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CO 2 coupling with epoxides catalysed by using one-pot synthesised, in situ activated zinc ascorbate under ambient conditions Feda’a M. Al-Qaisi, *a Abdussalam K. Qaroush, *b Amneh H. Smadi, a Fatima Alsoubani, a Khaleel I. Assaf, c Timo Repo d and Ala’a F. Eftaiha *a a Department of Chemistry, The Hashemite University, P.O. Box 150459, Zarqa 13115, Jordan. E-mails: [email protected]; [email protected] b Department of Chemistry, Faculty of Science, The University of Jordan, Amman 11942, Jordan. E-mail: [email protected] c Department of Chemistry, Faculty of Science, Al-Balqa Applied University, 19117 Al-Salt, Jordan. d Department of Chemistry, University of Helsinki A.I. Virtasen aukio 1, 00014 Helsinki, Finland. Electronic Supplementary Information (ESI) Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2020
Transcript of 0DWHULDO (6, IRU'DOWRQ7UDQVDFWLRQV …Feda’a M. Al-Qaisi,*a Abdussalam K. Qaroush,*b Amneh H....
CO2 coupling with epoxides catalysed by using one-pot
synthesised, in situ activated zinc ascorbate under ambient
conditions
Feda’a M. Al-Qaisi,*a Abdussalam K. Qaroush,*b Amneh H. Smadi,a Fatima Alsoubani,a Khaleel
I. Assaf,c Timo Repod and Ala’a F. Eftaiha*a
a Department of Chemistry, The Hashemite University, P.O. Box 150459, Zarqa 13115, Jordan.
E-mails: [email protected]; [email protected]
b Department of Chemistry, Faculty of Science, The University of Jordan, Amman 11942, Jordan.
E-mail: [email protected]
c Department of Chemistry, Faculty of Science, Al-Balqa Applied University, 19117 Al-Salt, Jordan.
d Department of Chemistry, University of Helsinki A.I. Virtasen aukio 1, 00014 Helsinki, Finland.
Electronic Supplementary Information (ESI)
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2020
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1
2
OH
OHOHO
O
HO
13
5
2
76
4
O
OHOHO
O
O
1
2
34
NaNa
5
4-54.86
34.68
23.71
13.42
3-44.14
23.50
13.38
68.297
11.01
Chemical Shift (ppm)
Fig. S1. 1H NMR spectra (in DMSO-d6) of ASC(OH)2 (black trace) and ASC(ONa)2 (red trace).
-150153045607590105120135150165180195210Chemical Shift (ppm)
176.1
155.2
7155.2
675.4
567.1 4
51.7Cl
456
OO
O7
Cl1
23
O2-1
3
A
B
Fig. S2. 13C NMR (in DMSO-d6) spectra of ECH conversion after 17 h (A) and 41 h (B) reaction time, respectively.
3305 broad peak(O-H) stretching
(2924-3003)(C-H) stretching
(2250,2125)Dimethyl sulfoxide- d6
1778Co2 chemiosorption
1728 (C=O)
1594 (C=C)
0
0.2
0.4
0.6
0.8
1
5001000150020002500300035004000
% T
rans
mitt
ance
Wavenumber (cm-1)
CO2 Chemisorption
DMSO- d6
1377(C-H) wagging
Fig. S3. ATR-FTIR spectra of ASC(O)2Zn before (black) and after bubbling (red trace) CO2.
