Water → 1-(2-Amino-5-bromophenyl)-2,2,2-trifluoroethanone

A solution of 1-(5-bromo-2-fluorophenyl)-2,2,2-trifluoroethanone (6.67 g, 24.6 mmol, Intermediate 8, step a) in DMSO (6.2 mL) was treated with NaN3 (1.76 g, 27.0 mmol) and stirred under air (lightly capped) at 95° C. for 1 hour. The brownish-red opaque reaction was then cooled to room temperature on an ice bath, diluted with EtOAc (49 mL), treated with SnCl2-dihydrate (6.66 g, 29.5 mmol) in several portions over ˜30 sec followed by water (1.33 mL, 73.8 mmol), and the mixture was stirred at room temperature for 30 min. The reddish solution with heavy off-white particulates was then treated with anhydrous Na2SO4 (˜6 g; ˜40 mmol; ˜400 mmol water capacity) and stirred vigorously for a few minutes. The mixture was then filtered over a bed of Celite®, and the cloudy orange filtrate was dry load flash chromatographed (˜60 g silica gel) with a heptane to 50% DCM/heptane gradient to provide the title compound as an orange oil that crystallized upon standing.

1. customlightly capped) at 95° C. for 1 hour
2. customThe brownish-red opaque reaction
3. stirringthe mixture was stirred at room temperature for 30 min
4. stirringstirred vigorously for a few minutes
5. filtrationThe mixture was then filtered over a bed of Celite®
6. customthe cloudy orange filtrate was dry load flash
7. customchromatographed (˜60 g silica gel) with a heptane to 50% DCM/heptane gradient

ORDレコード

ord-2d8d3a4a5a534f8aa68e068d2ae1916b

出典データセット

uspto-grants-2016_04

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US09309222B2