Ethyl bromodifluoroacetate → HCID 23075290, compound

HRID 2076443Notes

Reaction equation

HRID 2076443 reaction equation
[CH2:1]([O:3][C:4](=[O:9])[C:5](Br)([F:7])[F:6])[CH3:2].I[C:11]1[CH:16]=[CH:15][C:14]([NH:17][C:18]([C:20]2[CH:29]=[CH:28][C:27]3[C:26]([CH3:31])([CH3:30])[CH2:25][CH2:24][C:23]([CH3:33])([CH3:32])[C:22]=3[CH:21]=2)=[O:19])=[CH:13][CH:12]=1>CS(C)=O.[NH4+].[Cl-].[Cu]>[CH3:30][C:26]1([CH3:31])[CH2:25][CH2:24][C:23]([CH3:32])([CH3:33])[C:22]2[CH:21]=[C:20]([C:18]([NH:17][C:14]3[CH:15]=[CH:16][C:11]([C:5]([F:7])([F:6])[C:4]([O:3][CH2:1][CH3:2])=[O:9])=[CH:12][CH:13]=3)=[O:19])[CH:29]=[CH:28][C:27]1=2

Participants

6

Reactant 2

HCID 69585Ethyl bromodifluoroacetateHCID 23497814HCID 23497814, compound

Product 1

HCID 23075290HCID 23075290, compoundYield 74.6%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 679Dimethyl SulfoxideSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
58 °C

Procedure

Under a nitrogen atmosphere ethylbromodifluoroacetate (0.244 mL, 1.90 mmol) was added to a suspension of 5,6,7,8-tetrahydro-N-(4-iodophenyl)-5,5,8,8-tetramethylnaphthalene-2-carboxamide 22 (826 mg, 1.90 mmol), powder copper (99.999%, 588 mg) in anhydrous DMSO (16.7 mL). The reaction mixture was stirred at 58° C. for 18 h. After cooling, the mixture was poured in aqueous NH4Cl 5% (150 mL). This mixture was extracted with EtOAc (5×150 mL). The organic layer was washed with aqueous NH4Cl 5% (3×100 mL), brine (3×100 mL), dried over MgSO4, filtered and evaporated. The crude product was purified by column chromatography using as eluent cyclohexane:EtOAc=95:5. Ethyl 2-(4-(5,6,7,8-tetrahydro-5,5,8,8-tetramethylnaphthalene-2-carboxamido)phenyl)-2,2-difluoroacetate 23 was obtained (0.61 g, 74.6% yield) as a white solid.

Workup

  1. temperatureAfter cooling
  2. extractionThis mixture was extracted with EtOAc (5×150 mL)
  3. washThe organic layer was washed with aqueous NH4Cl 5% (3×100 mL), brine (3×100 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude product was purified by column chromatography

Sources & evidence

ORD record
ord-0592555359c6431aa16b7f0c698cef15
Source dataset
uspto-grants-2011_04
Patent number
US07923579B2

Reaction notes

Loading…