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

反応式

[N+:1]([C:4]([CH3:9])([CH2:7]O)[CH2:5][OH:6])([O-:3])=[O:2].[CH3:10][NH2:11].[CH2:12]=O>>[CH3:10][N:11]1[CH2:7][C:4]([CH3:9])([N+:1]([O-:3])=[O:2])[CH2:5][O:6][CH2:12]1

参加物

反応物 3

HCID 712Formaldehyde

HCID 6329Methylamine

HCID 64802-Methyl-2-nitro-1,3-propanediol

生成物 1

HCID 2018303,5-Dimethyl-5-nitro-1,3-oxazinane収率 63.7%

実験手順

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]+.