1,8-Diazabicyclo(5.4.0)undec-7-ene → Ethyl 5-vinyl-1,3-dioxane-5-carboxylate

HRID 2176246Notes

Reaction equation

S(O[CH:12]([C:14]1([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:19][O:18][CH2:17][O:16][CH2:15]1)[CH3:13])(C1C=CC(C)=CC=1)(=O)=O.C1CCN2C(=NCCC2)CC1>CCOCC>[CH2:23]([O:22][C:20]([C:14]1([CH:12]=[CH2:13])[CH2:19][O:18][CH2:17][O:16][CH2:15]1)=[O:21])[CH3:24]

Participants

Conditions

Temperature: 140 °C

Procedure

A mixture of ethyl 5-(1-(tosyloxy)ethyl)-1,3-dioxane-5-carboxylate (20.7 g, 58 mmol) and DBU (25 mL) was heated at 140° C. for 3 h. After being cooled to rt, the reaction mixture was poured into ether (300 mL), and the organic layer was washed with brine (3×). The ether layer was dried over sodium sulfate, and concentrated in vacuo. The residue was purified by silica gel chromatography eluting with petroleum ether/ether 30:1 to 20:1 to give a crude product, which was distilled under reduced pressure (45-49° C./0.3 mbar) to afford the title compound (3.6 g, 33%) as colorless oil. 1H NMR (400 MHz, CDCl3) δ 1.29 (t, J=11.0 Hz, 3H), 3.70 (d, J=11.6 Hz, 2H), 4.25 (t, J=7.2 Hz, 2H), 4.44 (t, J=11.2 Hz, 2H), 4.71 (d, J=8.0 Hz, 1H), 4.95 (d, J=6.0 Hz, 1H), 5.24 (m, 1H), 5.27 (m, 1H), 5.65 (m, 1H). This 1H spectral data is in good agreement with that reported for the synthesis of the title compound, the which is described in Borremans, F. et al. Bull. Soc. Chim. Belg. 1976, 85, 681-696.

Workup

temperatureAfter being cooled to rt
washthe organic layer was washed with brine (3×)
dry with materialThe ether layer was dried over sodium sulfate
concentrationconcentrated in vacuo
customThe residue was purified by silica gel chromatography
washeluting with petroleum ether/ether 30:1 to 20:1
customto give a crude product, which
distillationwas distilled under reduced pressure (45-49° C./0.3 mbar)

Sources & evidence

ORD record: ord-4b40dbc985204ac08b3806be128ca50c
Source dataset: uspto-grants-2015_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09062092B2

Reaction notes

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