1-Ethynyl-3-fluorobenzene → ethyl-6-Chloro-8-[(3-fluorophenyl)ethynyl]-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 855000Notes

Reaction equation

HRID 855000 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:7]([C:18]([F:21])([F:20])[F:19])[O:8][C:9]2[C:14]([CH:15]=1)=[CH:13][C:12]([Cl:16])=[CH:11][C:10]=2I)=[O:5])[CH3:2].[F:22][C:23]1[CH:24]=[C:25]([C:29]#[CH:30])[CH:26]=[CH:27][CH:28]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[CH2:1]([O:3][C:4]([C:6]1[CH:7]([C:18]([F:21])([F:20])[F:19])[O:8][C:9]2[C:14]([CH:15]=1)=[CH:13][C:12]([Cl:16])=[CH:11][C:10]=2[C:30]#[C:29][C:25]1[CH:26]=[CH:27][CH:28]=[C:23]([F:22])[CH:24]=1)=[O:5])[CH3:2]

Participants

5

Reactant 2

HCID 5202181-Ethynyl-3-fluorobenzeneHCID 21883552ethyl 6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 69517028ethyl-6-Chloro-8-[(3-fluorophenyl)ethynyl]-2-(trifluoromethyl)-2H-chromene-3-carboxylateYield 89.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Procedure

To 0.502 g (1.161 mmole) of ethyl-6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate was added 67 mg (0.060 mmole) tetrakis(triphenylphosphine)palladium(0), 22 mg (0.116 mmole) copper (I) iodide, 10 mL degassed toluene, 0.484 mL (3.48 mmole) degassed TEA, and 0.199 mL (1.74 mmole) 3-fluorophenylacetylene. The mixture was stirred overnight at room temperature. The mixture was concd and the resulting oil was purified using reverse phase chromatography to afford 0.440 g (89%) of a crystalline solid: 1H NMR (CDCl3/400 MHz) 1.35 (t,3H, J=6.8 Hz), 4.28-4.37 (m, 2H), 5.83 (q, 1H, J=6.8 Hz), 7.04-7.09 (m, 1H), 7.18 (d, 1H, J=2.4 Hz), 7.20-7.23 (m, 1H), 7.30-7.33 (m, 2H), 7.44 (d, 1H, J=2.8 Hz), 7.63 (s, 1H); MS (ES+) 425 (M+1, 100).

Workup

  1. customdegassed toluene, 0.484 mL (3.48 mmole)
  2. customthe resulting oil was purified

Sources & evidence

ORD record
ord-97cf7c47a7954bad89e6ebbbf6fb2fc8
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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