Sodium methanesulfinate → Methyl 3-methyl-6-(methylsulfonyl)-2-[4-(trifluoromethyl)phenyl]-4-quinolinecarboxylate

HRID 245241Notes

Reaction equation

HRID 245241 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[C:7]([C:12]1[CH:17]=[CH:16][C:15]([C:18]([F:21])([F:20])[F:19])=[CH:14][CH:13]=1)[C:6]([CH3:22])=[C:5]2[C:23]([O:25][CH3:26])=[O:24].[Na+].[CH3:28][S:29]([O-:31])=[O:30]>CS(C)=O.[Cu]I>[CH3:22][C:6]1[C:7]([C:12]2[CH:17]=[CH:16][C:15]([C:18]([F:21])([F:20])[F:19])=[CH:14][CH:13]=2)=[N:8][C:9]2[C:4]([C:5]=1[C:23]([O:25][CH3:26])=[O:24])=[CH:3][C:2]([S:29]([CH3:28])(=[O:31])=[O:30])=[CH:11][CH:10]=2

Participants

5

Reactant 2

HCID 2733271Sodium methanesulfinateHCID 67384046Methyl 6-bromo-3-methyl-2-[4-(trifluoromethyl)phenyl]-4-quinolinecarboxylate

Product 1

HCID 67384122Methyl 3-methyl-6-(methylsulfonyl)-2-[4-(trifluoromethyl)phenyl]-4-quinolinecarboxylate

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
120 °C

Procedure

Methyl 6-bromo-3-methyl-2-[4-(trifluoromethyl)phenyl]-4-quinolinecarboxylate (5.1 g, 12.02 mmol) was dissolved in dimethyl sulfoxide (60 mL) and copper(I) iodide (4.58 g, 24.04 mmol) and methanesulfinic acid sodium salt (2.455 g, 24.04 mmol) were added. The reaction vessel was evacuated and flushed with N2 three times, and heated at 120° C. overnight. The reaction mixture was diluted with CH2Cl2 and H2O, stirred for 30 min, filtered through the Celite, and washed with CH2Cl2. The filtrate was extracted three times with CH2Cl2, and the combined organic extracts were washed twice with brine, and dried over Na2SO4. The residue was purified via silica gel flash chromatography (0%-20% EtOAc/CH2Cl2) to afford the desired product as an off white solid (3.3 g, 65%). MS (m/z) 424.0 (M+H+).

Workup

  1. customThe reaction vessel was evacuated
  2. customflushed with N2 three times
  3. additionThe reaction mixture was diluted with CH2Cl2 and H2O
  4. filtrationfiltered through the Celite
  5. washwashed with CH2Cl2
  6. extractionThe filtrate was extracted three times with CH2Cl2
  7. washthe combined organic extracts were washed twice with brine
  8. dry with materialdried over Na2SO4
  9. customThe residue was purified via silica gel flash chromatography (0%-20% EtOAc/CH2Cl2)

Sources & evidence

ORD record
ord-19ba3ca096b34b5d85b82c89bc1bbdce
Source dataset
uspto-grants-2014_02
Patent number
US08658636B2

Reaction notes

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