6
Tetrahedron
1
solid; 93% yield; mp: 160-162˚C; H NMR (500 MHz,
2-(1-Allyl-5-fluoro-2-oxo-3-(2-oxo-2-
ACCEPTED MANUSCRIPT
CDCl3) δ 7.61-7.89 (m, 2H), 7.25-7.60 (m, 10H), 6.70 (d,
J= 10.0 Hz, 1H), 5.03-5.07 (m, 2H), 4.62 (s, 1H), 4.12 (d,
J= 18.0 Hz, 1H), 3.75 (d, J= 18.0 Hz, 1H); 13C (125 MHz,
CDCl3) δ 30.57, 42.65, 45.05, 49.35, 109.2, 110.3, 112.0,
116.3, 126.7, 127.4, 128.1, 128.9, 129.0, 133.6, 142.9,
173.6, 193.6; HRMS (ESI-TOF) m/z: calcd. for
C26H18BrN3O2 [M+Na]+ 506.0480; found 506.0467.
phenylethyl)indolin-3-yl)malononitrile (3i): Brown solid;
1
94% yield; mp: 112-114˚C; H NMR (500 MHz, CDCl3) δ
7.12-7.89 (m, 6H), 6.97-6.99 (m, 2H), 5.91-5.96 (m, 1H),
5.35-5.52 (m, 2H), 4.62 (s, 1H), 4.47-4.56 (m, 2H), 4.11 (d,
J= 18.0 Hz, 1H), 3.73 (d, J= 18.0 Hz, 1H); 13C (125 MHz,
CDCl3) δ 30.51, 42.45, 43.46, 49.48, 109.1, 110.3, 111.2,
111.3, 111.8, 112.1, 117.1, 117.2, 118.8, 126.6, 126.7,
128.1, 128.8, 130.5, 134.3, 135.2, 139.8, 158.3, 160.3,
173.4, 193.7; HRMS (ESI-TOF) m/z: calcd. for
C22H16FN3O2 [M+Na]+ 396.1124; found 396.1128.
2-(1-Benzyl-5-iodo-2-oxo-3-(2-oxo-2-
phenylethyl)indolin-3-yl)malononitrile (3e): Brown solid;
90% yield; mp: 151-153˚C; H NMR (500 MHz, CDCl3) δ
1
7.33-7.92 (m, 12H), 6.63 (d, J=10.0 Hz, 1H), 5.06-5.09 (m,
2H), 4.62 (s, 1H), 4.13 (d, J= 18.0 Hz, 1H), 3.75 (d, J=17.5
Hz, 1H); 13C (125 MHz, CDCl3) δ 30.55, 42.65, 45.00,
49.16, 86.03, 109.2, 110.3, 112.5, 127.4, 127.5, 128.1,
128.2, 128.9, 132.2, 134.3, 135.2, 139.6, 143.6, 173.4;
HRMS (ESI-TOF) m/z: calcd. for C26H18IN3O2 [M+Na]+
554.0341; found 554.0346.
2-(1-Allyl-5-chloro-2-oxo-3-(2-oxo-2-
phenylethyl)indolin-3-yl)malononitrile (3j): Light brown
1
solid; mp: 107-109˚C; 92% yield; H NMR (500 MHz,
CDCl3) δ 7.47-7.89 (m, 6H), 7.39-7.42 (m, 1H), 6.98 (d, J=
5.0 Hz, 1H), 5.91-5.96 (s, 1H), 5.35-5.52 (m, 2H), 4.59 (s,
1H), 4.44-4.52 (m, 2H), 4.12 (d, J= 17.5 Hz, 1H), 3.74 (d,
J= 18.0 Hz, 1H); 13C (125 MHz, CDCl3) δ 74.22, 95.02,
96.16, 101.9, 105.5, 117.8, 120.6, 124.8, 135.5, 136.9,
143.3, 147.5, 174.7; HRMS (ESI-TOF) m/z: calcd. for
C22H16ClN3O2 [M+Na]+ 412.0829; found 412.0824.
2-(1-Benzyl-5-methyl-2-oxo-3-(2-oxo-2-
phenylethyl)indolin-3-yl)malononitrile (3f): Light brown
solid; 91% yield; mp: 190-192˚C 1H NMR (500 MHz,
CDCl3) δ 7.31-7.93 (m, 10H), 7.28 (s, 1H), 7.12 (d, J= 8.0
Hz, 1H), 6.75 (d, J= 8.0 Hz, 1H), 5.07 (s, 2H), 4.68 (s, 1H),
4.14 (d, J= 17.5 Hz, 1H), 3.74 (d, J= 18.0 Hz, 1H), 2.31 (s,
3H); 13C (125 MHz, CDCl3) δ 21.12, 30.69, 42.43, 44.92,
49.43, 109.6, 110.3, 110.7, 124.2, 125.2, 127.4, 127.8,
128.2, 128.8, 128.9, 131.1, 133.4, 134.1, 134.9, 135.5,
141.3, 174.1, 193.9; HRMS (ESI-TOF) m/z: calcd. for
C27H21N3O2 [M+Na]+ 442.1531; found 442.1538.
