Phenylacetylene → HCID 18972712, compound

HRID 2394248Notes

Reaction equation

HRID 2394248 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)#[CH:2].C([Mg]Br)C.[NH2:13][C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][C:15]=1[C:21](=[O:26])[C:22]([Cl:25])([F:24])[F:23]>CCOCC.C1COCC1>[NH2:13][C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][C:15]=1[C:21]([OH:26])([C:2]#[C:1][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)[C:22]([Cl:25])([F:23])[F:24]

Participants

6

Reactant 3

HCID 10821PhenylacetyleneHCID 18972705HCID 18972705, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 18972712HCID 18972712, compoundYield 71.5%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a 100 mL, 3 necked, oven dried round bottomed flask, with a stirring bar, argon inlet, reflux condenser, and a septum was added ethynyl benzene (2.13 g, 20.83 mmol), dry THF (50 mL) and ethyl magnesium bromide (6.94 mL of a 3.0M solution in ether). This mixture was aged 2 h at ambient temperature then a solution of 1-(2-amino-5-chlorophenyl)-2-chloro-2,2-difluoroethanone (1.00 g, 4.17 mmol) in THF (6 mL) was added with a syringe. The resulting orange-red solution was stirred at ambient temperature for 21.5 h. The reaction was quenched by addition of 1N HCl (50 mL) then diluted with EtOAc. The solution was then made basic with concentrated NH4OH and the layers were separated. The organic phase was washed with water and brine. Drying (MgSO4), filtration, removal of the solvent in vacuo, and chromatography on silica gel using 20% EtOAc in hexane as eluant gave 1.02 g of (+/-) 2-(2-amino-5-chlorophenyl)-4-phenyl-1-chloro-1,1-difluoro-3-butyn-2-ol as an off white solid. 1H NMR (CDCl3): δ 4.42 (br s, 2H), 5.10 (br s, 1H), 6.65 (d, 1H, J=8.5 Hz), 7.15 (dd, 1H, J=2.4, 8.5 Hz), 7.38 (m, 3H), 7.55 (m, 2H), 7.70 (d, J=2.4 Hz).

Workup

  1. customTo a 100 mL, 3 necked, oven dried round bottomed flask
  2. temperaturewith a stirring bar, argon inlet, reflux condenser
  3. customThe reaction was quenched by addition of 1N HCl (50 mL)
  4. additionthen diluted with EtOAc
  5. customthe layers were separated
  6. washThe organic phase was washed with water and brine
  7. customDrying
  8. filtration(MgSO4), filtration, removal of the solvent in vacuo, and chromatography on silica gel using 20% EtOAc in hexane as eluant

Sources & evidence

ORD record
ord-6969a5807f8a41c3bc0a1a5b19b641a0
Source dataset
uspto-grants-1998_09
Patent number
US05811423

Reaction notes

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