G
Q.-W. Song et al.
Paper
Synthesis
m × 0.25 m) using a flame ionization detector using biphenyl (40
mg) as the internal standard. Then, the residue was obtained by re-
moving the solvent under vacuum and further purified by column
chromatography (petroleum ether/EtOAc 100:1–5:1) to obtain 5a and
6a.
1H NMR (400 MHz, CDCl3): = 3.88 (1 H, OH), 2.13 (s, 3 H), 1.67–1.55
(m, 2 H), 1.37–1.27 (m, 1 H), 1.26 (s, 3 H), 1.23–1.18 (m, 6 H), 1.00–
0.88 (m, 1 H), 0.79 (t, J = 6.8 Hz, 3 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 212.0, 78.4, 39.1, 31.2, 29.1,
24.9, 23.3, 22.9, 22.1, 13.6.
4-Methyl-1,3-dioxolan-2-one (5a)
1-(1-Hydroxycyclohexyl)ethanone (6c)
Colorless liquid; yield: 98 mg (95%).
1H NMR (400 MHz, CDCl3): = 4.84–4.92 (m, 1 H), 4.58 (t, J = 8.4 Hz, 1
H), 4.04 (t, J = 8.4 Hz, 1 H), 1.49 (d, J = 6.0 Hz, 3 H).
Slightly yellow liquid; yield: 126 mg (59%).
1H NMR (400 MHz, CDCl3): = 2.24 (s, 3 H), 1.75–1.64 (m, 6 H), 1.49
(d, J = 6.5 Hz, 2 H), 1.28 (dd, J = 15.1, 10.3 Hz, 2 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 155.1, 73.7, 70.7, 19.4.
13C{1H} NMR (100.6 MHz, CDCl3): = 212.7, 78.0, 33.8, 25.3, 23.7,
21.1.
4-Ethyl-1,3-dioxolan-2-one (5b)
Colorless liquid; yield: 112 mg (97%).
3-Hydroxy-3-phenylbutan-2-one (6d)
1H NMR (400 MHz, CDCl3): = 4.60–4.67 (m, 1 H), 4.50 (t, J = 8.2 Hz, 1
H), 4.06 (t, J = 8.0 Hz, 1 H), 1.71–1.77 (m, 2 H), 0.98 (t, J = 7.6 Hz, 3 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 155.1, 77.9, 68.9, 26.7, 8.3.
Colorless liquid; yield: 165 mg (67%); Rf = 0.26 (hexane/EtOAc 10:1).
1H NMR (400 MHz, CDCl3): = 7.44–7.42 (m, 2 H), 7.36 (t, J = 7.4 Hz, 2
H), 7.28 (t, J = 7.2 Hz, 1 H), 4.61 (s, 1 H), 2.05 (s, 3 H), 1.74 (s, 3 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 209.6, 141.3, 128.5, 127.8, 125.7,
79.8, 24.0, 23.3.
4-Butyl-1,3-dioxolan-2-one (5c)
Colorless liquid; yield: 140 mg (98%).
1H NMR (400 MHz, CDCl3): = 4.68–4.75 (m, 1 H), 4.54 (t, J = 8.0 Hz, 1
H), 4.08 (dd, J = 7.3, 8.0 Hz, 1 H), 1.64–1.87 (m, 2 H), 1.26–1.48 (m, 4
H), 0.93 (t, J = 7.2 Hz, 3 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 155.1, 77.1, 69.4, 33.5, 26.4,
22.2, 13.7.
3-Hydroxy-3-methylnonan-2-one (6b). Typical Procedure (Scheme 3)
A 50-mL stainless steel autoclave equipped with a magnetic stir bar
was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 2b
(154.1 mg, 1 mmol), H2O (27 mg, 1.5 mmol) and CH3CN (2.0 mL) suc-
cessively and sealed at r.t. Then, the pressure was adjusted to 1 MPa
with CO2 at the preset temperature (80 °C) and the autoclave was
heated at this temperature for 48 h. After the reaction was complete,
the reactor was cooled in ice-water bath, and then excess CO2 was
carefully vented. Then, the residue was obtained by removing the sol-
vent under vacuum and further purified by column chromatography
(petroleum ether/EtOAc 100:1–5:1) to obtain 6b.
