Potassium Phosphate, Dibasic → ethyl 3-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-2-carboxylate

HRID 623735Notes

Reaction equation

HRID 623735 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:12]=[CH:11][NH:10][C:9]=2[C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:4][CH:3]=1.OP([O-])([O-])=O.[K+].[K+].[C:25](S(Cl)(=O)=O)([F:28])([F:27])[F:26]>CCOC(C)=O.O.C1C=NC2C3N=CC=CC=3C=CC=2C=1.C1C=NC2C3N=CC=CC=3C=CC=2C=1.C1C=NC2C3N=CC=CC=3C=CC=2C=1.O.[Cl-].[Cl-].[Ru+2]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:12]=[C:11]([C:25]([F:28])([F:27])[F:26])[NH:10][C:9]=2[C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 24450Potassium Phosphate, DibasicHCID 79000Trifluoromethanesulfonyl chloride2×HCID 79327547Ethyl 3-(4-chlorophenyl)-1H-pyrrole-2-carboxylate

Product 1

HCID 86711826ethyl 3-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-2-carboxylateYield 288.4%

Reagents, catalysts & solvents 3

HCID 16212249dichlorotris(1,10-phenanthroline)-ruthenium(II) hydrateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

This reaction was carried out in 5 batches using the same procedure. To a mixture of ethyl 3-(4-chlorophenyl)-1H-pyrrole-2-carboxylate [for synthesis see ACI-01] (1.25 g, 5.01 mmol), K2HPO4 (2.62 g, 15 mmol) and dichlortris(1,10-phenanthroline)-ruthenium(II) hydrate (71 mg, 0.10 mmol) in argon degassed dry MeCN (35 mL) was added CF3SO2Cl (1.60 mL, 15 mmol). The reaction mixture was stirred for 16 h at room temperature adjacent to a fluorescent light bulb (E27-32W, 4000K, 65 mA). After 16 h, an additional amount of CF3SO2Cl (0.20 mL, 1.88 mmol) was added and the reaction mixture was stirred overnight at room temperature adjacent to a fluorescent light bulb. All reaction mixtures were combined and diluted with EtOAc (150 mL) and H2O was added. The aqueous layer was extracted with EtOAc (150 mL). The organic layers were combined and the solvent was evaporated to give an oil. The crude product was purified by flash chromatography (silica, gradient heptane/EtOAc, 1:0→1:1) to furnish the desired product (4.59 g, 58%).

Workup

  1. customdegassed dry MeCN (35 mL)
  2. customAll reaction mixtures
  3. additionwas added
  4. extractionThe aqueous layer was extracted with EtOAc (150 mL)
  5. customthe solvent was evaporated
  6. customto give an oil
  7. customThe crude product was purified by flash chromatography (silica, gradient heptane/EtOAc, 1:0→1:1)

Sources & evidence

ORD record
ord-592be9cc68064fd0961999e6f9fe138a
Source dataset
uspto-grants-2016_04
Patent number
US09302988B2

Reaction notes

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