The Journal of Organic Chemistry
Article
+
1
HRMS (ESI+) m/z calcd for C H N [M + H] : 367.1917, found:
0.7). H NMR (400 MHz, CDCl ) δ 14.01 (s, 1H), 7.81−7.79 (d, J =
2
4
23
4
3
3
67.1923.
(
8 Hz, 1H), 7.32−7.27 (m, 3H), 7.24−7.23 (m, 2H), 7.14−7.11 (t, J =
8 Hz, 1H), 6.98−6.90 (m, 3H), 6.86−6.83 (m, 2H), 2.97 (s, 1H),
2.44 (s, 3H), 2.41 (s, 3H) (solvent impurity at 1.5 and 1.3 ppm).
Z)-4-Methoxy-N-((Z)-3-(2-(4-methoxyphenyl)hydrazono)-1-
methylindolin-2-ylidene)aniline (3l). Following the general proce-
dure, the desired compound was prepared in 41% (120.8 mg) yield as
a red amorphous solid with m.p. 127 °C. The eluent was EtOAc/n-
hexane (5:95) (R = 0.4). H NMR (400 MHz, CDCl ) δ 13.62 (s,
1
3
1
C{ H} NMR (100 MHz, CDCl ) δ 147.5, 147.4, 144.2, 143.9,
3
1
39.3, 138.7, 129.2, 128.7, 127.6, 123.2, 122.5, 121.6, 118.9, 118.7,
115.02, 111.7, 107.8, 101.0, 32.0, 21.7, 21.6. HRMS (ESI+) m/z calcd
1
f
3
+
1
7
(
H), 7.76−7.75 (d, J = 4 Hz, 1H), 7.35−7.33 (d, J = 8 Hz, 2H),
for C H N [M + H] : 355.1917, found: 355.1929.
2
3
23
4
.25−7.21 (t, J = 8 Hz, 1H), 7.10−7.06 (t, J = 8 Hz, 1H), 7.00−6.98
(
Z)-3-Methyl-N-((Z)-7-methyl-3-(2-(m-tolyl)hydrazono)indolin-2-
ylidene)aniline (3r). Following the general procedure, the desired
compound was prepared in 69% (186.4 mg) yield as a red amorphous
d, J = 8 Hz, 2H), 6.91−6.89 (m, 4H), 6.84−6.82 (d, J = 8 Hz, 1H),
3
1
1
5
3
.84 (s, 3H), 3.81 (s, 3H), 2.98 (s, 3H) (solvent impurities at 1.5 and
.3 ppm). 13C{ H} NMR (100 MHz, CDCl ) δ 155.9, 147.6, 140.3,
1
3
solid with m.p. 122 °C. The eluent was EtOAc/n-hexane (5:95) (R =
f
1
27.6, 126.8, 122.8, 121.6, 118.4, 116.3, 114.8, 114.3, 107.9, 55.8,
5.7, 32.1, 29.8. HRMS (ESI+) m/z calcd for C H N O [M + H] :
0.7). H NMR (400 MHz, CDCl ) δ 13.72 (s, 1H), 7.60−7.59 (d, J =
3
+
2
3
23
4
2
4 Hz, 1H), 7.36−7.32 (t, J = 8 Hz, 1H), 7.22−7.20 (d, J = 8 Hz, 2H),
7.17−7.15 (d, J = 8 Hz, 1H), 7.10 (s,1H), 7.02−6.96 (m, 5H), 6.82−
6.80 (d, J = 8 Hz, 1H), 2.42 (s, 1H), 2.37 (s, 3H), 2.18 (s, 3H)
87.1816, found: 387.1822.