4-Hexyl-1,3-dioxolan-2-one (5d)
Colorless liquid; yield: 167 mg (98%).
1H NMR (400 MHz, CDCl3): = 4.71–4.66 (m, 1 H), 4.52 (t, J = 8.0 Hz, 1
H), 4.06 (t, J = 7.8 Hz, 1 H), 1.81–1.76 (m, 1 H), 1.70–1.63 (m, 1 H),
1.49–1.29 (m, 8 H), 0.88 (t, J = 6.6 Hz, 3 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 155.2, 77.0, 69.4, 33.9, 31.5,
28.8, 24.3, 22.4, 14.0.
Funding Information
Financial support from the National Natural Science Foundation of
China (21602232) and the Natural Science Foundation of Shanxi Prov-
4-Phenyl-1,3-dioxolan-2-one (5e)
Colorless liquid; yield: 133 mg (81%); Rf = 0.15 (hexane/EtOAc 3:1).
ince (201701D221057) are gratefully acknowledged.
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1H NMR (400 MHz, CDCl3): = 7.44 (d, J = 6.4 Hz, 3 H, C6H5), 7.36 (d,
J = 7.6 Hz, 2 H, C6H5), 5.70 (t, J = 8.0 Hz, 1 H, OCH), 4.80 (t, J = 8.4 Hz, 1
H, OCH2), 4.35 (t, J = 8.4 Hz, 1 H, OCH2).
13C{1H} NMR (100.6 MHz, CDCl3): = 157.7, 154.7, 129.6, 121.9, 114.6,
74.1, 68.8, 66.2.
Supporting Information
Supporting information for this article is available online at
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Hexahydro-1,3-benzodioxol-2-one (5f)
Slightly yellow liquid; yield: 134 mg (94%).
1H NMR (400 MHz, CDCl3): = 4.70 (s, 2 H), 1.91 (d, J = 5.4 Hz, 4 H),
References
(1) (a) Yang, Z.-Z.; He, L.-N.; Gao, J.; Liu, A.-H.; Yu, B. Energy Environ.
Sci. 2012, 5, 6602. (b) Aresta, M.; Dibenedetto, A.; Angelini, A.
Chem. Rev. 2014, 114, 1709. (c) Liu, Q.; Wu, L.; Jackstell, R.;
Beller, M. Nat. Commun. 2015, 6, 5933. (d) He, M.; Sun, Y.; Han,
B. Angew. Chem. Int. Ed. 2013, 52, 9620. (e) Wang, W. H.;
Himeda, Y.; Muckerman, J. T.; Manbeck, G. F.; Fujita, E. Chem.
Rev. 2015, 115, 12936. (f) Song, Q.-W.; Zhou, Z.-H.; He, L.-N.
Green Chem. 2017, 19, 3707. (g) Zhang, Q.; Yuan, H.-Y.; Fukaya,
N.; Yasuda, H.; Choi, J.-C. Green Chem. 2017, 19, 5614.
1.69–1.52 (m, 2 H), 1.51–1.34 (m, 2 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 155.4, 75.8, 26.8, 19.2.
3-Hydroxy-3-methylbutan-2-one (6a)
Slightly yellow liquid; yield: 102 mg (67%).
1H NMR (400 MHz, CDCl3): = 3.88 (s, 1 H), 2.02 (s, 3 H), 1.14 (s, 6 H).
13C{1H} NMR (100.6 MHz, CDCl3): = 212.5, 76.0, 25.8, 23.2.
(2) For selected reviews, see: (a) Lu, X.-B.; Darensbourg, D. J. Chem.
Soc. Rev. 2012, 41, 1462. (b) Zhang, H.; Liu, H.-B.; Yue, J.-M.
Chem. Rev. 2014, 114, 883. (c) Schäffner, B.; Schäffner, F.;
3-Hydroxy-3-methylnonan-2-one (6b)
Colorless liquid; yield: 161 mg (62%).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H