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S1
SUPPORTING PILsLevulinate amidinium protic ionic liquids (PILs) as suitable media for the dissolution and levulination of cellulose
Stefano Becherini, [a] Andrea Mezzetta, [a] Cinzia Chiappe, [a] and Lorenzo Guazzelli, *[a]
Supporting Information
Table of contents
1H- and 13C-NMR spectra of Lev PILs pages S2-S5
IR spectra of Lev PILs pages S6-S7
Thermal gravimetric analysis (TGA) of Lev PILs pages S8-S9
Images of dissolved MCC in Lev PILs at maximum wt% page S10
Optical microscopy of dissolved MCC in Lev PILs at maximum wt% pages S11- S12
IR spectra of pristine MCC and regenerated cellulose after dissolution in Lev (P)ILs
pages S13-S15
1H- and 13C-NMR spectra of Levulinic Anhydride pages S16-S17
IR spectra of cellulose after levulination reaction pages S18-S33
1H-NMR of propionyl-levulinyl cellulose pages S34-S49
[a] Dr A. Mezzetta, Mr S. Becherini, Prof. C. Chiappe, Dr L. GuazzelliDepartment of PharmacyUniversity of PisaVia Bonanno 6, Pisa (Italy)*E-mail: [email protected]
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
S2
Fig S1. 1H NMR of DBUHLev at 25 °C
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0chemical shift (ppm)
6.03
2.04
2.96
2.00
2.03
1.91
5.87
1.57
1.59
1.60
1.63
1.86
1.89
1.91
2.05
2.33
2.33
2.36
2.39
2.59
2.62
2.65
2.74
3.31
3.33
3.34
3.35
3.38
7.26
S3
Fig S2. 13C NMR of DBUHLev at 25 °C
102030405060708090100110120130140150160170180190200210220230chemical shift (ppm)
19.6
224
.09
26.9
529
.04
29.8
531
.80
31.8
9
37.8
940
.54
48.4
8
53.9
7
76.6
577
.16
77.6
7
165.
78
178.
26
209.
52
S4
Fig S3. 1H NMR of DBNHLev at 25 °C
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0chemical shift (ppm)
7.00
2.09
2.00
1.93
3.97
2.00
1.22
1.25
1.27
1.29
1.36
1.38
1.42
1.58
1.61
1.64
1.88
1.91
1.94
2.19
2.23
2.26
2.64
2.67
2.69
2.71
2.73
2.89
2.92
2.95
7.26
S5
Fig S4. 13C NMR of DBNHLev at 25 °C
102030405060708090100110120130140150160170180190200210220chemical shift (ppm)
17.2
817
.38
28.2
228
.51
30.4
1
36.4
338
.81
40.9
4
51.4
9
76.6
477
.16
77.6
8
162.
51
176.
12
207.
54
S6
Fig S5. IR of DBUHLev at 25 °C
3398
.8
3248
.6 3100
.0
3040
.5
2926
.3
2860
.6
2800
.9
2696
.3
1903
.1
1706
.3
1642
.7 1566
.2
1472
.014
46.0
1360
.213
21.6
1292
.1
1203
.411
59.4
1107
.5
984.
1
689.
6
606.
4 566.
6
DBU Lev
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
102
100
98
96
94
92
90
88
86
84
82
80
78
76
74
72
70
68
Wavenumber
%Tr
ansm
ittan
ce
S7
Fig S6. IR of DBNHLev at 25 °C
3384
.2
3042
.4
2946
.2
2882
.7
2752
.4
2615
.4
1904
.1
1705
.316
74.0
1566
.1
1376
.3 1303
.9
1203
.411
61.6
1129
.9
1064
.9
894.
8
732.
7
678.
6
609.