O
Cl1
2 3Cl
4 5 6
OO
O
2
56 4
1
3
Chemical Shift (ppm)
Fig. S4. 1H NMR spectrum (in DMSO-d6) of epichlorohydrin carbonate activated by ZnCl2/sodium ascorbate (Reaction Conditions: 17 h and 25 ºC)
δ (ppm)Fig. S5. 13C NMR spectra (in DMSO-d6) of PG (black trace), PG/NaH/CO2 (red trace) and PG/NaH/CO2/ZnBr2 (blue trace)
68.2
39.9
20.91
2
3
Chemical Shift (ppm)
OH
OH
1 23
Chemical Shift (ppm)
O
Cl1
2 3Cl
4 5 6
OO
O
2
5
6
4
3
1
Fig. S6. 1H NMR spectrum (in DMSO-d6) of epichloro carbonate (ECC) entry 1. (Reaction Conditions: 17 h and 20 ºC).1
Chemical Shift (ppm)
O
Cl1
2 3
Cl4 5 6
OO
O2
5
6
4
3
1
Fig. S7. 1H NMR spectrum (in DMSO-d6) of ECC entry 2. (Reaction Conditions: 17 h and 20 ºC). 1
O
Cl1
2 3Cl4 5 6
OO
O2
5
6
4
1
3
Chemical Shift (ppm)
Fig. S8. 1H NMR spectrum (in DMSO-d6) of ECC entry 3. (Reaction Conditions: 17 h and 20 ºC). 1
O
Cl1
2 3Cl4 5 6
OO
O
25
6
4
3
1
Chemical Shift (ppm)
0.00.51.01.52.02.53.03.54.04.55.05.56.0
0.46
0.54
Fig. S9. 1H NMR spectrum (in DMSO-d6) of ECC entry 4. (Reaction Conditions: 41 h and 20 ºC). 1
O
Cl1
2 3Cl4 5 6
OO
O2
5
6
4
3
1
Chemical Shift (ppm)
Fig. S10. 1H NMR spectrum (in DMSO-d6) of ECC entry 5 (Reaction Conditions: 17 h and 30 ºC).1
O
Cl1
2 3Cl4 5 6
OO
O
2
5
64
3
1
Chemical Shift (ppm)
Fig. S11 . 1H NMR spectrum (in DMSO-d6) of ECC entry 6 (Reaction Conditions: 17 h and 50 ºC). 1
12
O
3
4
OO
O
56
1
2
3
5
6
4
Chemical Shift (ppm)
Fig. S12 . 1H NMR spectrum (in DMSO-d6) of propylene carbonate entry 7 (Reaction Conditions: 17 h and 20 ºC).1
O
12
OO
O
3
41
3
2
4Aromatic peaks
Chemical Shift (ppm)
Fig. S13 . 1H NMR spectrum (in DMSO-d6) of styrene carbonate entry 8 (Reaction Conditions: 17 h and 50 ºC).1
Chemical Shift (ppm)
O
Br1
2 3
Br4 5 6
OO
O
2
5
64
3
1
Fig. S14. 1H NMR spectrum (in DMSO-d6) of epibromo carbonate entry 9 (Reaction Conditions: 17 h and 50 ºC).2
O1
33
2
4
5
6
1
2
64-5 3
Chemical Shift (ppm)
Figure S15 . 1H NMR spectrum (in DMSO-d6) of pinene oxide entry 10 (Reaction Conditions: 17 h and 50 ºC). Note: No signals above 5 in 1H NMR for carbonate product. 3
O
13
5
2
46
7
4
8
12345
6
78
Chemical Shift (ppm)
Fig. S16. 13C NMR spectrum (in DMSO-d6) of pinene oxide entry 10 (Reaction Conditions: 17 h and 50 ºC). Note: no appearance for signal in region between 150-160 ppm in 13C NMR.3
O
1
2
3
45
6
7
8
9
10
109
8
7-65
43-1
Chemical Shift (ppm)
Fig. S17. 13C NMR spectrum (in DMSO-d6) of limonene oxide entry 11 (Reaction Conditions: 17 h and 50 ºC). Note: No product as no signals above 5 in 1H NMR for carbonate product.2
(1) Zhang, S.; Han, F.; Yan, S.; He, M.; Miao, C.; He, L.-N. Efficient Catalysts In Situ Generated from Zinc, Amide and Benzyl Bromide for Epoxide/CO 2 Coupling Reaction at Atmospheric Pressure: Efficient Catalysts In Situ Generated from Zinc, Amide and Benzyl Bromide for Epoxide/CO 2 Coupling Reaction at Atmospheric Pressure. Eur. J. Org. Chem. 2019, 2019 (6), 1311–1316. https://doi.org/10.1002/ejoc.201801653.
(2) Qaroush, A. K.; Alsoubani, F. A.; Al-Khateeb, A. M.; Nabih, E.; Al-Ramahi, E.; Khanfar, M. F.; Assaf, K. I.; Eftaiha, A. F. An Efficient Atom-Economical Chemoselective CO 2 Cycloaddition Using Lanthanum Oxide/Tetrabutyl Ammonium Bromide. Sustainable Energy Fuels 2018, 2 (6), 1342–1349. https://doi.org/10.1039/C8SE00092A.
(3) Zhi, Y.; Shan, X.; Shan, S.; Jia, Q.; Ni, Y.; Zeng, G. Synthesis and Thermal Degradation Kinetics of New Terpolymer of Carbon Dioxide, Cyclohexene Oxide and Alpha-Pinene Oxide. Journal of CO2 Utilization 2017, 22, 299–306. https://doi.org/10.1016/j.jcou.2017.09.020.
