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Supplementary Information
Ring-opening hydrolysis of spiro-epoxyoxindoles using reusable sulfonic acid functionalized nitrogen rich carbon catalystParth Patel,a,b Raj Kumar Tak,a,c Bhavesh Parmar,a,c Shilpa Dabas,a Brijesh Patel,a,c Eringathodi
Suresh,c,d Noor-ul H. Khana,c* Saravanan Subramaniana,c*
aInorganic Materials and Catalysis Division, CSIR-Central Salt & Marine Chemicals Research Institute, G. B. Marg,
Bhavnagar-364002, Gujarat, India
bCharotar University of Science and Technology, Changa, Anand-388421, Gujarat, India
cAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India
dAnalytical and Environmental Science Division and Centralized Instrument Facility, CSIR-Central Salt & Marine
Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat (India)
E-mail: khan251293@yahoo.in; saravanans@csmcri.res.in
X-ray Crystallography
The crystallographic data and refinement for 2a, 2b, 2c, 2e and 2g are provided in Table
S1. Crystal of suitable size was selected from the mother liquor and immersed in
paratone oil and then mounted for data collection. Single crystal X-ray data was
collected using a Bruker D8 QUEST (PHOTON) diffractometer. The linear absorption
coefficients, scattering factors for the atoms, and the anomalous dispersion
corrections were obtained from International Tables for X-ray Crystallography. The
data integration and reduction were processed using SAINTPLUS software.S1 An
empirical absorption correction was applied to the collected reflections with SADABS
using XPREP.S2 The structure was solved by the direct method using SHELXTLS3 and was
refined on F2 by a full-matrix least-squares technique using the SHELXL-2014S4 program
package. Non-hydrogen atoms were refined anisotropically and the hydrogen atoms
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2021
attached to the organic moiety were stereochemically fixed. CCDC numbers 1961234-
1961238 corresponds to all the compounds reported in this manuscript and this data
can be obtained free of charge from The Cambridge Crystallographic Data Center via
www.ccdc.cam.ac.uk/data_request/cif
Table S1. Crystal Data and Refinement Parameters for 2a, 2b, 2c, 2e, and 2g.
Identification code 2a 2b 2c 2e 2g
Chemical formula C128H120N8O24 C10H11NO3 C12H13NO3 C17H17NO4 ClC16H14NO3
Formula weight (g/mol) 2154.31 193.20 219.23 299.31 303.73
Crystal Color Colorless Colorless Colorless Light Yellow ColorlessCrystal Size (mm)
0.44 x 0.08 x 0.05
0.29 x 0.24 x 0.22
0.33 x 0.12 x 0.04
0.60 x 0.40 x 0.10
0.36 x 0.07 x 0.06
Temperature (K) 301(2) 122(2) 150(2) 305(2) 301(2)
Crystal System Orthorhombic Monoclinic Orthorhombic Monoclinic OrthorhombicSpace Group P 21 21 21 P 21/n P 21 21 21 P c F d d 2a(Å ) 5.1638(3) 8.3175(11) 5.8505(12) 8.4593(5) 62.210(8)b(Å ) 19.3060(12) 10.2481(16) 11.594(2) 5.8691(4) 17.713(2)c(Å ) 27.209(2) 10.9658(17) 16.205(3) 30.718(2) 5.2259(7)(º) 90 90 90 90 90(º) 90 98.059(5) 90 97.420(2) 90(º) 90 90 90 90 90Z 1 4 4 4 16V(Å3) 2712.5(3) 925.5(2) 1099.2(4) 1512.33(18) 5758.6(13)Density (Mg/m3) 1.319 1.387 1.325 1.315 1.401
μ(mm-1) 0.092 0.103 0.096 0.094 0.274F(000) 1136 408 464 632 194Reflections Collected 20795 11988 5494 22546 18150
Independent Reflections 6671 2254 1934 5901 9343
Rint 0.1001 0.0426 0.0510 0.0409 0.0835Number of parameters 369 160 175 469 194
GOF on F2 0.994 1.135 1.114 1.043 1.009Final R1/wR2 (I ≥2(I)
0.0621/0.1019 0.0604/0.1858 0.0767/0.1348 0.0511/0.1309 0.0635/0.1328
Weighted R1/wR2 (all data)
0.2041/0.1476 0.0725/0.1953 0.0888/0.1387 0.0661/0.1430 0.1448/0.1730
CCDC number 1961235 1961236 1961234 1961237 1961238
Figure S1. XPS Deconvoluted Spectrum of N 1S.
Figure S2. Powder XRD pattern of Cal-CB6 and SO3H@N-C/CB6.
Figure S3. SEM image of SO3H@N-C/CB6.
