RSC Advances
Paper
+
1
32.9, 131.1, 128.0, 125.6, 125.4, 122.0, 111.3, 63.2, 13.8; HRMS 14.1; HRMS (ESI+) calcd for C14
H
14
N
2
NaO
5
(M + Na) , m/z
+
(ESI+) calcd for C H ClN O (M + H) , m/z 297.0273, found 313.0795, found 313.0798.
12 10 2 5
2
97.0274.
Ethyl (Z)-2-(5-methoxy-2-oxoindolin-3-ylidene)-2-nitroacetate
ꢀ
1
Ethyl (Z)-2-(4-bromo-2-oxoindolin-3-ylidene)-2-nitroacetate (3l). 54% yield, a dark red solid; mp. ¼ 154–155 C; H NMR (500
ꢀ
1
(
3e). 80% yield, a yellow solid; mp. ¼ 169–171 C; H NMR MHz, CDCl
3
) d 8.02 (s, 1H), 7.57 (d, J ¼ 2.4 Hz, 1H), 6.87 (dd, J ¼
(500 MHz, CDCl
3
) d 8.70 (s, 1H), 7.26–7.12 (m, 2H), 6.87 (dd, J ¼ 8.5, 2.5 Hz, 1H), 6.75 (d, J ¼ 8.5 Hz, 1H), 4.44 (m, 2H), 3.81 (s,
1
3
13
8
.8, 1.5 Hz, 1H), 4.42 (m, 2H), 1.35 (t, J ¼ 7.8 Hz, 3H); C NMR 3H), 1.40 (t, J ¼ 7.1 Hz, 3H); C NMR (125 MHz, CDCl
3
) d 165.8,
(125 MHz, CDCl
3
) d 166.4, 164.5, 143.8, 133.7, 132.3, 129.0, 163.3, 155.6, 135.4, 131.5, 126.5, 121.7, 116.6, 112.1, 110.5, 63.0,
+
1
26.3, 120.9, 118.4, 109.2, 63.0, 13.8; HRMS (ESI+) calcd for 55.9, 13.8; HRMS (ESI+) calcd for C13
H
13
N
2
O
6
(M + H) , m/z
+
C H BrN O (M + H) , m/z 340.9590, found 340.9599.
293.0695, found 293.0698.
1
2
10
2 5
Ethyl (Z)-2-(5-bromo-2-oxoindolin-3-ylidene)-2-nitroacetate
ꢀ
1
(
(
1
7
1
3f). 76% yield, a yellow solid; mp. ¼ 163–164 C; H NMR
500 MHz, CDCl
) d 8.10 (s, 1H), 7.86 (s, 1H), 7.44 (dd, J ¼ 8.3,
.9 Hz, 1H), 6.75 (d, J ¼ 8.3 Hz, 1H), 4.44 (m, 2H), 1.40 (t, J ¼
A representative procedure for TiCl /DMAP mediated
condensation reaction of isatins with activated methylenes
(4a–4d) and 4-methylbenzenesulfonamide (4e)
4
3
1
3
3
.2 Hz, 3H); C NMR (125 MHz, CDCl ) d 164.8, 159.0, 142.9,
34.7, 131.2, 129.6, 127.4, 126.0, 122.2, 113.9, 63.2, 13.4; HRMS A stirred solution of isatin (1a, 0.5 mmol, 1.0 equiv.) in anhy-
+
ꢀ
(ESI+) calcd for C12
H
9
BrNaN
2
O
5
(M + Na) , m/z 362.9587, found drous THF was cooled to 0 C, TiCl
2,2-dimethyl-1,3-dioxane-4,6-dione (4a, 0.5 mmol, 1.0 equiv.)
Ethyl (Z)-2-(6-bromo-2-oxoindolin-3-ylidene)-2-nitroacetate were added slowly, then DMAP (1.5 mmol, 3.0 equiv.) was
4
(1.0 mmol, 2.0 equiv.) and
3
62.9590.