(
Z)-N-((Z)-1-Allyl-3-(2-(4-methoxyphenyl)hydrazono)indolin-2-
ylidene)-4-methoxyaniline (3m). Following the general procedure,
the desired compound was prepared in 49% (128.6 mg) yield as a red
1
3
1
(
solvent impurity at 1.5 and 1.3 ppm). C{ H} NMR (100 MHz,
CDCl ) δ 149.6, 147.9, 143.7, 139.9, 139.3, 139.2, 129.7, 129.3, 129.1,
3
amorphous solid with m.p. 129 °C. The eluent was EtOAc/n-hexane
125.2, 123.2, 123.0, 122.8, 121.7, 118.5, 116.9, 114.8, 111.5, 21.7,
21.7, 16.2. HRMS (ESI+) m/z calcd for C H N [M + H] :
1
+
(
5:95) (R = 0.5). H NMR (400 MHz, CDCl ) δ 13.69 (s, 1H),
f
3
23 23
4
7
7
6
5
.76−7.74 (d, J = 8 Hz, 1H), 7.34−7.31 (d, J = 12 Hz, 2H), 7.24−
.13 (m, 2H), 7.09−7.05 (t, J = 8 Hz, 1H), 7.00−6.94 (m, 2H),
.90−6.85 (m, 4H), 6.81−6.79 (d, J = 8 Hz, 1H), 5.59−5.50 (m, 1H),
.14−5.06 (m, 1H), 4.98−4.88 (t, J = 20 Hz, 2H), 4.65−4.63 (d, J = 8
355.1917, found: 355.1923.
(Z)-N-((Z)-6-Methoxy-3-(2-(m-tolyl)hydrazono)indolin-2-yli-
dene)-3-methylaniline (3s). Following the general procedure, the
desired compound was prepared in 81% (203.9 mg) yield as a red
amorphous solid with m.p. 132 °C. The eluent was EtOAc/n-hexane
Hz, 1H), 3.83 (s, 3H), 3.81 (s, 3H) (solvent impurities at 1.5 and 1.3
ppm) (probably contains E/Z mixtures). C{ H} NMR (100 MHz,
1
3
1
1
(5:95) (R = 0.5). H NMR (400 MHz, CDCl ) δ 13.46 (s, 1H),
f
3
CDCl ) δ 133.9, 131.7, 130.0, 126.9, 126.0, 122.4, 121.7, 121.4, 120.0,
7.64−7.62 (d, J = 8 Hz, 1H), 7.34−7.30 (t, J = 8 Hz, 1H), 7.22−7.12
(m, 4H), 7.00−6.93 (m, 3H), 6.79−6.77 (d, J = 8 Hz, 1H), 6.61−6.58
(dd, J = 4 Hz, 8 Hz, 1H), 6.34 (d, J = 4 Hz, 1H), 3.80 (s, 3H), 2.40 (s,
3
1
5
4
19.5, 118.7, 118.4, 116.8, 116.1, 114.8, 114.3, 113.5, 109.6, 108.8,
+
5.8, 55.7, 16.0. HRMS (ESI+) m/z calcd for C H N O [M + H] :
2
5
25
4
2
1
3
1
13.1972, found: 413.1995.
Z)-4-Methoxy-N-((Z)-3-(2-(4-methoxyphenyl)hydrazono)-7-
3H), 2.36 (s, 3H) (solvent impurity at 1.5 and 1.3 ppm). C{ H}
(
NMR (100 MHz, CDCl ) δ 160.6, 150.1, 147.9, 143.9, 142.0, 139.8,
3
methylindolin-2-ylidene)aniline (3n). Following the general proce-
dure, the desired compound was prepared in 49% (144.4 mg) yield as
a red amorphous solid with m.p. 135 °C. The eluent was EtOAc/n-
139.3, 129.7, 129.2, 128.9, 125.2, 122.8, 122.6, 120.4, 118.8, 116.6,
114.5, 111.2, 107.3, 96.2, 55.7, 21.7, 21.6. HRMS (ESI+) m/z calcd
+
for C H N O [M + H] : 371.1866, found: 371.1872.
