Molecular Diversity
Methyl 2‑(3‑hydroxy‑1‑methyl‑2‑oxoindolin‑3‑yl)acrylate
(11) H NMR (200 MHz, DMSO-d6): δ 3.13 (s, 3H); 3.48
176.6. HRMS-ESI: m/z [M − H] calcd. for C12H9Cl2NO4:
299.9909; found: 299.9835.
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(s, 3H); 6.44 (d, J=1.2 Hz, 1H); 6.46 (d, J=1.2 Hz, 1H);
6.93–7.04 (m, 3H); 7.30 (m, 1H). 13C NMR (50 MHz,
DMSO-d6): δ 31.2, 56.9, 80.1, 113.7, 127.2, 128.1, 132.5,
134.7, 136.0, 144.9, 149.7, 169.6, 180.6.
Methyl 2‑(5,7‑dichloro‑3‑hydroxy‑1‑methyl‑2‑oxoindo‑
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lin‑3‑yl)acrylate (17) mp 72–73 °C; H NMR (400 MHz,
DMSO-d6): δ 3.45 (s, 3H, CH3), 3.55 (s, 3H, CH3); 6.54 (d,
J = 16.0 Hz, 2H, =CH2); 7.00 (s, 1H, Ar–H); 7.05 (s, 1H,
Ar–H); 7.49 (s, 1H, OH). 13C NMR (100 MHz, DMSO-d6):
δ 29.3, 52.1, 74.3, 114.9, 122.5, 126.7, 128.8, 130.6, 135.5,
138.4, 139.3, 164.4, 175.5. HRMS-ESI: m/z [M−H] calcd.
for C13H11Cl2NO4: 313.0065; found: 313.9993.
Methyl 2‑(1‑allyl‑3‑hydroxy‑2‑oxoindolin‑3‑yl)acrylate
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(12) H NMR (400 MHz, DMSO-d6): δ 2.25 (s, 3H, CH3);
3.05 (m, 2H, =CH2); 3.96 (dd, J=4.0 Hz, J=8.0 Hz, 2H,
CH2); 4.60 (m, 1H, =CH); 5.27 (dd, J=4.0 Hz, J=8.0 Hz,
2H, =CH2); 5.46, (s, 1H, OH); 5.71 (m, 2H, Ar–H); 5.80
(dd, J=4.0 Hz, J=4.0 Hz, 1H, Ar–H); 6.03 (td, J=4.0 Hz,
J=4.0 Hz, J=12.0 Hz, 1H, Ar–H). 13C NMR (100 MHz,
DMSO-d6) δ 41.7, 51.9, 74.9, 109.3, 117.2, 122.1, 123.1,
127.7, 129.5, 130.9, 143.7, 164.5, 175.3.
General procedure for the synthesis of MBHA
(18–21)
Reactions were carried out using the corresponding isatin
derivatives (0.5 mmol), Michael acceptors (0.6 mmol),
1.0 mL of THF as solvent and DABCO (56 mg, 0.5 mmol)
at room temperature under stirrer for the time indicated in
Table 2. After that, the solvent was removed and reaction
media were directly fltered through silica gel, using hex-
ane/ethyl acetate (7:3) as eluent. The reaction products were
concentrated under reduced pressure.
Methyl 2‑(3‑hydroxy‑5‑nitro‑2‑oxoindolin‑3‑yl)acrylate
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(13) H NMR (400 MHz, DMSO-d6): δ 3.55 (s, 3H, CH3);
6.55 (s, 1H, =CH2); 6.60 (s, 1H, =CH2); 7.00 (s, 1H, OH);
7.08 (d, J = 16 Hz, 1H, Ar–H); 7.79 (d, J = 12 Hz, 1H,
Ar–H); 8.19 (d, J=8.0 Hz, 1H, Ar–H); 11.17 (s, 1H, NH).
13C NMR (100 MHz, DMSO-d6): δ 52.0, 74.8, 109.9, 118.8,
126.9, 128.8, 132.8, 138.5, 141.9, 149.9, 164.5, 177.3.
2‑(3‑hydroxy‑1‑methyl‑2‑oxoindolin‑3‑yl)‑N‑(4‑nitrophenyl)
acrylamide (18) 1H NMR (400 MHz, DMSO-d6): δ 3.37
(s, 3H, CH3); 6.37 (d, 2H, =CH2); 6.62 (s, 1H, OH); 6.97
(m, 2H, Ar–H); 7.09 (d, J =4.0 Hz, 1H, Ar–H); 7.29 (td,
J = 4.0 Hz, J =8 Hz, J =16 Hz, 1H, Ar–H); 7.75 (s, 1H,
Ar–H); 7.77 (s, 1H, Ar–H); 8.14 (s, 1H, Ar–H); 8.17 (s, 1H,
Ar–H); 10.66 (s, 1H, NH). 13C NMR (100 MHz, DMSO-d6):
δ 26.2, 75.3, 108.5, 119.5, 122.0, 122.8, 123.0, 124.8, 129.5,
131.1, 142.3 143.8, 144.6, 144.9, 165.3. HRMS-ESI: m/z
[M−H] calcd. for C18H15N3O5: 352.1012; found: 352.0941.
