 8.5 Hz, 1 H), 7.68–7.66 (m,
1 H), 7.55–7.53 (m, 2 H), 7.28–7.25 (m, 1 H), 6.88–6.82 (m, 2 H),
3.30 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 168.5, 144.3,
137.1, 133.6, 133.0, 132.4, 129.8, 129.3, 128.4, 128.2, 127.8, 127.3,
127.2, 126.7, 126.4, 122.7, 121.8, 121.2, 108.2, 26.2 ppm. IR (KBr):
108.3, 26.0 ppm. IR (KBr): ν = 1788, 1675, 1569 cm–1. LRMS (EI,
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70 eV): m/z (%) = 280 (24) [M]+, 250 (41), 207 (100), 158 (26). Data
for (E) isomer: red solid; m.p. 167.6–168.5 °C. 1H NMR (500 MHz,
CDCl3): δ = 8.33 (d, J = 9.0 Hz, 2 H), 7.80–7.78 (m, 3 H), 7.43 (d,
J = 8.0 Hz, 1 H), 7.32 (t, J = 8.0 Hz, 1 H), 6.90 (t, J = 8.0 Hz, 1
H), 6.85 (d, J = 7.5 Hz, 1 H), 3.29 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 167.7, 147.9, 144.8, 141.8, 133.3, 130.9,
130.0, 129.9, 124.0, 122.9, 122.1, 120.3, 108.6, 26.3 ppm. IR (KBr):
ν = 1749, 1648, 1563 cm–1. LRMS (EI, 70 eV): m/z (%) = 285 (100)
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[M]+, 207 (18), 158 (37), 142 (19).
(E)-1-Methyl-3-(pyridin-2-ylmethylene)indolin-2-one (2n):[12b] Yel-
ν = 1788, 1675, 1569 cm–1. LRMS (EI, 70 eV): m/z (%) = 280 (26)
low solid; m.p. 113.7–114.3 °C. H NMR (500 MHz, CDCl3): δ =
1
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[M]+, 250 (45), 207 (100), 158 (28).
9.00 (d, J = 7.5 Hz, 1 H), 8.85 (d, J = 4.5 Hz, 1 H), 7.76 (t, J =
8.0 Hz, 1 H), 7.72 (s, 1 H), 7.59 (d, J = 8.0 Hz, 1 H), 7.33–7.27 (m,
2 H), 7.05 (t, J = 7.5 Hz, 1 H), 6.80 (d, J = 8.0 Hz, 1 H), 3.28 (s,
3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 169.0, 153.8, 149.5,
144.8, 136.5, 134.4, 130.4, 129.1, 127.8, 123.5, 122.1 (2 C), 121.5,
3-(3-Chlorobenzylidene)-1-methylindolin-2-one (2k): (Z/E, 1.3:1).
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Data for (Z) isomer: yellow solid; m.p. 106.9–108.4 °C. H NMR
(500 MHz, CDCl3): δ = 8.35 (s, 1 H), 8.14–8.12 (m, 1 H), 7.51 (d,
J = 7.5 Hz, 1 H), 7.44 (s, 1 H), 7.39–7.35 (m, 2 H), 7.31 (t, J =
7.5 Hz, 1 H), 7.07 (t, J = 7.5 Hz, 1 H), 6.82 (d, J = 7.5 Hz, 1 H),
3.28 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 165.9, 142.6,
135.4, 135.0, 134.1, 131.4, 130.2, 129.9, 129.4 (2 C), 127.4, 124.0,
107.6, 26.2 ppm. IR (KBr): ν = 1764, 1655, 1534 cm–1. LRMS (EI,
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70 eV): m/z (%) = 236 (70) [M]+, 208 (64), 158 (100), 130 (40).