0
DBN Lev
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
102
100
98
96
94
92
90
88
86
84
82
80
78
76
74
72
70
68
66
Wavenumber
%Tr
ansm
ittan
ce
S8
Fig S7. Thermal gravimetric analysis (TGA) of DBUHLev
S9
Fig S8. Thermal gravimetric analysis (TGA) of DBNHLev
S10
Fig S9. Pictures of dissolved MCC in DBUHLev: 80 °C, 12.5 wt% (A); 100 °C, 15 wt%(B)
Fig S10. Pictures of dissolved MCC in DBNHLev: 60 °C, 12 wt% (A); 80 °C, 16 wt% (B); 100 °C, 20 wt%(C)
A B
A B C
S11
Fig S11. Optical microscopy of microcrystalline cellulose dissolved in DBNHLev (100 °C, 20 wt%), 4x(A) and 15x (B)
A B
S12
Fig S12. Optical microscopy of microcrystalline cellulose dissolved in DBUHLev (100 °C, 15 wt%), 4x(A) and 15x (B)
A B
S13
Fig S13. IR of MCC
S14
Fig S14. IR of regenerated cellulose after dissolution in DBUHLev at 100 °C
S15
Fig S15. IR of regenerated cellulose after dissolution in DBNHLev at 100 °C
S16
Fig S16. 1H-NMR of Levulinic Anhydride
012345678910chemical shift (ppm)
6.00
7.95
2.15
2.65
2.67
2.69
2.73
2.75
2.77
7.26
S17
Fig S17. 13C-NMR of Levulinic Anhydride at 25 °C
020406080100120140160180200220240chemical shift (ppm)
29.0
429
.75
37.3
1
76.6
577
.16
77.6
7
168.
53
205.
97
S18
Fig S18. IR of cellulose levulinate from DBNHLev, 20 eq Lev2O, 80°C, 0.5 ml DMSO
1029
.4
1738
.0
3464
.7 2922
.6
1712
.0
1408
.113
60.3
1313
.2
1233
.7
1153
.3
1054
.7
931.
8
765.
7
669.
3
594.
0
N 80 20eq
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100
99
98
97
96
95
94
93
92
91
90
Wavenumber
%Tr
ansm
ittan
ce
S19
Fig S19. IR of cellulose levulinate from DBNHLev, 10 eq Lev2O, 80°C, 0.5 ml DMSO
3483
.3
2925
.9
1736
.717
10.2
1651
.1
1410
.213
59.7
1314
.9
1204
.3
1151
.6
1052
.110
29.8
929.
4
829.
8
763.
1
DBN 80C 0.5 DMSO
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100.5
100.0
99.5
99.0
98.5
98.0
97.5
97.0
96.5
96.0
95.5
95.0
Wavenumber
%Tr
ansm
ittan
ce
S20
Fig S20. IR of cellulose levulinate from DBNHLev, 10 eq Lev2O, 50°C, 0.5 ml DMSO
FT-IR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 50°C, 0.5 ml DMSO
3481
.2
2914
.5
1738
.617
13.5
1414
.7
1361
.013
12.8
1234
.712
05.5
1154
.3
1056
.610
29.0
923.
9
837.
0
765.
2
DBN 50C 0.5 DMSO 10eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100
99
98
97
96
95
94
93
92
91
90
89
Wavenumber
%Tr
ansm
ittan
ce
S21
Fig S21. IR of cellulose levulinate from DBNHLev, 10 eq Lev2O, 25°C, 0.5 ml DMSO
1736
.7
3457
.8
2916
.2
1711
.8
1408
.213
60.7
1313
.7
1235
.112
04.7
1153
.7 1052
.410
25.8
936.
5
765.
7
663.
4 601.
9
DBN TA 0.5 DMSO 10eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
101
100
99
98
97
96
95
94
93
92
91
Wavenumber
%Tr
ansm
ittan
ce
S22
Fig S22. IR of cellulose levulinate from DBNHLev, 3 eq Lev2O, 80°C, 0.5 ml DMSO
901.
6
1658
.3
3373
.2
2885
.1
1710
.7
1414
.1
1362
.213
12.4
1257
.9
1156
.6
1020
.1
662.
