tert-Butyldimethylsilyl glycidyl ether → 1-{[tert-butyl(dimethyl)silyl]oxy}-3-(2,4-dinitro-1H-imidazol-1-yl)-2-propanol

HRID 2066620Notes

Reaction equation

[N+:1]([C:4]1[NH:5][CH:6]=[C:7]([N+:9]([O-:11])=[O:10])[N:8]=1)([O-:3])=[O:2].[O:12]1[CH2:14][CH:13]1[CH2:15][O:16][Si:17]([C:20]([CH3:23])([CH3:22])[CH3:21])([CH3:19])[CH3:18]>CCOC(C)=O>[Si:17]([O:16][CH2:15][CH:13]([OH:12])[CH2:14][N:5]1[CH:6]=[C:7]([N+:9]([O-:11])=[O:10])[N:8]=[C:4]1[N+:1]([O-:3])=[O:2])([C:20]([CH3:23])([CH3:22])[CH3:21])([CH3:19])[CH3:18]

Participants

Conditions

Temperature: 70 °C

Procedure

A mixture of 2,4-dinitroimidazole (86) (2.02 g, 12.8 mmol) and tert-butyl(dimethyl)silyl 2-oxiranylmethyl ether (87) (3.84 g, 20.4 mmol) was stirred at 70° C. for 16 h. The resulting cooled mixture was diluted with EtOAc (300 mL) and washed with aqueous NaHCO3 (3×50 mL), water (2×50 mL) and brine (50 mL), and then the solvent was removed. Chromatography of the residue on silica gel, eluting with 10-20% EtOAc/petroleum ether, gave 1-{[tert-butyl(dimethyl)silyl]oxy}-3-(2,4-dinitro-1H-imidazol-1-yl)-2-propanol (88) (reported by Otera et al., US 2006063929A1, starting from 2,4-dinitroimidazole and glycidol) (2.63 g, 60%) as a yellow oil; 1H NMR (CDCl3) δ 8.01 (s, 1H), 4.78 (dd, J=13.9, 2.9 Hz, 1H), 4.46 (dd, J=14.0, 8.3 Hz, 1H), 4.08 (m, 1H), 3.76 (dd, J=10.4, 4.6 Hz, 1H), 3.67 (dd, J=10.5, 5.0 Hz, 1H), 2.60 (br s, 1H), 0.92 (s, 9H), 0.11 (s, 6H); APCI MS m/z 300 [M+H—HNO2]+.

Workup

temperatureThe resulting cooled mixture
washwashed with aqueous NaHCO3 (3×50 mL), water (2×50 mL) and brine (50 mL)
customthe solvent was removed
washChromatography of the residue on silica gel, eluting with 10-20% EtOAc/petroleum ether

Sources & evidence

ORD record: ord-10c074e186ed45adae3c595480840597
Source dataset: uspto-grants-2012_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08293734B2

Reaction notes

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