1H & 13C NMR analysis of hydrolysis products of spiro epoxyoxindoles
N
O
O
BnN
HO
O
Bn
OH
1a 2a
2a: 1H NMR (600 MHz, CDCl3), δ 7.41 (d, J = 7.5 Hz, 1H), 7.28 – 7.20 (m, 5H), 7.17 (t, J = 7.5 Hz,
1H), 7.02 (t, J = 7.6 Hz, 1H), 6.67 (d, J = 7.9 Hz, 1H), 4.91 (d, J = 15.9 Hz, 1H), 4.73 (d, J = 15.7
Hz, 1H), 3.89 (s, 2H). 13C NMR (151 MHz, CDCl3 ) δ 177.98, 142.59, 135.26, 129.90, 128.90,
127.75, 127.19, 124.59, 123.46, 109.70, 76.23, 66.92, 43.78.
N
O
O
MeN
HO
O
Me
OH
1b 2b
2b: 1H NMR (600 MHz, CDCl3), δ 7.39 (d, J = 7.2 Hz, 1H), 7.35 (t, J = 7.9 Hz, 1H), 7.11 (t, J = 7.5
Hz, 1H), 6.85 (d, J = 7.8 Hz, 1H), 3.86 – 3.77 (m, 2H), 3.19 (s, 3H), 1.67 (s, 1H). 13C NMR (151
MHz, CDCl3) δ 177.66, 143.66, 130.32, 127.57, 124.42, 123.52, 108.76, 75.42, 66.92, 26.29.
N
O
ON
HO
OOH
1c 2c
2c : 1H NMR (600 MHz, CDCl3) δ 7.40 (d, J = 7.3 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H), 7.09 (t, J = 7.5
Hz, 1H), 6.83 (d, J = 7.9 Hz, 1H), 5.80 (ddd, J = 21.6, 10.3, 5.3 Hz, 1H), 5.25 – 5.18 (m, 2H), 4.36
– 4.32 (m, 1H), 4.24 (dd, J = 16.5, 4.9 Hz, 1H), 3.89 – 3.79 (m, 2H), 3.17 (s, 1H). 13C NMR (151
MHz, CDCl3) δ 177.49, 142.82, 130.90, 130.14, 127.72, 124.50, 123.45, 117.94, 109.64, 75.57,
67.02, 42.35.
N
O
O
BnN
HO
O
Bn
OHH3C H3C
1d 2d
2d : 1H NMR (600 MHz, CDCl3) δ 7.31 – 7.27 (m, 2H), 7.26 – 7.22 (m, 4H), 7.01 (d, J = 7.9 Hz,
1H), 6.59 (d, J = 8.0 Hz, 1H), 4.96 – 4.72 (m, 2H), 3.88 (dt, J = 21.2, 11.4 Hz, 2H), 3.16 – 3.00
(m, 1H), 2.29 (s, 3H). 13C NMR (151 MHz, CDCl3) δ 177.78, 140.36, 135.31, 133.25, 130.44,
128.94, 127.82, 127.21, 125.25, 109.61, 75.59, 67.09, 43.79, 21.09.
N
O
O
BnN
HO
O
Bn
OHMeO MeO
1e 2e
2e : 1H NMR (600 MHz,CDCl3) δ 7.34 – 7.29 (m, 2H), 7.27 (d, J = 5.9 Hz, 4H), 7.02 (t, J = 2.0 Hz,
1H), 6.77 – 6.73 (m, 1H), 6.62 (d, J = 8.6 Hz, 1H), 4.93 (d, J = 15.7 Hz, 1H), 4.80 (d, J = 15.7 Hz,
1H), 3.88 (d, J = 13.8 Hz, 2H), 3.76 (s, 3H), 2.90 (s, 1H). 13C NMR (151 MHz, CDCl3) δ 129.04,
127.95, 127.28, 111.48, 110.52, 67.21, 55.97, 43.93.
N
O
O
BnN
HO
O
Bn
OH
1f 2f
F F
2f : 1H NMR (600 MHz,CDCl3) δ 7.30 – 7.21 (m, 5H), 7.17 (dd, J = 7.9, 2.3 Hz, 1H), 6.88 (td, J =
8.6, 2.4 Hz, 1H), 6.60 (dd, J = 8.6, 4.0 Hz, 1H), 4.91 (d, J = 15.7 Hz, 1H), 4.78 (s, 1H), 4.75 (d, J =
15.6 Hz, 1H), 3.89 (s, 2H), 3.54 (s, 1H). 13C NMR (151 MHz, CDCl3) δ 177.73, 160.45, 138.42,
134.87, 129.78, 129.73, 129.03, 127.97, 127.16, 116.36, 116.21, 112.98, 112.81, 110.53,
110.47, 76.22, 66.93, 43.97.
