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%, 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, eluting from silica gel with a gradient of 50-100% ethyl acetate in hexanes to give 15.4 g of desired product (63% yield). 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 (d of trip, 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): 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
6. washeluting from silica gel with a gradient of 50-100% ethyl acetate in hexanes

ORD record

ord-cb1f1373129548129785a5776bc53158

Source dataset

uspto-grants-2014_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08729112B2