ꢀ
1
(
(
7
7
1
3g). 75% yield, a dark red solid, mp. ¼ 151–153 C; H NMR added, the resulting mixture was stirred at rt. Aer the reaction
500 MHz, CDCl
) d 8.10 (s, 1H), 7.82 (d, J ¼ 6.5 Hz, 1H), 7.23– was complete (monitored by TLC), DCM (10 mL) was added and
.21 (m, 1H), 7.05 (d, J ¼ 2.0 Hz, 1H), 4.44 (m, 2H), 1.41 (t, J ¼ the mixture was ltered through a pad of celite; the celite pad
3
1
3
.2 Hz, 3H); C NMR (125 MHz, CDCl
3
) d 165.7, 163.1, 142.5, was then washed by DCM (5.0 mL each) for two times; the
32.2, 126.4, 125.7, 125.4, 125.3, 119.7, 113.7, 63.2, 13.8; HRMS combined organic layers were dried and concentrated under
+
(ESI+) calcd for C12
H10BrN
2
O
5
(M + H) , m/z 340.9590, found reduced pressure. The resulting residue was puried by ash
chromatography (EtOAc/hexane) to provide 5a.
3
40.9592.
Ethyl (Z)-2-(7-bromo-2-oxoindolin-3-ylidene)-2-nitroacetate
2,2-Dimethyl-5-(2-oxoindolin-3-ylidene)-1,3-dioxane-4,6-dione
ꢀ
1
ꢀ
1
(
(
(
3h). 78% yield, a dark red solid; mp. ¼ 175–177 C; H NMR (5a). 71 yield, an orange solid; mp. ¼ 146–147 C; H NMR (500
500 MHz, CDCl
) d 7.94–7.92 (m, 1H), 7.75 (s, 1H), 7.46–7.44 MHz, CDCl ) d 8.86 (s, 1H), 8.51 (d, J ¼ 7.9 Hz, 1H), 7.41 (t, J ¼
m, 1H), 7.00–6.97 (m, 1H), 4.44 (m, 2H), 1.39 (t, J ¼ 7.2 Hz, 3H); 7.7 Hz, 1H), 7.02 (t, J ¼ 7.7 Hz, 1H), 6.93 (d, J ¼ 7.8 Hz, 1H), 1.83
3
3
1
3
13
C NMR (125 MHz, CDCl
3
3
) d 164.2, 162.9, 140.6, 133.6, 129.3, (s, 6H); C NMR (125 MHz, CDCl ) d 165.9, 160.1, 158.7, 145.5,
1
26.2, 124.2, 123.8, 122.0, 103.2, 63.3, 13.8; HRMS (ESI+) calcd 142.4, 136.4, 130.6, 123.3, 121.0, 120.0, 111.2, 105.6, 27.2; HRMS
+
+
for C12
H
9
BrNaN
2
O
5
(M + Na) , m/z 362.9587, found 362.9579.
5
(ESI+) calcd for C14H11NNaO (M + Na) , m/z 296.0529, found
Ethyl (Z)-2-(7-methyl-2-oxoindolin-3-ylidene)-2-nitroacetate 296.0533.
ꢀ
1
(
(
7
3i). 61% yield, a dark red solid; mp. ¼ 124–127 C; H NMR
2-(2-Oxoindolin-3-ylidene)malononitrile (5b). 97% yield,
ꢀ
18
ꢀ
1
500 MHz, CDCl ) d 10.10 (s, 1H), 7.78 (d, J ¼ 6.8 Hz, 1H), 7.13– a dark red solid; mp. ¼ 234–235 C (lit. mp. 232–233 C); H
3
.11 (m, 1H), 6.99–6.95 (m, 1H), 4.40 (m, 2H), 2.27 (s, 3H), 1.40 NMR (500 MHz, CDCl ) d 8.13 (s, 1H), 7.62 (d, J ¼ 7.5 Hz, 1H),
3
13
(
1
1
t, J ¼ 7.1 Hz, 3H); C NMR (125 MHz, CDCl
3
) d 167.4, 164.4, 7.54 (d, 7.9 Hz, 1H), 7.15 (d, J ¼ 9.0 Hz, 1H), 6.98 (d, J ¼ 5.8 Hz,
1
3
40.8, 132.7, 131.3, 126.9, 122.9, 122.6, 120.3, 119.9, 62.9, 16.1, 1H); C NMR (125 MHz, DMSO) d 164.2, 159.8, 138.3, 126.3,
+
3.8; HRMS (ESI+) calcd for C13
H
13
N
2
O
5
(M + H) , m/z 277.0746, 125.1, 123.4, 123.2, 119.1, 112.7, 112.1, 81.1; HRMS (ESI+) calcd
+
found 277.0744.
