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Synthesis of cyclic carbonates catalysed by aluminium heteroscorpionate complexes
Supporting Information
José A. Castro-Osma,a,b Carlos Alonso-Moreno,b Agustín Lara-Sánchez,b Javier Martínez,b Michael Northa* and Antonio Oterob*
a Green Chemistry Centre of Excellence, Department of Chemistry, The University of York,
Heslington, York, YO10 5DD (UK). Fax: +44 1904-432-705; Tel: +44 1904 324-545; E-mail: [email protected]
b Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, 13071 Ciudad Real, Spain, Fax: +34 926-295-318; Tel: +34 926-295-300; E-mail: [email protected]
Contents NMR Spectra for ethylene carbonate 2a 2 Chemical ionization mass spectrum for ethylene carbonate 2a 3 NMR Spectra for propylene carbonate 2b 4 Chemical ionization mass spectrum for proplene carbonate 2b 5 NMR Spectra for styrene carbonate 2c 6 Electron ionization mass spectrum for styrene carbonate 2c 7 NMR Spectra for 1,2-butylene carbonate 2d 8 Chemical ionization mass spectrum for butylene carbonate 2d 9 NMR Spectra for 1,2-hexylene carbonate 2e 10 Chemical ionization mass spectrum for hexylene carbonate 2e 11 NMR Spectra for 1,2-decylene carbonate 2f 12 Chemical ionization mass spectrum for decylene carbonate 2f 13 NMR Spectra for 4-chlorostyrene carbonate 2g 14 Chemical ionization mass spectrum for 4-chlorostyrene carbonate 2g 15 NMR Spectra for 4-bromostyrene carbonate 2h 16 Electron ionization mass spectrum for 4-bromostyrene carbonate 2h 17 NMR Spectra for glycerol carbonate 2i 18 Electron ionization mass spectrum for glycerol carbonate 2i 19 NMR Spectra for 3-chloropropylene carbonate 2j 20 Chemical ionization mass spectrum for 3-chloropropylene carbonate 2j 21 NMR Spectra for 3-phenoxypropylene carbonate 2k 22 Electron ionization mass spectrum for 3-phenoxypropylene carbonate 2k 23 NMR Spectra for cyclohexyl carbonate 29 24 Electron ionization mass spectrum for cyclohexyl carbonate 29 25 Kinetic plots to determine the order with respect to complex 27 26 Plot of log(kobs avg) against log[27] 27 Kinetic plots to determine the order with respect to Bu4NBr 28 Plot of log(kobs avg) against log[Bu4NBr] 29 Plot showing that complex 27 (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate 30 Plot showing that Bu4NBr (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate 30
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
2
NMR Spectra for ethylene carbonate 2a in CDCl3
4.5422
64.3229
154.9957
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
3
Chemical ionization mass spectrum for ethylene carbonate 2a
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
4
NMR Spectra for propylene carbonate 2b in CDCl3
3.08
1.02
1.02
1.00
1.4928
1.5137
4.0125
4.0366
4.0404
4.0646
4.5411
4.5668
4.5683
4.5947
4.8150
4.8358
4.8567
4.8610
4.8820
4.9030
4.9061
4.9271
19.2459
70.4992
73.2499
154.6618
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
5
Chemical ionization mass spectrum for propylene carbonate 2b
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
6
NMR Spectra for styrene carbonate 2c in CDCl3
1.00
1.04
1.01
5.12
4.3317
4.3580
4.3604
4.3867
4.7926
4.8202
4.8485
5.6696
5.6962
5.7229
70.9649
76.5198
76.9440
77.3671
77.8315
125.7238
129.1661
129.5924
136.0084
154.5486
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
7
Chemical ionization mass spectrum for styrene carbonate 2c
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
8
NMR Spectra for 1,2-butylene carbonate 2d in CDCl3
2.92
2.28
1.03
1.04
1.00
0.9742
0.9928
1.0115
1.6644
1.6787
1.6830
1.6976
1.7008
1.7150
1.7187
1.7332
1.7370
1.7518
1.7553
1.7703
1.7884
1.7924
1.8065
1.8242
1.8282
1.8427
4.0363
4.0538
4.0572
4.0747
4.4777
