Triethylamine → 6-Nitromethylene-[1,4]dioxepane

Temperature

-78 °C

A stirred mixture of 6-nitromethyl-[1,4]dioxepan-6-ol (0.74 g, 4.18 mmol) and triethylamine (1.86 g, 2.56 mL, 18.4 mmol) in dichloromethane (20 mL), under nitrogen, was cooled to −78° C. and methanesulfonyl chloride (1.43 g, 970 μL, 12.5 mmol) was added dropwise. The reaction mixture was stirred for 30 minutes and then quenched with saturated ammonium chloride solution. The mixture was removed from the cooling bath and allowed to warm to ambient temperature. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate, filtered and evaporated. The residue was purified by silica gel chromatography using a gradient of pentane/diethyl ether 3:1 to 1:1 to give the title compound (512 mg, 77%) as a yellow oil. 1H NMR (300 MHz, CDCl3) δ 3.81-3.90 (m, 4H), 4.36 (d, J=0.5 Hz, 2H), 5.04 (d, J=2.5 Hz, 2H), 7.02 (t, J=2.5 Hz, 1H). LCMS (m/z) 182.1.0 [M+Na], Tr=1.04 min.

1. customquenched with saturated ammonium chloride solution
2. customThe mixture was removed from the cooling bath
3. temperatureto warm to ambient temperature
4. customThe organic layer was separated
5. extractionthe aqueous layer was extracted with dichloromethane
6. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
7. filtrationfiltered
8. customevaporated
9. customThe residue was purified by silica gel chromatography

ORD record

ord-7b801ca0abd9417c98b666507de17301

Source dataset

uspto-grants-2015_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09062092B2