Formaldehyde → 3,5-Dimethyl-5-nitro-1,3-oxazinane

To a solution of 2-nitro-2-methyl-1,3-propanediol (20.4 g, 151 mmol) in 40% aqueous methylamine (11.7 g, 151 mmol), was added an aqueous solution of formaldehyde (37% formaldehyde, 12.2 g, 151 mmol). The reaction was stirred at room temperature for one week, then extracted with ether three times. The organic fractions were dried over sodium sulfate and concentrated under reduced pressure to give a crude oil which was purified by column chromatography (50 to 100% ethyl acetate in hexanes) to give the desired product (15.4 g, 96.1 mmol, 63%). 1H NMR (400 MHz, CDCl3) δ 1.45 (s, 3H), 2.32 (s, 3H), 2.63-2.66 (d, J=13.2 Hz, 1H), 3.51-3.54 (d, J=12.6 Hz, 1H), 3.67-3.71 (dt, J=1.9, 13.2 Hz, 1H), 3.86-3.89 (d, J=8.5 Hz, 1H), 4.29-4.32 (dd, J=1.2, 8.6 Hz, 1H), 4.61-4.66 (dd, J=2.4, 12.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 22.0, 39.9, 59.8, 71.2, 83.1, 86.1. LRMS (ESI/APCI) m/z 161 [M+H]+.

1. extractionextracted with ether three times
2. dry with materialThe organic fractions were dried over sodium sulfate
3. concentrationconcentrated under reduced pressure
4. customto give a crude oil which
5. customwas purified by column chromatography (50 to 100% ethyl acetate in hexanes)

ORD-Eintrag

ord-763f22c6f1194c498805a7445679fcc6

Quelldatensatz

uspto-grants-2016_02

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09248117B2