2
3
23
4
1
hexane (5:95) (R = 0.4). H NMR (400 MHz, CDCl ) δ 13.61 (s,
(Z)-4-Methoxy-N-((Z)-6-methoxy-3-(2-(4-methoxyphenyl)-
hydrazono)indolin-2-ylidene)aniline (3t). Following the general
procedure, the desired compound was prepared in 55% (150.4 mg)
yield as a red amorphous solid with m.p. 120 °C. The eluent was
f
3
1
7
2
1
1
H), 7.57−7.55 (d, J = 8 Hz, 1H), 7.33−7.31 (d, J = 8 Hz, 2H),
.14−7.11 (m, 3H), 7.00−6.96 (m, 4H), 6.92−6.89 (d, J = 12 Hz,
H), 3.86 (s, 3H), 3.81 (s, 3H), 2.19 (s, 3H) (solvent impurities at
.5 and 1.3 ppm). 13C{ H} NMR (100 MHz, CDCl ) δ 140.9, 128.7,
1
1
EtOAc/n-hexane (5:95) (R = 0.3). H NMR (400 MHz, CDCl ) δ
3
f
3
27.9, 123.1, 123.0, 121.7, 116.7, 115.5, 115.2, 114.9, 55.8, 55.7, 29.9.
7.60−7.58 (d, J = 8 Hz, 1H), 7.22 (s, 1H), 7.09−7.07 (d, J = 8 Hz,
3H), 6.98−6.96 (d, J = 8 Hz, 3H), 6.90−6.88 (d, J = 8 Hz, 3H),
6.60−6.58 (dd, J = 8, 4 Hz, 1H), 6.35−6.34 (d, J = 4 Hz, 1H), 3.84 (s,
3H), 3.81 (s, 3H), 3.80 (s, 3H) (solvent impurity at 1.5 and 1.3 ppm).
+
HRMS (ESI+) m/z calcd for C H N O [M + H] : 387.1816,
2
3
23
4
2
found: 387.1818.
(
Z)-3-Methyl-N-((Z)-3-(2-(m-tolyl)hydrazono)indolin-2-ylidene)-
+
aniline (3o). Following the general procedure, the desired compound
HRMS (ESI+) m/z calcd for C H N O [M + H] : 403.1765,
2
3
23
4
3
was prepared in 69% (203.9 mg) yield as a red amorphous solid with
found: 403.1764.
1
m.p. 130 °C (R = 0.5). The eluent was EtOAc/n-hexane (5:95). H
(Z)-2-Chloro-N-((Z)-3-(2-(2-chlorophenyl)hydrazono)indolin-2-
ylidene)aniline (3u). Following the general procedure, the desired
compound was prepared in 49% (159.5 mg) yield as a red amorphous
f
NMR (400 MHz, CDCl ) δ 13.68 (s, 1H), 7.75−7.73 (d, J = 8 Hz,
3
1
H), 7.35−7.31 (t, J = 8 Hz, 1H), 7.25−7.16 (m, 5H), 7.07−6.95 (m,
4
H), 6.83−6.81 (d, J = 8 Hz, 1H), 6.78−6.76 (d, J = 8 Hz, 1H), 2.41
solid with m.p. 114 °C. The eluent was EtOAc/n-hexane (5:95) (R =
f
1
3
1
1
(
s, 3H), 2.38 (s, 3H). C{ H} NMR (100 MHz, CDCl ) δ 149.7,
0.5). H NMR (400 MHz, CDCl ) δ 13.87 (s, 1H), 7.93−7.90 (dd, J
3
3
47.9, 143.7, 140.5, 139.8, 139.3, 129.7, 129.3, 128.9, 127.9, 125.2,
= 4, 8 Hz, 1H), 7.77−7.75 (d, J = 8 Hz, 1H), 7.52−7.49 (dd, J = 4, 8
Hz, 1H), 7.34−7.29 (m, 3H), 7.22−7.19 (m, 2H), 7.14−7.06 (m,
3H), 6.95−6.90 (m, 1H), 6.81−6.79 (d, J = 8 Hz, 1H) (solvent
+
2
2
21
4
1
3
1
found: 341.1777.
