for facile synthesis of dihydro-2-oxypyrrole derivatives uio-66-so … · electronic supplementary...
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Electronic Supplementary Information (ESI)
UiO-66-SO3H metal-organic framework as a green catalyst
for facile synthesis of dihydro-2-oxypyrrole derivatives
Ramin Ghorbani-Vaghei,*aDavood Azarifar,a Saba Dalirana and Ali Reza Oveisib
aFaculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
bDepartment of Chemistry, Faculty of Science, University of Zabol, Zabol, Iran
*Corresponding author: Phone: +989183122123; Fax: +988138380709; E-mail address:
[email protected] (Ramin Ghorbani-Vaghei)
Table of Contents Page numberS1.Characterizationdata fordimethyl 2-((4-chlorophenyl)amino)maleate S1S2. Characterization datafor1a S2S3.Characterization datafor2a S3S4. Characterization datafor3a S4S5. Characterization datafor4a S5S6. Characterization datafor5a S6S7. Characterization datafor6a S7S8. Characterization datafor7a S9S9. Characterization datafor8a S10S10. Characterization datafor9a S11S11. Characterization datafor10a S13
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
S1
S1. Characterization data fordimethyl 2-((4-chlorophenyl)amino)maleate.
Pale yellow solid,mp:decomposed at 305°C. 1H NMR (DMSO-d6, 300 MHz):δH(ppm)9.77 (br, s,
1H, NH), 8.13 (d, 2H, 3J = 8.7 Hz, Ar–H), 7.05 (d, 2H, 3J = 8.7 Hz, Ar–H), 5.75 (s, 1H, =CH),
3.74 (s, 3H, OCH3), 3.67 (s, 3H, OCH3).
Fig. S1 The 1H NMR (300MHz) spectrum of dimethyl 2-((4-chlorophenyl)amino)maleate
HN
MeO2CH
CO2Me
Cl
S2
S2. Characterizationdatafor methyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-5-oxo-2,5-
dihydro-1H-pyrrole-3-carboxylate 1a (Table 3, Entry 1):
N
OHN
MeO2C
ClCl
Cream solid,mp: 174-175 °C (lit.: 175-176 °C [3]). FT-IR (KBr):ῡ(cm-1) 3275, 1693, 1634,
1594, 1546, 1493, 1454, 1362, 1263, 1137, 826, 756.1H NMR (CDCl3, 250 MHz):δH(ppm)7.97
(br, s, 1H, NH), 7.66 (d, 2H, 3J= 9.25 Hz, Ar–H), 7.28 (d, 2H, 3J= 8 Hz, Ar–H), 7.21 (d, 2H, 3J=8.26 Hz, Ar–H), 7.00 (d, 2H, 3J= 8.6 Hz,Ar–H), 4.43 (s, 2H, NCH2), 3.71 (s, 3H, OCH3).
Fig. S2The 1H NMR(250MHz)spectrum of product (1a)
S3
S3. Characterization dataformethyl 5-oxo-1-(p-tolyl)-4-(p-tolylamino)-2,5-dihydro-1H-pyrrole-3-carboxylate 2a (Table 3, Entry 2):
N
OHN
MeO2C
MeMe
Pale yellow solid,mp: 176-177 °C (lit.: 175-176 °C [3]). FT-IR (KBr):ῡ (cm-1) 3282, 1685,1657,
1544, 1439, 1360, 1300, 1132. 1H NMR (CDCl3, 250 MHz):δH(ppm)7.93 (br, s, 1H, NH), 7.68
(d, 2H, 3J= 8.76 Hz, Ar–H), 7.19 (s, 2H, Ar–H), 7.11 (d, 2H, 3J= 8.76 Hz, Ar–H), 7.00 (d, 2H, 3J= 12.76 Hz, Ar–H), 4.43 (s, 2H, NCH2), 3.67 (s, 3H, OCH3),2.26 (s, 6H, Ar-Me).
Fig. S3 The 1H NMR(250MHz)spectrum of product (2a)
S4
S4. Characterization dataformethyl 1-(4-methoxyphenyl)-4-((4-methoxyphenyl)amino)-5-oxo-
2,5-dihydro-1H-pyrrole-3-carboxylate 3a (Table 3, Entry 3):
N
MeO2C
HN
O
OMeMeO
White solid,mp:161-162 °C (lit.: 160-162 °C [3]). FT-IR (KBr):ῡ (cm-1) 3282, 1685, 1657, 1543,
1513, 1402, 1300, 1034. 1H NMR (CDCl3, 300 MHz):δH(ppm) 8.01 (br, s, 1H, NH), 7.67 (d, 2H, 3J= 8 Hz, Ar–H), 7.11 (d, 2H, 3J=8.7 Hz, Ar–H), 6.93-6.84 (m, 4H, Ar–H), 4.48 (s, 2H, NCH2),
3.82 (s, 6H, OCH3), 3.75 (s, 3H, OCH3).