4
DBN 80C 0.5 DMSO 3eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100.2
100.0
99.8
99.6
99.4
99.2
99.0
98.8
98.6
98.4
98.2
98.0
97.8
97.6
97.4
97.2
97.0
96.8
96.6
96.4
Wavenumber
%Tr
ansm
ittan
ce
S23
Fig S23. IR of cellulose levulinate from DBNHLev, 20 eq Lev2O, 80°C, 0.5 ml - valerolactone
3483
.9 2925
.9
1738
.617
13.5
1415
.0
1360
.613
14.2
1205
.4
1153
.6
1058
.510
31.0
917.
3
765.
8
N 80 g-val 20eq
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
101
100
99
98
97
96
95
94
93
92
91
Wavenumber
%Tr
ansm
ittan
ce
S24
Fig S24. IR of cellulose levulinate from DBNHLev, 10 eq Lev2O, 80°C, 0.5 ml - valerolactone
3455
.7
2949
.029
09.7
1737
.517
11.4
1410
.413
61.3
1313
.3
1235
.3
1154
.4
1055
.110
29.3
931.
5
765.
6
671.
3
DBN 80C 0.5 g-val 10eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100.5
100.0
99.5
99.0
98.5
98.0
97.5
97.0
96.5
96.0
95.5
95.0
94.5
94.0
Wavenumber
%Tr
ansm
ittan
ce
S25
Fig S25. IR of cellulose levulinate from DBNHLev, 10 eq Lev2O, 50°C, 0.5 ml - valerolactone
3470
.5
2914
.1
1737
.817
12.7
1414
.8
1361
.513
14.5
1236
.4
1154
.6
1051
.810
27.1
918.
3
N50g-val
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100
99
98
97
96
95
94
93
92
91
90
89
Wavenumber
%Tr
ansm
ittan
ce
S26
Fig S26. IR of cellulose levulinate from DBNHLev, 10 eq Lev2O, 25°C, 0.5 ml - valerolactone
3463
.6
2921
.6
1736
.617
13.2
1415
.1
1362
.013
12.3
1239
.112
07.1
1154
.9
1051
.510
26.3
930.
8
765.
0
NTAg-val
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
101
100
99
98
97
96
95
94
93
92
91
90
Wavenumber
%Tr
ansm
ittan
ce
S27
Fig S27. IR of cellulose levulinate from DBNHLev, 10eq Lev2O, 80°C, 3.5gr DMSO
3451
.3
2917
.2
1733
.417
12.5
1573
.3
1410
.413
60.8
1311
.8
1236
.0
1153
.6
1026
.2
934.
5
658.
6
DBN/DMSO 1:1 80C 10eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
101.0
100.5
100.0
99.5
99.0
98.5
98.0
97.5
97.0
96.5
96.0
95.5
95.0
94.5
94.0
93.5
93.0
92.5
92.0
Wavenumber
%Tr
ansm
ittan
ce
S28
Fig S28. IR of cellulose levulinate from DBUHLev, 10 eq Lev2O, 80°C, 0.5 ml DMSO
1030
.0
1738
.5
3461
.7 2919
.0
1713
.3
1409
.513
60.7
1313
.9
1205
.7
1153
.9
1056
.9
929.
4
766.
7
668.
9
U 80 20eq
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100
99
98
97
96
95
94
93
92
91
Wavenumber
%Tr
ansm
ittan
ce
S29
Fig S29. IR of cellulose levulinate from DBUHLev, 10 eq Lev2O, 80°C, 0.5 ml DMSO
3443
.1
2916
.4
1737
.017
09.8
1647
.8
1411
.513
61.3
1315
.4
1237
.3
1157
.0
1053
.0
915.
6
672.
0 604.
8
DBU 80C 0.5 DMSO
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100.5
100.0
99.5
99.0
98.5
98.0
97.5
97.0
96.5
96.0
95.5
95.0
94.5
94.0
93.5
93.0
Wavenumber
%Tr
ansm
ittan
ce
S30
Fig S30. IR of cellulose levulinate from DBUHLev, 10 eq Lev2O, 50°C, 0.5 ml DMSO
1738
.1
3444
.6
2907
.6
1712
.4
1650
.8
1415
.9
1361
.013
15.9
1238
.9
1156
.1
1026
.8
913.