Ethyl (Z)-2-(5-uoro-2-oxoindolin-3-ylidene)-2-nitroacetate
for C11H
5
N
3
NaO (M + Na) , m/z 218.0325, found 218.0326.
Ethyl (E)-2-cyano-2-(2-oxoindolin-3-ylidene)acetate (5c). 95%
ꢀ
1
ꢀ
10a
ꢀ
(
(
7
(
3j). 73% yield, a yellow solid; mp. ¼ 163–165 C; H NMR yield, a dark red solid; mp. ¼ 204–205 C, (lit. mp. 208–209 C);
1
500 MHz, CDCl ) d 8.24 (s, 1H), 7.71 (dd, J ¼ 8.6, 2.5 Hz, 1H),
H NMR (500 MHz, CDCl ) d 8.68 (s, 1H), 8.03 (d, J ¼ 7.8 Hz, 1H),
3
3
.04 (td, J ¼ 8.7, 2.5 Hz, 1H), 6.79 (dd, J ¼ 8.5, 4.2 Hz, 1H), 4.44 7.39–7.41 (m, 1H), 7.08–7.10 (m, 1H), 6.90 (d, J ¼ 7.9 Hz, 1H),
1
3
1
3
m, 2H), 1.41 (t, J ¼ 7.1 Hz, 3H); C NMR (125 MHz, CDCl
3
)
4.41–4.44 (m, 2H), 1.39 (t, J ¼ 7.0 Hz, 3H); C NMR (125 MHz,
d 165.7, 163.0, 159.6 (d, JC–F ¼ 225.5 Hz), 137.63 (d, J ¼ 21.5 Hz), CDCl ) d 165.4, 160.6, 143.6, 140.4, 134.8, 125.5, 123.4, 119.2,
3
1
1
32.90, 125.93 (d, J ¼ 23.7 Hz), 121.74 (d, J ¼ 12.5 Hz), 117.81, 114.0, 111.1, 106.5, 63.6, 13.7; HRMS (ESI+) calcd for C13
11 2 3
H N O
+
12.99 (d, J ¼ 11.4 Hz), 110.69, 63.19, 13.75; HRMS (ESI+) calcd (M + H) , m/z 243.0764, found 243.0757.
+
for C H FN O (M + H) , m/z 281.0568, found 281.0563.
Diethyl 2-(2-oxoindolin-3-ylidene)malonate (5d). 85% yield,
1
2
10
2 5
ꢀ
1
Ethyl
(Z)-2-(4,6-dimethyl-2-oxoindolin-3-ylidene)-2- a dark red solid; mp. ¼ 186–188 C; H NMR (500 MHz, CDCl )
3
nitroacetate (3k). 74% yield, a dark red solid; mp. ¼ 184– d 8.72 (s, 1H), 8.32 (d, J ¼ 7.9 Hz, 1H), 7.31 (td, J ¼ 7.7, 1.1 Hz,
ꢀ
1
1
7
8
1
86 C; H NMR (500 MHz, CDCl
3
) d 8.34 (s, 1H), 7.63 (s, 1H), 1H), 7.03 (m, 1H), 6.82 (d, J ¼ 7.8 Hz, 1H), 4.39–4.44 (m, 4H),
13
.07 (s, 1H), 4.46 (m, 2H), 2.29 (s, 3H), 2.20 (s, 3H), 1.40 (t, J ¼ 1.35–1.39 (m, 6H); C NMR (125 MHz, CDCl ) d 167.8, 165.3,
3
1
3
.4 Hz, 3H); C NMR (125 MHz, CDCl
42.2, 137.7, 131.5, 129.5, 127.5, 120.5, 117.1, 62.4, 21.0, 16.6, 62.1, 13.9, 13.8; HRMS (ESI+) calcd for C15
90.1023, found 290.1016.
3
) d 165.0, 159.0, 143.3, 162.9, 143.6, 134.7, 133.1, 129.6, 129.0, 122.8, 119.8, 110.3, 62.3,
+
H
5
16NO (M + H) , m/z
2
51356 | RSC Adv., 2017, 7, 51352–51358
This journal is © The Royal Society of Chemistry 2017