Fig. S4 The 1H NMR(300MHz)spectrum of product (3a)
S5
S5. Characterization dataformethyl 1-(4-bromophenyl)-4-((4-bromophenyl)amino)-5-oxo-2,5-
dihydro-1H-pyrrole-3-carboxylate 4a (Table 3, Entry 4):
N
OHN
MeO2C
BrBr
White solid,mp: 180-182 °C (lit.: 181-182 °C [3]). FT-IR (KBr):ῡ (cm-1)3274, 1691, 1651, 1533,
1353, 1217, 813. 1H NMR (CDCl3, 300 MHz):δH(ppm) 8.05 (br, s, 1H, NH), 7.74 (d, 2H, 3J= 8.7
Hz, Ar–H), 7.34-7.27 (m, 4H, Ar–H), 7.07 (d, 2H, 3J=8.4 Hz, Ar–H), 4.51 (s, 2H, NCH2), 3.79
(s, 3H, OCH3).
Fig. S5 The 1H NMR(300MHz)spectrum of product (4a)
S6
S6. Characterization dataformethyl 5-oxo-1-phenyl-4-(phenylamino)-2,5-dihydro-1H-pyrrole-
3-carboxylate 5a(Table 3, Entry 5):
N
OHN
MeO2C
Yellow solid, mp: 160-161 °C (lit.: 160-162 °C [3]). FT-IR (KBr):ῡ (cm-1) 3285, 1684, 1648,
1510, 1444, 1437, 1267, 1242, 841. 1H NMR (CDCl3, 250 MHz):δH(ppm)7.94 (br, s, 1H, NH),
7.73-7.69 (m, 2H, Ar–H), 7.36-7.05 (m, 8H, Ar–H), 4.47 (s, 2H, NCH2), 3.67 (s, 3H, OCH3).
Fig. S6 The 1H NMR(250MHz)spectrum of product (5a)
S7
S7. Characterization dataformethyl 5-oxo-2-phenyl-1-(p-tolyl)-4-(p-tolylamino)-2,5-dihydro-
1H-pyrrole-3-carboxylate 6a (Table 3, Entry 6):
N
OHN
MeO2CMe
Me
White solid,mp: 167-168 °C. FT-IR (KBr):ῡ (cm-1) 3274, 1691, 1651, 1533, 1514, 1391, 1353,
1217, 811. 1H NMR (CDCl3, 250 MHz):δH(ppm) 8.06 (br, s, 1H, NH), 7.23-7.02 (m, 13H, Ar–
H), 5.69 (s, 1H, NCH), 3.47 (s, 3H, OCH3), 2.26 (s, 3H, Ar-Me), 2.15 (s, 3H, Ar-Me). 13C NMR
(CDCl3,100 MHz):δC(ppm) 168.14, 166.90, 137.05, 136.15, 135.91, 135.43, 134.63, 133.96,
129.38, 129.02, 128.41, 128.02, 127.58, 123.21, 123.17, 122.72, 63.13, 51.05, 20.99, 20.89.
MS (m/z): 412.5(M+), 379.5, 353.5 (100%), 278.4, 194.4, 158.3, 142.3, 121.3, and 91.3.
Elemental anal. Calcd (%) for C26H24N2O3: C, 75.71; H, 5.86; N, 6.79. Found: C, 75.72; H, 5.85;
N, 6.79.
Fig. S7 The 1H NMR(250MHz)spectrum of product (6a)
S8
Fig. S8The 13C NMR (100MHz) spectrumof product (6a)
4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 2 4 0 2 6 0 2 8 0 3 0 0 3 2 0 3 4 0 3 6 0 3 8 0 4 0 00
5 0 0 0 0 0
1 0 0 0 0 0 0
1 5 0 0 0 0 0
2 0 0 0 0 0 0
2 5 0 0 0 0 0
3 0 0 0 0 0 0
3 5 0 0 0 0 0
4 0 0 0 0 0 0
4 5 0 0 0 0 0
5 0 0 0 0 0 0
5 5 0 0 0 0 0
6 0 0 0 0 0 0
6 5 0 0 0 0 0
7 0 0 0 0 0 0
7 5 0 0 0 0 0
8 0 0 0 0 0 0
m / z - ->
A b u n d a n c e
S c a n 5 8 ( 0 . 6 6 9 m in ) : 3 0 0 2 5 1 6 7 1 4 . D \ d a t a . m s3 5 3 . 5 4 1 2 . 5
9 1 . 32 7 8 . 4
1 9 4 . 46 5 . 3 3 2 5 . 5
1 2 1 . 3 3 7 9 . 52 4 6 . 42 2 0 . 4
1 5 8 . 3
Fig. S9 The MS spectrum of product (6a)
S9
S8. Characterization dataformethyl1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-5-oxo-2-
phenyl-2,5-dihydro-1H-pyrrole-3-carboxylate 7a (Table 3, Entry 7):
N
OHN
MeO2CCl
Cl
Yellow solid,mp: 176-177 °C (lit.: 175-177 °C [3]). FT-IR (KBr):ῡ (cm-1) 3289, 1676, 1649,
1537, 1516, 1441, 1399, 1294, 1150, 1224, 1150, 811. 1H NMR (CDCl3, 250 MHz):δH(ppm)
8.13 (br, s, 1H, NH), 7.36-7.06 (m, 13H, Ar–H), 5.69 (s, 1H, NCH), 3.51 (s, 3H, OCH3).