N
O
O
BnN
HO
O
Bn
OH
1g 2g
Cl Cl
2g : 1H NMR (600 MHz,CDCl3 ) δ 7.35 – 7.26 (m, 4H), 7.25 (d, J = 7.3 Hz, 3H), 7.05 (d, J = 8.3 Hz,
1H), 6.72 (s, 1H), 4.91 (s, 1H), 4.78 (d, J = 15.6 Hz, 1H), 3.85 (d, J = 3.3 Hz, 2H), 2.68 (s, 1H). 13C
NMR (151 MHz,CDCl3) δ 129.14, 128.14, 127.17, 125.48, 123.45, 110.49, 66.87, 43.90.
N
O
O
MeN
HO
O
Me
OH
1j 2j
Me Me
2j : 1H NMR (200 MHz, CDCl3) δ 7.37 – 7.08 (m, 2H), 6.76 (d, J = 7.9 Hz, 1H), 4.43 (s, 1H), 3.85
(s, 2H), 3.19 (s, 3H), 2.36 (s, 3H). 13C NMR (50 MHz, CDCl3) δ 177.61, 141.13, 133.11, 130.30,
127.75, 125.18, 108.40, 66.90, 26.24, 21.05.
N
O
O
BnN
O
O
Bn
OH
1k 2k
2k : 1H NMR (600 MHz,CDCl3 ) δ 7.39 (d, J = 7.2 Hz, 1H), 7.32 – 7.23 (m, 6H), 7.08 (t, J = 7.5 Hz,
1H), 6.75 (d, J = 7.9 Hz, 1H), 4.93 (s, 2H), 3.91 (q, J = 11.4 Hz, 2H), 3.13 (s, 3H), 2.69 (s, 1H). 13C
NMR (151 MHz,CDCl3) δ 175.04, 143.45, 135.50, 130.25, 128.96, 127.85, 127.27, 125.20,
125.02, 123.27, 109.76, 82.74, 66.85, 53.49, 43.90.
2.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.8f1 (ppm)
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
1.89
0.84
0.92
0.70
0.86
0.92
4.76
0.87
3.89
4.71
4.74
4.90
4.92
6.66
6.68
7.00
7.02
7.03
7.16
7.17
7.18
7.20
7.22
7.23
7.25
7.25
7.26
7.28
7.40
7.42
N
O
OHOH
Figure S4. 1H NMR of 2a.
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.2843.7
8
66.9
2
76.2
3
109.
70
123.
4612
4.59
127.
1912
7.75
128.
9012
9.90
135.
2614
2.59
177.
98
Figure S5. 13C NMR of 2a.
1.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
0
1
2
3
4
5
6
7
8
9
101.
56
3.00
1.96
1.03
1.00
1.88
1.67
3.19
3.78
3.80
3.80
3.82
3.84
6.85
6.86
7.10
7.11
7.12
7.34
7.35
7.37
7.38
7.40
N
CH3
O
OHOH
Figure S6. 1H NMR of 2b.
0102030405060708090100110120130140150160170180190200f1 (ppm)
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
26.2
9
66.9
2
75.4
2
108.
76
123.
5212
4.42
127.
5713
0.32
143.
66
177.
66
N
CH3
O
OHOH
Figure S7. 13C NMR of 2b.
1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
0.92
2.05
1.08
1.14
2.06
1.01
1.00
1.01
1.01
1.00
3.17
3.80
3.82
3.85
3.87
4.22
4.23
4.25
4.26
4.32
4.33
4.33
4.35
4.36
5.20
5.21
5.23
5.77
5.78
5.79
5.80
5.81
5.82
5.83
5.84
6.83
6.84
7.08
7.09
7.10
7.25
7.29
7.30
7.31
7.40
7.41
N
O
OHOH
CH2
Figure S8. 1H NMR of 2c.
2030405060708090100110120130140150160170180190f1 (ppm)
-0.004
-0.002
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
0.020
0.022
0.024
0.026
0.028
0.030
0.032
0.034
0.036
0.038
0.040
42.3
5
67.0
2
75.5
7
109.
64
117.
9412
3.45
124.
5012
7.72
130.
1413
0.90
142.
82
177.
49
N
O
OHOH
CH2
Figure S9. 13C NMR of 2c.
2.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.8f1 (ppm)
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
3.03
0.96
2.04
2.04
1.00
1.01
4.10
2.03
2.29
3.09
3.10
3.13
3.84
3.86
3.88
3.89
3.91
4.76
4.79
4.90
4.93
6.59
6.60
7.00
7.02
7.22
7.24
7.25
7.28
7.29
7.30
N
O
CH3
OHOH
Figure S10. 1H NMR of 2d.
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.005
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.06021.0
9
43.7
9
67.0
9
75.5
9
109.
61
125.