3-Heptylidene-1-methylindolin-2-one (2o): (Z/E, 1:1). Data for mix-
122.0, 119.1, 108.0, 26.0 ppm. IR (KBr): ν = 1745, 1689, 1539 cm–1. ture of (Z) and (E) isomers: yellow solid. 1H NMR (500 MHz,
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LRMS (EI, 70 eV): m/z (%) = 271 (34) [M + 2]+, 269 (99) [M]+,
204 (21), 158 (100), 117 (23). HRMS (ESI): calcd. for C16H13ClNO 7.07–7.02 (m, 2 H), 6.83 (d, J = 8.0 Hz, 1 H), 3.24 (s, 3 H), 2.70–
CDCl3): δ = 7.54 (d, J = 4.0 Hz, 1 H), 7.28 (t, J = 8.0 Hz, 1 H),
[M + H]+ 270.0680; found 270.0681. Data for (E) isomer: yellow
solid; m.p. 80.4–81.6 °C. 1H NMR (500 MHz, CDCl3): δ = 7.76 (s,
1 H), 7.61 (s, 1 H), 7.54–7.50 (m, 2 H), 7.41–7.40 (m, 2 H), 7.29 (t,
J = 8.0 Hz, 1 H), 6.90 (t, J = 7.5 Hz, 1 H), 6.83 (d, J = 8.0 Hz, 1
H), 3.28 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 168.2,
144.5, 136.8, 135.0, 134.7, 130.2, 130.0, 129.4, 129.0, 128.3, 127.3,
2.65 (m, 2 H), 1.68–1.62 (m, 2 H), 1.46–1.39 (m, 2 H), 1.33–1.31
(m, 4 H), 0.89 (t, J = 4.0 Hz, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 168.0, 143.6, 142.4, 128.7, 127.5, 123.4, 122.4, 122.0,
108.0, 31.6, 29.4, 29.2, 28.6, 26.0, 22.6, 14.1 ppm. IR (KBr): ν =
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1749, 1648, 1563 cm–1. LRMS (EI, 70 eV): m/z (%) = 243 (91)
[M]+, 174 (90), 161 (100), 145 (62). HRMS (ESI): calcd. for
C16H22NO [M + H]+ 244.1696; found 244.1688.
122.8, 122.0, 120.7, 108.3, 26.2 ppm. IR (KBr): ν = 1745, 1689,
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1539 cm–1. LRMS (EI, 70 eV): m/z (%) = 271 (36) [M + 2]+, 269
Butyl 2-(1-Methyl-2-oxoindolin-3-ylidene)acetate (2p):[13] (Z/E,
(96) [M]+, 204 (25), 158 (100), 117 (26).
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1:1.4). Data for (Z) isomer: yellow solid; m.p. 162.5–163.7 °C. H
3-(3-Methoxybenzylidene)-1-methylindolin-2-one (2l): (Z/E, 1.3:1).
Data for (Z) isomer: yellow solid; m.p. 106.9–108.4 °C. H NMR
NMR (500 MHz, CDCl3): δ = 7.72 (d, J = 7.5 Hz, 1 H), 7.22 (t, J
= 7.5 Hz, 1 H), 6.99 (t, J = 7.5 Hz, 1 H), 6.62 (d, J = 7.5 Hz, 1 H),
4.68 (s, 1 H), 4.17–4.13 (m, 1 H), 4.00–3.96 (m, 1 H), 3.04 (s, 3 H),
1.50–1.43 (m, 2 H), 1.22–1.19 (m, 2 H), 0.83 (t, J = 7.5 Hz, 3
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 175.2, 170.4, 144.2,
132.4, 129.4, 125.8, 125.3, 122.8, 122.5, 107.6, 64.6, 30.5, 26.0, 18.8,
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(400 MHz, CDCl3): δ = 8.34 (s, 1 H), 8.64 (d, J = 8.0 Hz, 1 H),
7.52 (d, J = 8.0 Hz, 2 H), 7.36–7.26 (m, 2 H), 7.04 (t, J = 8.0 Hz,
1 H), 7.06 (d, J = 8.0 Hz, 1 H), 6.81 (d, J = 8.0 Hz, 1 H), 3.92 (s,