2-(1-Allyl-5-bromo-2-oxo-3-(2-oxo-2-
phenylethyl)indolin-3-yl)malononitrile (3k): Brown solid;
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91% yield; mp: 122-124˚C; H NMR (500 MHz, CDCl3) δ
7.63-7.90 (m, 2H), 7.47-7.62 (m, 5H), 6.93 (d, J= 5.0 Hz,
1H), 5.91-5.96 (m, 1H), 5.35-5.52 (m, 2H), 4.58 (s, 1H),
4.44-4.54 (m, 2H), 4.12 (d, J= 17.5 Hz, 1H), 3.74 (d, J=
18.0 Hz, 1H); 13C (125 MHz, CDCl3) δ 30.58, 42.59, 43.42,
49.23, 109.1, 110.3, 111.9, 116.2, 118.8, 126.7, 128.2,
128.9, 130.3, 130.7, 133.7, 134.3, 142.9, 173.2, 193.6;
HRMS (ESI-TOF) m/z: calcd. for C22H16BrNO5 [M+Na]+
456.0324; found 456.0320.
2-(1-Benzyl-5-methoxy-2-oxo-3-(2-oxo-2-
phenylethyl)indolin-3-yl)malononitrile (3g): Brown solid;
1
92% yield; mp: 158-160˚C; H NMR (500 MHz, CDCl3) δ
7.90-7.92 (m, 2H), 7.39-7.50 (m, 6H), 7.12 (d, J= 5.0 Hz,
2H), 6.74-6.83 (m, 3H), 5.06 (s, 1H), 4.69 (s, 1H), 4.12 (d,
J= 18.1 Hz, 1H), 3.75 (s, 3H), 3.72 (s, 1H); 13C (125 MHz,
CDCl3) δ 30.61, 42.39, 44.99, 49.69, 55.74, 109.5, 110.6,
111.1, 111.4, 114.8, 126.4, 127.5, 127.8, 128.1, 128.8,
128.9, 134.1, 134.8, 135.5, 136.9, 156.5, 173.7, 193.9;
HRMS (ESI-TOF) m/z: calcd. for C27H21N3O3 [M+Na]+
458.1481; found 458.1488.
2-(1-Allyl-5-iodo-2-oxo-3-(2-oxo-2-phenylethyl)indolin-
3-yl)malononitrile (3l): Brown solid; 90% yield; mp: 140-
1
142˚C; H NMR (500 MHz, CDCl3) δ 7.73-7.89 (m, 4H),
7.47-7.65 (m, 3H), 6.82 (d, J= 8.0 Hz, 1H), 5.90-5.95 (m,
1H), 5.35-5.52 (m, 2H), 4.57 (s, 1H), 4.43-4.53 (m, 2H),
4.11 (d, J= 18.0 Hz, 1H), 3.73 (d, J= 18.0 Hz, 1H); 13C (125
MHz, CDCl3) δ 30.59, 42.59, 43.37, 49.03, 85.92, 109.1,
110.3, 112.3, 118.8, 127.5, 128.2, 128.8, 130.3, 132.2,
134.3, 135.2, 139.6, 143.6, 173.0, 193.6; HRMS (ESI-TOF)
m/z: calcd. for C22H16IN3O2 [M+Na]+ 504.0185; found
504.0181.
2-(1-Allyl-2-oxo-3-(2-oxo-2-phenylethyl)indolin-3-
yl)malononitrile (3h): Brown solid; 89% yield; mp: 101-
1
103˚C; H NMR (500 MHz, CDCl3) δ 7.41-7.89 (m, 7H),
7.03-7.15 (m, 2H), 5.93-5.99 (m, 1H), 5.34-5.53 (m, 2H),
4.63 (s, 1H), 4.48-4.57 (m, 2H), 4.13 (d, J= 18.0 Hz, 1H),
3.71 (d, J=17.5 Hz, 1H); 13C (125 MHz, CDCl3) δ 30.67,
42.36, 43.31, 49.25, 109.4, 110.4, 110.6, 118.6, 123.5,
123.6, 125.2, 128.1, 128.8, 130.6, 130.7, 134.1, 143.8,
173.6, 193.9; HRMS (ESI-TOF) m/z: calcd. for C22H17N3O2
[M+Na]+ 378.1218; found 378.1229.
2-(1-Allyl-5-methyl-2-oxo-3-(2-oxo-2-
phenylethyl)indolin-3-yl)malononitrile (3m): Brown
1
solid; 90% yield; mp: 160-162˚C; H NMR (500 MHz,
CDCl3) δ 7.88-7.90 (m, 2H), 7.61 (s, 1H), 7.45-7.48 (m,
2H), 7.29 (d, J= 10.0 Hz, 2H), 6.92 (d, J= 8.0 Hz, 1H),
5.92-5.98 (m, 1H), 5.32-5.52 (m, 2H), 4.62 (s, 1H), 4.45-
4.51 (m, 2H), 4.11 (d, J= 17.5 Hz, 1H), 3.70 (d, J= 17.5 Hz,