Potassium Carbonate → Methyl 7-(4-fluorophenyl)-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylate

HRID 1978574Notes

Reaction equation

HRID 1978574 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[S:11](=[O:13])(=[O:12])[CH2:10][CH2:9][C:8]([C:14]([O:16][CH3:17])=[O:15])=[CH:7][C:6]=2[CH:18]=1.B([O-])([O-])O[C:21]1[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=1.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.C(O)C.O.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>[F:27][C:24]1[CH:25]=[CH:26][C:21]([C:2]2[CH:3]=[CH:4][C:5]3[S:11](=[O:13])(=[O:12])[CH2:10][CH2:9][C:8]([C:14]([O:16][CH3:17])=[O:15])=[CH:7][C:6]=3[CH:18]=2)=[CH:22][CH:23]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 21995732Methyl 7-bromo-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylateHCID 867561584-Fluorophenyl borate

Product 1

HCID 21995794Methyl 7-(4-fluorophenyl)-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylateYield 62.8%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 86587398Ethanol toluene waterSolvent

Procedure

Under argon atmosphere, a mixture of methyl 7-bromo-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylate (1.0 g), 4-fluorophenyl borate (0.465 g) and potassium carbonate (0.84 g) in toluene/ethanol/water (30/3/3 ml) was stirred at room temperature for 1 hour. To the mixture was added tetrakistriphenylphosphinepalladium (0.17 g), and the mixture was refluxed for 20 hours, cooled, extracted with ethyl acetate, saturated brine, dried with magnesium sulfate and concentrated under reduced pressure. The residue was purified with column chromatography (ethyl acetate/hexane=1:1) and recrystallized from ethyl acetate/hexane=1:1 to give pale yellow crystals of methyl 7-(4-fluorophenyl)-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylate (656.3 mg).

Workup

  1. temperaturethe mixture was refluxed for 20 hours
  2. temperaturecooled
  3. extractionextracted with ethyl acetate, saturated brine
  4. dry with materialdried with magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified with column chromatography (ethyl acetate/hexane=1:1)
  7. customrecrystallized from ethyl acetate/hexane=1:1

Sources & evidence

ORD record
ord-d4606f473fb4420b9025bc0acdfcbd70
Source dataset
uspto-grants-2001_05
Patent number
US06235771B1

Reaction notes

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