Dimethylformamide → 1-[2-methyl-2-((R)-1-oxiranylmethoxy)-propyl]-3-nitro-1H-pyrazole

HRID 1807096Notes

Reaction equation

[CH3:1][C:2]([OH:13])([CH3:12])[CH2:3][N:4]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[N:5]1.CN(C=O)C.[H-].[Na+].[C:21]([O:24][CH2:25][CH3:26])(=O)C>[NH4+].[Cl-]>[CH3:12][C:2]([O:13][CH2:26][C@H:25]1[CH2:21][O:24]1)([CH3:1])[CH2:3][N:4]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[N:5]1

Participants

Conditions

Temperature: 0 °C

Procedure

A mixture of 2-methyl-1-(3-nitro-pyrazol-1-yl)-propan-2-ol (1.31 g, 7.07 mmol), and DMF (60 mL) was stirred at 0° C. for 5 min, then NaH (60% dispersion in oil, 0.85 g, 21.2 mmol) was added and stirred 20 min at 0° C. R-(−)-glycidyl-3-nitrobenzenesulfonate (2.75 g, 10.6 mmol) was added and stirred at 0° C. for 1 h then warmed to rt for 14 h. The mixture was then diluted with NH4Cl(s), ethyl acetate, the organic phase was separated, washed with NaHCO3(satd) dried with Na2SO4, and filtered. The mixture was then concentrated and purified by column chromatography (40-240 g Analogix column, 70% EtoAc/heptane to yield the product 1-[2-methyl-2-((R)-1-oxiranylmethoxy)-propyl]-3-nitro-1H-pyrazole as a white solid (0.7 g, 41%).

Workup

stirringstirred 20 min at 0° C
stirringstirred at 0° C. for 1 h
temperaturethen warmed to rt for 14 h
customthe organic phase was separated
washwashed with NaHCO3(satd)
dry with materialdried with Na2SO4
filtrationfiltered
concentrationThe mixture was then concentrated
custompurified by column chromatography (40-240 g Analogix column, 70% EtoAc/heptane

Sources & evidence

ORD record: ord-3cc07add70584f5da951a92046d70d73
Source dataset: uspto-grants-2013_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08354444B2

Reaction notes

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