0 665.
8
DBU 50C 0.5 DMSO 10eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100.5
100.0
99.5
99.0
98.5
98.0
97.5
97.0
96.5
96.0
95.5
95.0
94.5
94.0
93.5
93.0
Wavenumber
%Tr
ansm
ittan
ce
S31
Fig S31. IR of cellulose levulinate from DBUHLev, 10 eq Lev2O, 25°C, 0.5 ml DMSO
1737
.6
3464
.4
2915
.8
1711
.5
1407
.813
59.6
1313
.9
1234
.8
1153
.7
1056
.410
25.9
765.
5
670.
1
DBU TA 0.5 DMSO 10eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100.0
99.5
99.0
98.5
98.0
97.5
97.0
96.5
96.0
95.5
95.0
94.5
94.0
93.5
93.0
92.5
92.0
Wavenumber
%Tr
ansm
ittan
ce
S32
Fig S32. IR of cellulose levulinate from DBUHLev, 3 eq Lev2O, 80°C, 0.5 ml DMSO
1731
.6
3400
.4
2882
.7
1712
.6
1409
.113
61.1 13
15.3 12
56.4
1155
.2
1011
.0
951.
1
899.
4
702.
266
5.4
DBU 80C 0.5 DMSO 3eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100.5
100.0
99.5
99.0
98.5
98.0
97.5
97.0
96.5
96.0
95.5
95.0
94.5
94.0
93.5
93.0
92.5
Wavenumber
%Tr
ansm
ittan
ce
S33
Fig S33. IR of cellulose levulinate from DBUHLev, 10eq Lev2O, 80°C, 3.5gr DMSO
3438
.5
2921
.5
2359
.0
1711
.5
1648
.5
1412
.4
1361
.013
16.8
1236
.9
1157
.1
1054
.310
30.3
665.
4 593.
7 561.
7
DBU/DMSO 1:1 80C 10eq Lev2O
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
100
99
98
97
96
95
94
93
92
91
90
89
Wavenumber
%Tr
ansm
ittan
ce
S34
Fig S34. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 80°C, 0.5 ml DMSO
12345678910chemical shift (ppm)
3.39
7.00
1.03
1.14
1.23
2.10
2.14
2.44
2.62
3.81
4.16
4.33
4.61
4.78
5.02
5.19
7.26
S35
Fig S35. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 80°C, 0.5 ml DMSO
1234567891011chemical shift (ppm)
3.69
7.00
1.01
1.05
2.11
2.16
2.45
2.63
3.81
4.15
4.34
4.62
4.80
5.04
5.20
5.64
6.11
7.26
S36
Fig S36. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 50°C, 0.5 ml DMSO
12345678910chemical shift (ppm)
4.76
7.00
1.00
1.03
1.07
1.15
1.18
2.10
2.15
2.39
2.61
2.85
3.80
4.15
4.36
4.61
4.78
5.04
5.19
5.66
6.08
7.26
S37
Fig S37. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 25°C, 0.5 ml DMSO
1234567891011chemical shift (ppm)
4.90
7.00
1.01
1.04
1.07
1.16
1.24
2.12
2.17
2.36
2.61
2.88
3.81
4.14
4.35
4.62
4.80
5.05
5.20
5.65
6.11
7.26
S38
Fig S38. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 3 eq Lev2O, 80°C, 0.5 ml DMSO
12345678910chemical shift (ppm)
7.82
7.00
1.01
1.05
1.08
1.14
1.17
1.20
2.18
2.36
2.60
3.25
3.48
3.73
4.07
4.37
4.62
4.78
5.05
5.21
5.64
6.12
7.26
S39
Fig S39. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 20 eq Lev2O, 80°C, 0.5 ml - valerolactone
