JOURNAL OF CHEMICAL RESEARCH 2014 681
Table 2 Catalysed transesterification of various glycols with dimethyl
Chemicals (JSBGFC13006), the Specialised Research Fund for
the Doctoral Program of Higher Education (G2014006) and the
National Key Technology R&D Program in the 12th Five year
Plan of China (2012BAD32B03).
carbonate (DMC)a
O
HO
R
OH
KF/Ca-Mg-Al HT
80 oC, 0.5 h
O
O
O
+
MeO
MeO
R
Received 25 September 2014; accepted 17 October 2014
Paper 1402915 doi: 10.3184/174751914X14138850796063
Published online: 13 November 2014
R = H, Me, CH2OH, Ph
Substrates
Products
Yield/%b
Ethylene glycol
Propylene glycol
Glycerol
Ethylene carbonate
Propylene carbonate
Glycerol carbonate
Styrene carbonate
98
76
99
91
References
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Styrene glycol
aReaction conditions: KF/Ca–Mg–Al HT (5 wt%), substrate (2.0 mmol),
DMC (6 mmol), 80 °C, 0.5 h.
3
4
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Catalysed transesterification
Glycerol (0.184 g, 2 mmol), dimethyl carbonate (0.54 g, 6 mmol)
and 5 wt% KF/Ca–Mg–Al hydrotalcite were added to a 25 mL flask
equipped with a magnetic stirrer, condenser and thermometer. The
reaction was carried out at 80 °C for 0.5 h with vigorous stirring. The
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of the reaction, the solution was filtered. The filtrate was evaporated
under reduced pressure, and finally the crude glycerol carbonate was
obtained. The catalyst was reused for the next run.
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residue was purified with silica gel column chromatography (AcOEt).
All products were identified by comparing their melting points,
1H NMR and 13C NMR spectra and MS with those of standard samples.
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1
Glycerol carbonate: Oil; H NMR (DMSO‑d6) δ 3.47–3.50 (m, 1H,
CH2), 3.62–3.67 (m, 1H, CH2), 4.28 (d,d, J=5.9, 8.4 Hz, 1H, CH2), 4.48
(t, J=8.4 Hz, 1H, CH2), 4.73–4.81 (m, 1H, CH), 5.26 (t, J=5.7 Hz, 1H,
OH); 13C NMR (DMSO‑d6) δ 61.7, 66.8, 77.1, 156.1; MS m/z: 118 (M+).
Ethylene carbonate: M.p. 35–37 °C (ether) (lit.26 36–37 °C); 1H NMR
(CDCl3) δ 4.51 (s, 4H, CH2); 13C NMR (CDCl3) δ 65.5, 156.4; MS m/z:
88 (M+).
Propylene carbonate: Oil; 1H NMR (CDCl3) δ 1.53 (d, J=6.2 Hz, 3H,
CH3), 4.05 (d, d, J=8.4, 8.4 Hz, 1H, CH2), 4.51 (d, d, J=8.4, 8.4 Hz, 1H,
CH2); 13C NMR (CDCl3) δ 18.7, 71.5, 73.5, 154.7; MS m/z: 102 (M+).
Styrene carbonate: M.p. 52–54.0 °C (EtOH) (lit.27 53–54 °C);
1H NMR (CDCl3) δ 4.37 (t, J=8.2 Hz, 1H, CH2), 4.85 (t, J=8.2 Hz, 1H,
CH2), 5.71 (t, J=8.2 Hz, 1H, CH), 7.32–7.46 (m, 5H, CH); 13C NMR
(CDCl3) δ 72.1, 77.5, 126.8, 129.3, 129.8, 134.7, 155.6; MS m/z: 164 (M+).
The work was supported by the Natural Science Foundation
of Jiangsu Province (China) (No. BK20140969), the open
fund of Jiangsu Key Lab of Biomass‑based green Fuels and
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