Trimethylsilylacetylene → Ethyl 2-(4-fluoro-5-nitro-2-(2-(trimethylsilyl)ethynyl)phenyl)acetate

HRID 1930306Notes

Reaction equation

Br[C:2]1[CH:7]=[C:6]([F:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14].[CH3:18][Si:19]([C:22]#[CH:23])([CH3:21])[CH3:20]>CCN(CC)CC.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[F:8][C:6]1[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]([CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:2]([C:23]#[C:22][Si:19]([CH3:21])([CH3:20])[CH3:18])[CH:7]=1

Participants

Conditions

Temperature: 50 °C

Procedure

Ethyl 2-(2-bromo-4-fluoro-5-nitrophenyl)acetate (1.00 g, 3.27 mmol), PdCl2(PPh3)2 (115 mg, 0.16 mmol), CuI (44 mg, 0.23 mmol), and trimethylsilylacetylene (0.7 mL, 4.9 mmol) were dissolved in Et3N (5 mL). The mixture was immediately degassed by vacuum, and the flask was charged with N2. The mixture was heated overnight at 50° C. Water was added and then the solution was extracted with EtOAc (3×). The organic was washed with NH4Cl, brine and dried (MgSO4). The solvent was removed and then the residue was purified by silica gel column chromatography to obtain ethyl 2-(4-fluoro-5-nitro-2-(2-(trimethylsilyl)ethynyl)phenyl)acetate (0.66 g, 62% yield).

Workup

customThe mixture was immediately degassed by vacuum
additionthe flask was charged with N2
additionWater was added
extractionthe solution was extracted with EtOAc (3×)
washThe organic was washed with NH4Cl, brine
dry with materialdried (MgSO4)
customThe solvent was removed
customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record: ord-a432874ef411409fa020589fb6343476
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08188113B2

Reaction notes

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