Organic Process Research & Development
Communication
ethyl chloroformate (6′) (12 mL, 129 mmol) was added to the
solution. The mixture was cooled to 0 °C and stirred for 15
min. Calcium hydroxide (4.81 g, 65 mmol) was then added in
portions, and the mixture was slowly warmed to 25 °C. After
stirring overnight, the reaction mixture was filtered, and the
filtrate was analyzed by GC and distilled under reduced
pressure. Ethyl 2,2,2-trifluoroethyl carbonate (1a′) was
ASSOCIATED CONTENT
Supporting Information
■
*
S
NMR spectra of the compounds (PDF)
obtained as a colorless oil (19.8 g, 89%).
AUTHOR INFORMATION
234.
1
■
*
7
H NMR (400 MHz, CDCl ): δ 4.43 (qd, J = 8.3, 1.3 Hz,
3
1
3
2
H), 4.15−4.21 (m, 2H), 1.25 (tt, J = 7.2, 1.3 Hz, 3H). C
NMR (101 MHz, CDCl ): δ 156.03, 124.79 (q, J
= 278.8
3
C−F
Hz), 67.27, 65.19 (q, JC−F = 36.8 Hz), 15.83. 19F NMR (376
ORCID
MHz, CDCl ): δ −74.87 to −74.91 (m).
3
Ethyl Methyl Carbonate (1b). Ethanol (7b) (7.52 mL,
1
29 mmol) was dissolved in dodecane (130 mL), and 6 (10
Author Contributions
mL, 129 mmol) was added to the solution. The mixture was
The manuscript was written through contributions from all of
the authors, and all of the authors approved the final version of
the manuscript.
cooled to 0 °C and stirred for 15 min. Calcium hydroxide
(
4.81 g, 65 mmol) was then added in portions, and the mixture
was slowly warmed to 25 °C. After stirring overnight, the
reaction mixture was filtered, and the filtrate was analyzed by
GC and distilled under reduced pressure. Ethyl methyl
Notes
The authors declare no competing financial interest.
carbonate (1b) was obtained as a colorless oil (10.6 g, 79%).
ACKNOWLEDGMENTS
The authors thank our group members for daily discussions
and their suggestions during the preparation of the manuscript.
1
■
H NMR (400 MHz, CDCl ): δ 3.95−4.01 (m, 2H), 3.55 (t,
3
13
J = 1.8 Hz, 3H), 1.09 (td, J = 7.2, 1.7 Hz, 3H). C NMR (101
MHz, CDCl ): δ 155.36, 63.42, 53.95, 13.70.
3
Allyl Methyl Carbonate (1c). Allyl alcohol (7c) (8.83 mL,
29 mmol) was dissolved in dodecane (130 mL), and 6 (10
mL, 129 mmol) was added to the solution. The mixture was
cooled to 0 °C and stirred for 15 min. Calcium hydroxide
4.81 g, 65 mmol) was then added in portions, and the mixture
ABBREVIATIONS
DMC, dimethyl carbonate; EMC, ethyl methyl carbonate; EC,
ethylene carbonate; NMR, nuclear magnetic resonance
1
■
(
was slowly warmed to 25 °C. After stirring overnight, the
reaction mixture was filtered, and the filtrate was analyzed by
GC and distilled under reduced pressure. Allyl methyl
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■
(
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H NMR (400 MHz, CDCl ): δ 5.74−5.84 (m, 1H), 5.20
15.
3
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dq, J = 17.0, 1.4 Hz, 1H), 5.11 (dq, J = 10.4, 1.2 Hz, 1H),
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.46−4.48 (m, 2H), 3.63 (t, J = 1.4 Hz, 3H). C NMR (101
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3
Methyl Phenyl Carbonate (1d). Phenol (7d) (12.1 g, 129
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(
4.81 g, 65 mmol) was then added in portions, and the mixture
was slowly warmed to 25 °C. After stirring overnight, the
reaction mixture was filtered, and the filtrate was analyzed by
GC and distilled under reduced pressure. Methyl phenyl
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A Compatible Carbonate Electrolyte with Lithium Anode for High
Performance Lithium Sulfur Battery. Electrochim. Acta 2018, 282,
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carbonate (1d) was obtained as a colorless oil (15.1 g, 77%).
1
H NMR (400 MHz, CDCl ): δ 7.35−7.39 (m, 2H), 7.18−
3
13
7
.24 (m, 3H), 3.84 (t, J = 1.4 Hz, 3H). C NMR (101 MHz,
(6) Jia, H.; Onishi, H.; von Aspern, N.; Rodehorst, U.; Rudolf, K.;
CDCl ): δ 153.95, 150.89, 129.15, 125.68, 120.72, 54.89.
3
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Glycerol 1,2-Carbonate (10). Glycerol (9) (11.9 g, 129
mmol) was dissolved in toluene (130 mL), and 6 (10 mL, 129
mmol) was added to the solution. The mixture was cooled to 0
°
C and stirred for 15 min. Calcium hydroxide (4.81 mg, 65
(7) Wang, L.; Liu, S.; Zhao, K.; Li, J.; Yang, Y.; Jia, G. Improving the
Rate Performance and Stability of LiNi Co Mn O in High
mmol) was added in portions. After 6 h of stirring and slow
warming to room temperature, the reaction mixture was stirred
under reflux for 24 h in a Dean−Stark apparatus. The resulting
mixture was filtered at 25 °C, and the filtrate was analyzed by
GC and distilled under vacuum. Glycerol 1,2-carbonate (10)
0.6
0.2
0.2
2
Voltage Lithium-ion Battery by Using Fluoroethylene Carbonate as
Electrolyte Additive. Ionics 2018, 24, 3337−3346.
(8) Shaikh, A. G.; Sivaram, S. Organic Carbonates. Chem. Rev. 1996,
9
(
6, 951−976.
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was obtained as a colorless oil (11.0 g, 72%).
Disproportionation of Unsymmetrical Carbonate. J. Org. Chem. 1959,
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1
H NMR (400 MHz, CDCl ): δ 4.82−4.78 (m, 1H), 4.53−
3
13
4
.44 (m, 2H), 3.99−3.70 (m, 2H). C NMR (101 MHz,
acetone-d ): δ 155.95, 77.42, 66.18, 61.41.
6
F
Org. Process Res. Dev. XXXX, XXX, XXX−XXX