Methyl 2‑(3‑hydroxy‑1‑methyl‑5‑nitro‑2‑oxoindolin‑3‑yl)
acrylate (14) 1H NMR (400 MHz, DMSO-d6): δ 3.25 (s,
3H, CH3); 3.53 (s, 3H, CH3); 6.60 (s, 1H, =CH2); 6.62
(s, 1H, =CH2); 7.09 (s, 1H, OH); 7.29 (d, J = 8.0 Hz, 1H,
Ar–H); 7.85 (d, J=4.0 Hz, 1H, Ar–H); 8.33 (dd, J=4.0 Hz,
1H, Ar–H). 13C NMR (100 MHz, DMSO-d6): δ 26.6, 52.1,
74.3, 109.0, 118.3, 127.0, 128.9, 131.9, 138.4, 142.4, 150.6,
164.4, 175.8.
Methyl 2‑(1‑allyl‑3‑hydroxy‑5‑nitro‑2‑oxoindolin‑3‑yl)
acrylate (15) mp 129–131 °C; 1H NMR (400 MHz, DMSO-
d6): δ 3.54 (s, 3H, CH3); 4.42 (m, 2H, CH2); 5.23 (dd,
J = 4.0 Hz, J = 12.0 Hz, 1H, =CH2); 5.40 (dd, J = 4.0 Hz,
1H, =CH2); 5.85 (m, 1H, CH); 6.63 (d, J = 12.0 Hz, 2H,
=CH2); 7.14 (s, 1H, OH); 7.19 (d, J = 8 Hz, 1H, Ar–H);
7.85 (d, J = 4.0 Hz, 1H, Ar–H); 8.30 (dd, J = 4.0 Hz, 1H,
Ar–H). 13C NMR (100 MHz, DMSO-d6): δ 42.0, 52.1,
74.3, 109.6, 117.6, 118.4, 126.8, 129.2, 131.2, 132.0, 138.2,
149.7, 164.4, 175.5. HRMS-ESI: m/z [M − H] calcd. for
C15H14N2O6: 317.0852; found: 317.0779.
2‑(5,7‑dichloro‑3‑hydroxy‑1‑methyl‑2‑oxoindolin‑3‑yl)‑N‑(4
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nitrophenyl)acrylamide (19) mp 125–128 °C; H NMR
(400 MHz, DMSO-d6): δ 3.35 (s, 3H, CH3); 3.44 (s, 1H,
OH); 6.47 (s, 1H, =CH2); 6.52 (s, 1H, =CH2); 7.77 (d,
J = 8 Hz, 2H, Ar–H); 8.18 (m, 4H, Ar–H); 10.69 (s, 1H,
NH). 13C NMR (100 MHz, DMSO-d6): δ 74.5, 113.9, 114.8,
119.6, 119.7, 122.2, 124.8, 126.5, 127.5, 130.5, 135.9,
139.4, 142.4, 142.5, 144.7, 156.3, 164.9, 175.6. HRMS-ESI:
m/z [M − H] calcd. for C18H13Cl2N3O5: 420.0232; found:
420.0160.
Methyl 2‑(5,7‑dichloro‑3‑hydroxy‑2‑oxoindolin‑3‑yl)acrylate
(16) mp 121–123 °C; H NMR (400 MHz, DMSO-d6): δ
2‑(1‑allyl‑3‑hydroxy‑2‑oxoindolin‑3‑yl)‑N‑(4‑nitrophenyl)
acrylamide (20) mp 126–128 °C; H NMR (400 MHz,
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2.71 (s, 3H, CH3); 5.64 (s, 1H, =CH2); 5.69 (s, 1H, =CH2);
6.09 (s, 1H, Ar–H); 6.15 (d, J=4.0 Hz, 1H, Ar–H); 10.17
(s, 1H, NH). 13C NMR (100 MHz, DMSO-d6): δ 52.0, 75.7,
114.5, 122.3, 125.9, 128.5, 128.8, 135.0, 138.5, 140.2, 164.5,
DMSO-d6): δ 4.31 (s, 2H, CH2); 5.19 (dd, J = 4.0 Hz,
J=12 Hz, 1H, =CH2); 5.40 (dd, J=4.0 Hz, J=20 Hz, 1H,
=CH2); 5.85 (m, 1H, =CH); 6.39 (d, J=4.0 Hz, 2H, =CH2);
6.68 (s, 1H, OH); 6.94 (m, 2H, Ar–H); 7.12 (dd, J=4.0 Hz,
J =4.0 Hz, 1H, Ar–H); 7.24 (td, J = 4.0 Hz, J =8.0 Hz,
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