1234567891011chemical shift (ppm)
3.54
7.00
1.01
1.04
1.07
1.10
1.15
2.11
2.16
2.45
2.63
3.80
4.19
4.39
4.62
4.79
5.03
5.21
5.66
6.09
7.26
S40
Fig S40. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 80°C, 0.5 ml - valerolactone
12345678910chemical schift (ppm)
4.39
7.00
0.99
1.02
1.14
2.09
2.14
2.40
2.61
2.83
3.79
4.13
4.35
4.60
4.77
5.04
5.18
5.64
6.07
7.26
S41
Fig S41. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 50°C, 0.5 ml - valerolactone
1234567891011chemical shift (ppm)
4.55
7.00
1.03
1.14
2.11
2.16
2.37
2.60
2.85
3.79
3.88
4.14
4.34
4.62
4.79
5.03
5.19
5.66
6.09
7.26
S42
Fig S42. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10 eq Lev2O, 25°C, 0.5 ml - valerolactone
01234567891011chemical shift (ppm)
4.67
7.00
0.99
1.02
1.05
1.10
1.14
1.17
2.09
2.15
2.34
2.59
2.68
2.87
3.78
4.11
4.34
4.60
4.77
5.01
5.17
5.64
6.07
7.26
S43
Fig S43. 1H NMR of propionyl-levulinyl cellulose from DBNHLev, 10eq Lev2O, 80°C, 3.5gr DMSO
1234567891011chemical shift (ppm)
6.08
7.00
1.01
1.05
1.08
1.13
1.17
1.19
2.13
2.18
2.38
2.62
3.48
3.79
4.13
4.37
4.62
4.80
5.05
5.21
7.26
S44
Fig S44. 1H NMR of propionyl-levulinyl cellulose from DBUHLev, 20 eq Lev2O, 80°C, 0.5 ml DMSO
1234567891011chemical shift (ppm)
5.53
7.00
1.04
1.14
2.13
2.16
2.36
2.62
3.79
4.13
4.38
4.79
5.04
5.17
5.64
6.10
7.26
S45
Fig S45. 1H NMR of propionyl-levulinyl cellulose from DBUHLev, 10 eq Lev2O, 80°C, 0.5 ml DMSO
01234567891011chemical shift (ppm)
5.64
7.00
1.00
1.05
2.12
2.17
2.20
2.36
2.60
3.78
4.37
4.78
5.05
5.19
5.63
6.12
7.26
S46
Fig S46. 1H NMR of propionyl-levulinyl cellulose from DBUHLev, 10 eq Lev2O, 50°C, 0.5 ml DMSO
01234567891011chemical shift (ppm)
6.26
7.00
1.02
1.04
1.07
1.16
2.13
2.17
2.36
2.60
2.72
3.73
4.15
4.37
4.62
4.79
5.04
5.18
5.64
6.12
7.26
S47
Fig S47. 1H NMR of propionyl-levulinyl cellulose from DBUHLev, 10 eq Lev2O, 25°C, 0.5 ml DMSO
01234567891011chemical shift (ppm)
5.69
7.00
1.02
1.05
1.07
1.16
2.12
2.17
2.37
2.62
3.79
4.14
4.38
4.63
4.79
5.05
5.21
5.69
6.11
7.26
S48
Fig S48. 1H NMR of propionyl-levulinyl cellulose from DBUHLev, 3 eq Lev2O, 80°C, 0.5 ml DMSO
1234567891011chemical shift (ppm)
8.47
7.00
1.06
1.10
1.15
1.16
1.18
2.15
2.20
2.27
2.37
2.60
3.51
3.73
4.08
4.39
4.79
5.07
5.23
5.67
6.11
7.26
S49
Fig S49. 1H NMR of propionyl-levulinyl cellulose from DBUHLev, 10eq Lev2O, 80°C, 3.5gr DMSO
1234567891011chemical shift (ppm)
6.25
7.00
1.00
1.04
1.08
1.16
1.19
2.13
2.18
2.36
2.61
3.22
3.49
3.73
4.09
4.37
4.62
4.77
4.81
5.05
5.21
5.64
6.11
7.26