Fig. S10 The 1H NMR(250MHz)spectrum of product (7a)
S10
S9. Characterization dataformethyl 1-(4-methoxyphenyl)-4-((4-methoxyphenyl)amino)-5-oxo-
2-phenyl-2,5-dihydro-1H-pyrrole-3-carboxylate 8a (Table 3, Entry 8):
N
OHN
MeO2CMeO
OMe
White solid,mp: 167-168 °C. FT-IR (KBr):ῡ (cm-1) 3282, 1686, 1667, 1544, 1514, 1495, 1439,
1395, 1242, 1232, 1034, 1093, 834. 1H NMR (CDCl3, 250 MHz):δH(ppm) 8.08 (br, s, 1H, NH),
7.23-7.06 (m, 9H, Ar–H), 6.78 (d, 2H, 3J =7.6 Hz, Ar–H), 6.68 (d, 2H, 3J=7.6 Hz, Ar–H), 5.62
(s, 1H, NCH), 3.73 (s, 3H, OCH3), 3.64 (s, 3H, OCH3), 3.47 (s, 3H, OCH3).MS (m/z): 444.2
(M+), 385.1, 339.1, 294.1, 235.1, 188.1(100%), 160.0, 132.0, and77.1.Elemental anal. Calcd (%)
for C26H24N2O5: C, 70.26; H, 5.44; N, 6.30. Found: C, 70.25; H, 5.45; N, 6.31.
Fig. S11 The 1H NMR(250MHz)spectrum of product (8a)
S11
50 100 150 200 250 300 350 400 450 500 550 600 6500
500000
1000000
1500000
2000000
2500000
3000000
3500000
m/z-->
Abundance
Scan 46 (0.527 min): DIRECT PROB_123.D\data.ms188.1
385.1444.2
132.077.1294.1
235.1339.1 503.0 647.1548.0 595.2
Fig. S12The MS spectrum of product (8a)
S10. Characterization dataformethyl 5-oxo-1,2-diphenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate 9a (Table 3, Entry 9):
N
OHN
MeO2C
Cream solid,mp:155-156 °C. FT-IR (KBr):ῡ (cm-1) 3282, 1685, 1657, 1543, 1513, 1402, 1300,
1242,1034, 834. 1H NMR (CDCl3, 250 MHz):δH(ppm) 8.08 (br, s, 1H, NH), 7.41-7.10 (m, 15H,
Ar–H), 5.75 (s, 1H, NCH), 3.47 (s, 3H, OCH3).13C NMR (CDCl3, 100 MHz):δC(ppm) 164.69,
164.00, 138.56, 136.76, 128.83, 128.56, 128.47, 127.56, 126.15 125.43, 124.84, 124.60. 122.96,
122.76, 109.31, 63.17, 51.13.MS (m/z): 384.5 (M+),325.5 (100%), 297.4, 264.4, 232.3, 204.4,
180.4, 144.3, 102.3, and 77.3. Elemental anal. Calcd (%) for C24H20N2O3: C, 74.98; H, 5.24; N,
7.29. Found: C, 74.98; H, 5.24; N, 7.29.
S12
Fig. S13The 1H NMR(250MHz)spectrum of product (9a)
Fig. S14The 13C NMR (100MHz) spectrumof product (9a)
S13
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 3800
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
6000000
6500000
7000000
7500000
8000000
m/z-->
Abundance
Scan 37 (0.491 min): 3002516713.D\data.ms325.5
384.5
77.3
180.4 297.4264.451.3 204.4102.3
144.3 232.3 351.5
Fig. S15 The MSspectrumof product (9a)
S11. Characterization dataforMethyl 5-oxo-1-phenyl-4-(phenylamino)-2-(p-tolyl)-2,5-dihydro-
1H-pyrrole-3-carboxylate 10a (Table 3, Entry 10):
N
O
MeO2C
HN
Me
White solid,mp:163-164 °C. FT-IR (KBr):ῡ (cm-1) 3283, 1674, 1648, 1554, 1538, 1440, 1373,
1266, 1150, 1094, 831. 1H NMR (CDCl3, 250 MHz):δH(ppm) 8.04 (br, s, 1H, NH), 7.41-6.98 (m,
14H, Ar–H), 5.71 (s, 1H, NCH), 3.47 (s, 3H, OCH3), 2.18(s, 3H, Ar-Me). 13C NMR (CDCl3, 100
MHz):δC(ppm) 164.69, 164.05, 141.94, 138.66, 137.81, 136.51, 133.60, 129.22, 128.81, 128.46,
127.41, 125.65, 124.75, 122.86, 122.75, 109.53, 62.05, 51.13, 21.16. Elemental anal. Calcd (%)
for C25H22N2O3: C, 75.36; H, 5.57; N, 7.03. Found: C, 75.35; H, 5.58; N, 7.01.
S14
Fig. S16 The 1H NMR(250MHz)spectrum of product (10a)
Fig. S17 The 13C NMR (100MHz) spectrumof product (10a)