3 H), 3.28 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.2,
159.5, 142.3, 137.1, 135.2, 129.1, 128.9, 126.2, 125.2, 124.4, 121.8,
13.6 ppm. IR (KBr): ν = 1718, 1654, 1571 cm–1. LRMS (EI, 70 eV):
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118.9, 117.6, 115.8, 107.9, 55.5, 26.0 ppm. IR (KBr): ν = 1745,
m/z (%) = 259 (43) [M]+, 186 (55), 159 (100), 130 (54). Data for
(E) isomer: yellow solid; m.p. 184.8–185.3 °C. 1H NMR (500 MHz,
CDCl3): δ = 8.55 (d, J = 7.5 Hz, 1 H), 7.37 (t, J = 7.5 Hz, 1 H),
7.06 (t, J = 7.5 Hz, 1 H), 6.91 (s, 1 H), 6.79 (d, J = 7.5 Hz, 1 H),
4.27 (t, J = 6.5 Hz, 2 H), 3.23 (s, 3 H), 1.75–1.69 (m, 2 H), 1.49–
1.41 (m, 2 H), 0.97 (t, J = 6.5 Hz, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 167.6, 165.8, 145.9, 137.8, 132.4, 128.7, 122.8, 122.5,
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1689, 1539 cm–1. LRMS (EI, 70 eV): m/z (%) = 271 (34) [M + 2]+,
269 (99) [M]+, 204 (21), 158 (100), 117 (23). HRMS (ESI): calcd.
for C16H13ClNO [M + H]+ 270.0680; found 270.0681. Data for
(E) isomer: yellow solid; m.p. 80.4–81.6 °C. 1H NMR (400 MHz,
CDCl3): δ = 7.75 (s, 1 H), 7.59 (d, J = 8.0 Hz, 1 H), 7.30 (t, J =
8.0 Hz, 1 H), 7.21–7.15 (m, 2 H), 7.08 (s, 1 H), 6.88 (d, J = 8.0 Hz,
1 H), 6.81 (t, J = 8.0 Hz, 1 H), 6.75 (t, J = 8.0 Hz, 1 H), 3.76 (s, 3
H), 3.20 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.4,
159.6, 144.2, 137.0, 136.2, 129.8, 129.7, 127.3, 122.9, 121.8, 121.7,
119.8, 108.1, 65.0, 30.6, 26.2, 19.1, 13.7 ppm. IR (KBr): ν = 1718,
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1654, 1571 cm–1. LRMS (EI, 70 eV): m/z (%) = 259 (41) [M]+, 186
(52), 159 (100), 130 (52).
121.1, 115.4, 114.2, 108.1, 55.3, 26.1 ppm. IR (KBr): ν = 1745,
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(E)-2-(1-Methyl-2-oxoindolin-3-ylidene)acetonitrile (2q):[14] Yellow
solid; m.p. 232.7–233.4 °C. H NMR (500 MHz, CDCl3): δ = 8.06
(d, J = 7.5 Hz, 1 H), 7.45 (t, J = 7.5 Hz, 1 H), 7.13 (t, J = 7.5 Hz,
1 H), 6.84 (d, J = 8.0 Hz, 1 H), 6.32 (s, 1 H), 3.23 (s, 3 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 165.2, 145.6, 143.5, 133.7, 124.9,
1689, 1539 cm–1. LRMS (EI, 70 eV): m/z (%) = 271 (36) [M + 2]+,
1
269 (96) [M]+, 204 (25), 158 (100), 117 (26).
1-Methyl-3-(naphthalen-2-ylmethylene)indolin-2-one (2m): (Z/E,
1
1.8:1). Data for (Z) isomer: yellow solid; m.p. 213.4–215.2 °C. H
NMR (500 MHz, CDCl3): δ = 8.72 (s, 1 H), 8.46 (d, J = 8.0 Hz, 1
123.2, 119.2, 116.1, 108.8, 97.5, 26.3 ppm. IR (KBr): ν = 1756,
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