4.4790
4.4977
4.4987
4.5185
4.5198
4.6041
4.6216
4.6367
4.6386
4.6405
4.6547
4.6583
4.6731
8.5723
27.0081
69.1269
76.8525
77.1719
77.4897
78.1350
155.2495
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
9
Chemical ionization mass spectrum for butylene carbonate 2d
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
10
NMR Spectra for 1,2-hexylene carbonate 2e in CDCl3
2.80
3.83
2.14
1.00
1.01
1.00
0.8808
0.9051
0.9277
4.0330
4.0570
4.0609
4.0849
4.4954
4.5218
4.5494
4.6545
4.6727
4.6791
4.6973
4.7041
4.7224
4.7291
4.7473
13.4920
22.0938
26.3257
33.4045
69.2477
76.5454
76.9339
76.9688
77.3924
154.7954
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
11
Chemical ionization mass spectrum for hexylene carbonate 2e
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
12
NMR Spectra for 1,2-decylene carbonate 2f in CDCl3
A DEPT spectrum showed that the CH2O peak was exactly coincident with the CHCl3 peak at 77 ppm
3.43
13.28
2.11
1.08
1.09
1.00
0.8406
0.8583
0.8752
4.0262
4.0443
4.0472
4.0653
4.4841
4.5013
4.5037
4.5051
4.5247
4.6469
4.6605
4.6657
4.6794
4.6845
4.6981
4.7034
4.7170
14.1681
22.7071
24.4512
29.1903
29.2251
29.3859
31.8601
33.9778
69.4871
76.8033
77.1216
77.4396
155.1895
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
13
Chemical ionization mass spectrum for decylene carbonate 2f
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
14
NMR Spectra for 4-chlorostyrene carbonate 2g in CDCl3
1.00
1.04
1.00
2.151.93
4.2866
4.3131
4.3153
4.3415
4.7914
4.8197
4.8476
5.6504
5.6769
5.7034
7.3033
7.3319
7.4142
7.4426
70.7098
76.4711
76.8937
77.0297
77.3172
127.0735
129.4437
134.5462
135.8115
154.1438
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
15
Electron ionization mass spectrum for 4-chlorostyrene carbonate 2g
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
16
NMR Spectra for 4-bromostyrene carbonate 2h in CDCl3
1.17
1.02
1.00
2.32
2.26
4.2769
4.3051
4.3317
4.7868
4.8147
4.8429
5.6306
5.6572
5.6837
7.2369
7.2648
7.2760
7.5654
7.5934
70.6958
76.5085
76.9319
77.0818
77.3553
123.8223
127.3339
132.4305
135.0218
154.2014
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
17
Chemical ionization mass spectrum for 4-bromostyrene carbonate 2h
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
18
NMR Spectra for glycerol carbonate 2i in CD3OD
0.94
1.30
1.13
1.20
1.11
1.00
3.4717
3.4825
3.5138
3.5247
3.6349
3.6442
3.6771
3.6855
3.7230
4.2817
4.3007
4.4563
4.4842
4.5115
4.7644
4.7743
4.7835
4.7935
5.2639
39.0099
39.2872
39.5650
39.8421
40.1219
60.6412
65.8117
76.9344
155.0067
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
19
Chemical ionization mass spectrum for glycerol carbonate 2i
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
20
NMR Spectra for 3-chloropropylene carbonate 2j in CDCl3
2.03
1.00
1.02
1.00
3.7069
3.7194
3.7474
3.7599
3.7820
3.7996
3.8225
3.8401
4.4203
4.4394
4.5736
4.6012
4.6031
4.9557
4.9682
4.9734
4.9747
4.9832
4.9859
4.9871
4.9924
4.9957
5.0009
5.0022
5.0048
5.0134
5.0146
5.0199
5.0324
43.8660
67.0662
74.4089
76.8571
77.1751
77.4931
154.3639
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
21
Chemical ionization mass spectrum for 3-chloropropylene carbonate 2j
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
22
NMR Spectra for 3-phenoxypropylene carbonate 2k in CDCl3
2.15
1.99
0.98
3.24
2.38
4.1364
4.1480
4.1715
4.1833
4.2352
4.2490
4.2703
4.2841
4.5592
4.5790
4.6343
5.0135
5.0260
5.0324
5.0397
5.0457
5.0535
5.0593
5.0654
5.0732
5.0856
6.9152
6.9413
6.9440
7.0102
7.0126
7.0350
7.0368
7.0593
7.0617
7.2776
7.2797
7.3038
7.3307
7.3557
66.1920
67.3169
74.0210
76.4688
76.8916
77.0831
77.3153
114.8798
122.0894
129.6184
154.2526
157.9551
