5-Amino-4-fluoro-2-methylphenyl Methoxyformate → (4-Fluoro-5-hydroxy-2-methylphenyl) methyl carbonate

HRID 1384552Notes

Reaction equation

N([O-])=[O:2].[Na+].[F:5][C:6]1[CH:12]=[C:11]([CH3:13])[C:10]([O:14][C:15]([O:17][CH3:18])=[O:16])=[CH:9][C:7]=1N>O.S(=O)(=O)(O)O.O.O.O.[N+]([O-])([O-])=O.[Cu+2].[N+]([O-])([O-])=O.[Cu]=O>[F:5][C:6]1[CH:12]=[C:11]([CH3:13])[C:10]([O:14][C:15]([O:17][CH3:18])=[O:16])=[CH:9][C:7]=1[OH:2]

Participants

Conditions

Temperature: 0 °C

Procedure

A solution of sodium nitrite (1.63 g, 23 mmol) in water (19 ml) and ice (48 g) was added dropwsie to a solution of 2-fluoro-5-methoxycarbonyloxy-4-methylaniline (3.93 g, 20 mmol) in 35% sulphuric acid (48 ml) at 0° C. The reaction mixture was stirred at 0° C. for 30 minutes and a solution of copper(II)nitrate trihydrate (467 g, 1.93 mol) in water (780 ml) followed by copper(II)oxide (2.65 g, 18 mmol) were added. The solution was extracted with ethyl acetate, the organic layer was washed with brine, dried (MgSO4) and the solvent removed by evaporation. The residue was purified by column chromatography eluting with petroleum ether/ethyl acetate (8/2) to give 2-fluoro-5-methoxycarbonyloxy-4-methylphenol (2.13 g, 53%) as a yellow solid. 1H NMR Spectrum (CDCl3): 2.13(s, 3H); 3.91(s, 3H); 5.11(br s, 1H); 6.78(d, 1H); 6.93(d, 1H)

Workup

additionwere added
extractionThe solution was extracted with ethyl acetate
washthe organic layer was washed with brine
dry with materialdried (MgSO4)
customthe solvent removed by evaporation
customThe residue was purified by column chromatography
washeluting with petroleum ether/ethyl acetate (8/2)

Sources & evidence

ORD record: ord-701bebb8bc794d5aa3ca72a5953dd5b3
Source dataset: uspto-grants-2001_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06258951B1

Reaction notes

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