impurity at 1.5 and 1.3 ppm). C{ H} NMR (100 MHz, CDCl ) δ
3
(Z)-4-Methoxy-N-((Z)-3-(2-(4-methoxyphenyl)hydrazono)-1,7-di-
149.4, 144.9, 140.8, 140.6, 130.9, 130.7, 129.6, 128.6, 127.9, 125.4,
methylindolin-2-ylidene)aniline (3p). Following the general proce-
dure, the desired compound was prepared in 51% (140.7 mg) yield as
a red amorphous solid with m.p. 105 °C. The eluent was EtOAc/n-
122.9, 122.5, 122.0, 119.8, 114.7, 109.8. HRMS (ESI+) m/z calcd for
+
C H N Cl [M + H] : 381.0668, found: 381.0695.
2
0
15
4
2
(Z)-2-Chloro-N-((Z)-3-(2-(2-chlorophenyl)hydrazono)-1-methyl-
indolin-2-ylidene)aniline (3v). Following the general procedure, the
desired compound was prepared in 52% (156.7 mg) yield as a red
1
hexane (5:95) (R = 0.5). H NMR (400 MHz, CDCl ) δ 7.68−7.67
f
3
(
d, J = 4 Hz, 1H), 7.38−7.37 (d, J = 8 Hz, 2H), 7.07−7.05 (d, J = 8
Hz, 2H), 7.01−6.99 (d, J = 8 Hz, 2H), 6.93−6.91 (m, 5H), 3.84 (s,
amorphous solid with m.p. 109 °C. The eluent was EtOAc/n-hexane
1
3
H), 3.82 (s, 3H), 3.20 (s, 3H), 2.52 (s, 3H) (solvent impurity at 1.3
(5:95) (R
f
= 0.7). H NMR (400 MHz, CDCl
) δ 14.25 (s, 1H),
3
13
1
ppm). C{ H} NMR (100 MHz, CDCl ) δ 156.2, 155.9, 140.0,
7.91−7.89 (dd, J = 8 Hz, 1H), 7.77−7.75 (d, J = 8 Hz, 1H), 7.43−
7.41 (dd, J = 8 Hz, 1H), 7.33−7.30 (m, 3H), 7.24−7.23 (m, 1H),
7.12−7.08 (m, 2H), 7.06−7.02 (m, 1H), 6.92−6.88 (m, 1H), 6.83−
6.81 (d, J = 8 Hz, 1H), 2.94 (s, 3H) (solvent impurity at 1.5 and 1.3
3
1
2
4
30.0, 122.7, 122.2, 120.6, 116.7, 116.5, 114.7, 114.5, 55.8, 55.7, 36.2,
+
9.8, 19.5. HRMS (ESI+) m/z calcd for C H N O [M + H] :
2
4
25
4
2
01.1972, found: 401.1983.
1
3
1
(Z)-3-Methyl-N-((Z)-1-methyl-3-(2-(m-tolyl)hydrazono)indolin-2-
ppm). C{ H} NMR (100 MHz, CDCl ) δ 147.5, 145.0, 144.4,
3
ylidene)aniline (3q). Following the general procedure, the desired
140.6, 129.7, 129.6, 128.5, 127.9, 127.1, 126.3, 124.1, 123.3, 122.3,
compound was prepared in 71% (191.8 mg) yield as a red amorphous
121.9, 119.1, 114.6, 108.0, 30.7. HRMS (ESI+) m/z calcd for
+
solid with m.p. 115 °C. The eluent was EtOAc/n-hexane (5:95) (R =
C H N Cl [M + H] : 395.0825, found: 395.0850.
f
21 17
4
2
3
754
J. Org. Chem. 2020, 85, 3748−3756