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
23
Electron ionization mass spectrum for 3-phenoxypropylene carbonate 2k
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
24
NMR Spectra for cyclohexene carbonate 29 in CDCl3
2.27
2.17
4.15
2.00
19.2380
26.8419
75.8548
76.8466
77.1655
77.4833
155.4811
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
25
Chemical ionization mass spectrum for cyclohexene carbonate 29
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
26
Kinetic plots to determine the order with respect to complex 27 3 mol% catalyst (42 mM): run 1 3 mol% catalyst (42 mM): run 2
4 mol% catalyst (56 mM): run 1 4 mol% catalyst (56 mM): run 2
5 mol% catalyst (70 mM): run 1 5 mol% catalyst (70 mM): run 2
6 mol% catalyst (84 mM): run 1 6 mol% catalyst (84 mM): run 2
y = -0.00004x + 0.47628R² = 0.99
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000 30000
ln[1c] Time (s)
y = -0.00004x + 0.49325R² = 0.99
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000
ln[1c] Time (s)
y = -0.00006x + 0.46280R² = 0.99
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000 30000
ln[1c]
Time (s)
y = -0.00005x + 0.49604R² = 0.99
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000ln[1c] Time (s)
y = -0.00006x + 0.53318R² = 0.99
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000ln[1c] Time (s)
y = -0.00006x + 0.46787R² = 0.99
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000ln[1c] Time (s)
y = -0.00008x + 0.46176R² = 0.99
-1.6-1.4-1.2
-1-0.8-0.6-0.4-0.2
00.20.40.6
0 10000 20000 30000
ln[1c]
Time (s)y = -0.00007x + 0.49820
R² = 0.99
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000ln[1c] Time (s)
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
27
Plot of log(kobs avg) against log[27]
y = 0.93x - 3.11R² = 0.99
-4.45
-4.35
-4.25
-4.15-1.4 -1.3 -1.2 -1.1 -1
log
(ko
bs a
vg)
log[27]
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
28
Kinetic plots to determine the order with respect to Bu4NBr 3 mol% Bu4NBr (42 mM): run 1 3 mol% Bu4NBr (42 mM): run 2
4 mol% Bu4NBr (42 mM): run 1 4 mol% Bu4NBr (42 mM): run 2
5 mol% Bu4NBr (42 mM): run 1 5 mol% Bu4NBr (42 mM): run 2
6 mol% Bu4NBr (42 mM): run 1 6 mol% Bu4NBr (42 mM): run 2
y = -0.00003x + 0.43591R² = 0.99
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0 5000 10000 15000 20000 25000 30000
ln[1c]
Time (s)
y = -0.00004x + 0.48024R² = 0.98930
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0 5000 10000 15000 20000 25000 30000
ln[1c]
Time (s)
y = -0.00005x + 0.47424R² = 0.99
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000 30000ln[1c] Time (s)
y = -0.00005x + 0.51690R² = 0.99
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000 30000
ln[1c] Time (s)
y = -0.00006x + 0.53318R² = 0.99
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000
ln[1c]
Time (s)
y = -0.00006x + 0.48262R² = 1.00
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000
ln[1c]
Time (s)
y = -0.00007x + 0.52723R² = 0.99
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000
ln[1c]
Time (s)
y = -0.00007x + 0.48636R² = 0.99
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0 5000 10000 15000 20000 25000
ln[1c]
Time (s)
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
29
Plot of log(kobs avg) against log[Bu4NBr]
y = 1.09x + 2.04R² = 0.99
0.5
0.6
0.7
0.8
0.9
-1.4 -1.3 -1.2 -1.1 -1
log
(kob
sav
g)
log [Bu4NBr]
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014
30
Plot showing that complex 27 (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate
Plot showing that Bu4NBr (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0 2 4 6 8
conv
ersi
on %
time h
0
2
4
6
8
10
12
14
0 2 4 6 8
con
vers
ion
%
time h
Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014