A Structural Study of Epoxidized Natural Rubber (ENR-50) and Its Cyclic Dithiocarbonate Derivative Using NMR Spectroscopy Techniques
Abstract
:1. Introduction
1H chemical shift δ (ppm) | 13C chemical shiftδ (ppm) | HMQC | HMBC Coupling correlation | COSY Coupling correlation | |||||
---|---|---|---|---|---|---|---|---|---|
Ref: 14–15 | Ref: 11 | This work | Ref: 11 | This work | Triad assignment | Middle unit | Within same unit | Middle unit | Within same unit |
δ (ppm) | δ (ppm) | δ (ppm) | δ (ppm) | ||||||
1.31 | 1.29 | 1.30 | 22.1 | 22.3 | E10 | 29.7 (E8), 60.7 (E6), 64.5 (E7) | None | None | None |
1.38 | 1.55 | 1.56 | 29.5 | 29.7 | EE8C, E8 | 22.3 (E10), 60.7 (E6), 64.5 (E7) | 24.7 (E9), 64.5 (E7) | None | 1.68–1.70 (E9) |
33.0 | 33.1 | CE8C, CE8E | 22.3 (E10), 60.7 (E6), 64.5 (E7) | 23.9 (C4), 125.0 (C2) | None | 2.15–2.19 (C4) | |||
26.9 | 27.0 | CE9C, EE9C | 60.7 (E6), 64.5 (E7) | 28.7 (C3), 134.7 (C1) | 2.72 (E7) | 2.15–2.19 (C3) | |||
1.42 | 1.68 | 1.68–1.70 | 23.3 | 23.4 | C5 | 32.0 (C3), 125.0 (C2), 134.7 (C1) | None | None | None |
1.38 | 24.6 | 24.7 | CE9E, E9 | 60.7 (E6), 64.5 (E7) | 29.7 (E8), 60.7 (E6) | 2.72 (E7) | 1.56 (E8) | ||
2.00 | 2.05 | 2.06 | 26.2 | 26.3 | C4, EC4C | 125.0 (C2), 134.7 (C1) | 32.0 (C3), 134.7 (C1) | 5.12–5.17 (C2) | 2.06 (C3) |
32.0 | 32.0 | C3, CC3E | 23.4 (C5), 125.0 (C2), 134.7 (C1) | 26.3 (C4), 125.0 (C2) | None | 2.06 (C4) | |||
1.96 | 2.15 | 2.15-2.19 | 23.7 | 23.9 | CC4E, EC4E | 125.0 (C2), 134.7 (C1) | 33.1 (E8), 60.7 (E6) | 5.12–5.17 (C2) | 1.56 (E8) |
28.5 | 28.7 | EC3C, EC3E | 23.4 (C5), 125.0 (C2), 134.7 (C1) | 27.0 (E9), 64.5 (E7) | None | 1.56 (E9) | |||
- | - | - | 60.3 | 60.7 | E6 | - | - | - | - |
2.51 | 2.70 | 2.72 | 64.0 | 64.5 | E7 | 22.3 (E10), 24.7 (E9), 29.7 (E8), 60.7 (E6) | 29.7 (E8), (None) | 1.68-1.70 (E9) | None |
5.20 | 5.10 | 5.12–5.17 | 125.0 | 125.0 | C2 | 23.4 (C5), 26.3 (C4), 32.0 (C3), 134.7 (C1) (NOT DETECTED) | 32.0 (C3) | 2.06 (C4) | None |
- | - | - | 135.0 | 134.7 | C1 | - | - | - | - |
2. Results and Discussion
2.1. Epoxidized Natural Rubber
2.1.2. HMQC
2.1.3. HMBC
2.1.4. COSY
2.2. Cyclic Dithiocarbonate Derivative of ENR-50
2.2.1. FTIR Spectroscopy
2.2.2. 1H and 13C-NMR Spectroscopy
Chemical shift δ (ppm) | Triad assignment | |||
---|---|---|---|---|
1H | 13C | |||
ENR-50 * | Cyclic dithiocarbonate derivative | ENR-50 * | Cyclic dithiocarbonate derivative | |
1.30 | 1.31 | 22.3 | 22.4 | E10 |
1.56 | 1.58–1.63 | 29.7 | 29.8 | EE8C, E8 |
33.1 | 33.1 | CE8C, CE8E | ||
27.0 | 27.0 | CE9C, EE9C | ||
1.68–1.70 | 1.70–1.71 | 23.4 | 23.5 | C5 |
24.7 | 24.8 | CE9E, E9 | ||
2.06 | 2.08 | 26.3 | 26.4 | C4, EC4C |
32.0 | 32.2 | C3, CC3E | ||
2.15–2.19 | 2.12–2.19 | 23.9 | 24.0 | CC4E, EC4E |
28.7 | 28.7 | EC3C, EC3E | ||
- | - | 60.7 | 61.0 | E6 |
2.72 | 2.73 | 64.5 | 64.8 | E7, E7of five-membered ring |
- | - | - | 94.0 | E6 of five-membered ring |
5.12–5.17 | 5.15–5.19 | 125.0 | 125.1 | C2 |
- | - | 134.7 | 134.9 | C1 |
- | - | - | 210.5 | CS2 carbon of five-membered ring |
2.2.3. Proposed Mechanism for the Formation of Cyclic Dithiocarbonate
3. Experimental
3.1. Materials
3.2. Preparative Procedure
3.2.1. Purification of ENR-50 [19]
3.2.2. Reaction of Purified ENR-50 with CS2 [24]
3.3. Measurements and Characterization Techniques
3.4. Theoretical Treatments
4. Conclusions
Acknowledgments
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Hamzah, R.; Bakar, M.A.; Khairuddean, M.; Mohammed, I.A.; Adnan, R. A Structural Study of Epoxidized Natural Rubber (ENR-50) and Its Cyclic Dithiocarbonate Derivative Using NMR Spectroscopy Techniques. Molecules 2012, 17, 10974-10993. https://doi.org/10.3390/molecules170910974
Hamzah R, Bakar MA, Khairuddean M, Mohammed IA, Adnan R. A Structural Study of Epoxidized Natural Rubber (ENR-50) and Its Cyclic Dithiocarbonate Derivative Using NMR Spectroscopy Techniques. Molecules. 2012; 17(9):10974-10993. https://doi.org/10.3390/molecules170910974
Chicago/Turabian StyleHamzah, Rosniza, Mohamad Abu Bakar, Melati Khairuddean, Issam Ahmed Mohammed, and Rohana Adnan. 2012. "A Structural Study of Epoxidized Natural Rubber (ENR-50) and Its Cyclic Dithiocarbonate Derivative Using NMR Spectroscopy Techniques" Molecules 17, no. 9: 10974-10993. https://doi.org/10.3390/molecules170910974
APA StyleHamzah, R., Bakar, M. A., Khairuddean, M., Mohammed, I. A., & Adnan, R. (2012). A Structural Study of Epoxidized Natural Rubber (ENR-50) and Its Cyclic Dithiocarbonate Derivative Using NMR Spectroscopy Techniques. Molecules, 17(9), 10974-10993. https://doi.org/10.3390/molecules170910974