2512
7.21
127.
8212
8.94
130.
4413
3.25
135.
3114
0.36
177.
78
N
O
CH3
OHOH
Figure S11. 13C NMR of 2d.
2.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.6f1 (ppm)
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
1.02
3.10
2.17
1.02
1.05
1.02
0.98
1.00
4.11
2.16
2.90
3.76
3.85
3.86
3.89
3.91
4.79
4.81
4.92
4.95
6.62
6.63
6.75
6.76
6.76
7.02
7.02
7.02
7.26
7.27
7.30
7.32
7.33
N
O
OHOHO
CH3
Figure S12. 1H NMR of 2e.
2030405060708090100110120130140150160170180f1 (ppm)
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
43.9
3
55.9
7
67.2
1
110.
5211
1.48
127.
2812
7.95
129.
04
N
O
OHOHO
CH3
Figure S13. 13C NMR of 2e.
2.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.2f1 (ppm)
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
1.00
2.14
1.15
0.92
1.07
1.05
1.05
1.02
5.24
3.54
3.89
4.74
4.76
4.78
4.90
4.93
6.58
6.59
6.60
6.61
6.87
6.87
6.88
6.89
6.90
6.90
7.16
7.16
7.17
7.18
7.22
7.23
7.24
7.25
7.27
7.29
7.30
N
O
OHOHF
Figure S14. 1H NMR of 2f.
0102030405060708090100110120130140150160170180f1 (ppm)
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.0943.9
7
66.9
3
76.2
2
110.
4711
0.53
112.
8111
2.98
116.
2111
6.36
127.
1612
7.97
129.
0312
9.73
129.
7813
4.87
138.
42
158.
8416
0.45
177.
73
N
O
OHOHF
Figure S15. 13C NMR of 2f.
2.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0.95
2.01
0.99
1.00
0.96
0.98
3.19
4.08
2.68
3.84
3.85
4.76
4.79
4.91
6.72
7.04
7.06
7.25
7.26
7.31
7.32
7.33
N
OH
O
Bn
OH
Cl
Figure S16. 1H NMR of 2g.
0102030405060708090100110120130140150160170f1 (ppm)
-0.002
-0.001
0.000
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009
0.010
0.011
0.012
0.013
0.014
0.015
0.016
0.017
0.018
0.019
0.020
0.021
0.022
0.023
43.9
0
66.8
7
110.
49
123.
4512
5.48
127.
1712
8.14
129.
14
N
OH
O
Bn
OH
Cl
Figure S17. 13C NMR of 2g.
2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
-5.0×107
0.0
5.0×107
1.0×108
1.5×108
2.0×108
2.5×108
3.0×108
3.5×108
4.0×108
4.5×108
5.0×108
5.5×108
6.0×108
6.5×108
7.0×108
7.5×108
3.00
3.13
2.02
0.96
0.98
2.04
2.36
3.19
3.85
4.43
6.74
6.78
7.15
7.19
7.26
7.29
N
CH3
O
OHOHCH3
Figure S18. 1H NMR of 2j.
102030405060708090100110120130140150160170180190200210f1 (ppm)
-1.00×108
0.00
1.00×108
2.00×108
3.00×108
4.00×108
5.00×108
6.00×108
7.00×108
8.00×108
9.00×108
1.00×109
1.10×109
1.20×109
21.0
5
26.2
4
66.9
0
75.6
5 CD
Cl3
108.
40
125.
1812
7.75
130.
3013
3.11
141.
13
177.
61N
CH3
O
OHOHCH3
Figure S19. 13C NMR of 2j.
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
0.90
3.00
2.00
2.05
0.97
1.00
6.04
1.00
2.69
3.13
3.88
3.90
3.92
3.94
4.90
4.93
4.96
6.74
6.75
7.07
7.08
7.10
7.23
7.24
7.25
7.26
7.26
7.28
7.29
7.30
7.39
7.40
N
OOH
O
CH3
Figure S20. 1H NMR of 2k.
102030405060708090100110120130140150160170180f1 (ppm)
-0.02
-0.01
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
43.9
0
53.4
9
66.8
5
82.7
4
109.
7612
3.27
125.
0212
5.20
127.
2712
7.85
128.
9613
0.25
135.
5014
3.45
175.
04
N
O
OCH3
OH
Figure S21. 13C NMR of 2k.
References:
S1. SAINT+, 6.02 ed, Bruker AXS, Madison, WI, 1999.
S2. XPREP, 5.1 ed, Siemens Industrial Automation Inc., Madison, WI, 1995.
S3. Sheldrick, G. M. SHELXTL Reference Manual: Version 5.1; Bruker AXS, Madison, WI, 1997.
S4. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Cryst. C 2015, 71, 3-8.
Recommended