Potassium Carbonate → 7-(3-Chloro-4-methoxy-phenyl)-2,2-difluoro-benzo[1,3]dioxole-5-carboxylic Acid Methyl Ester

HRID 1475804Notes

Reaction equation

HRID 1475804 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:15]=[C:14](B2OCC(C)(C)CO2)[C:8]2[O:9][C:10]([F:13])([F:12])[O:11][C:7]=2[CH:6]=1)=[O:4].Br[C:25]1[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[C:27]([Cl:33])[CH:26]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH3:1][O:2][C:3]([C:5]1[CH:15]=[C:14]([C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[C:27]([Cl:33])[CH:26]=2)[C:8]2[O:9][C:10]([F:12])([F:13])[O:11][C:7]=2[CH:6]=1)=[O:4]

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 30165374-Bromo-2-chloroanisoleHCID 67170313Methyl 7-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-2,2-difluorobenzo[d][1,3]dioxole-5-carboxylate

Product 1

HCID 671707817-(3-Chloro-4-methoxy-phenyl)-2,2-difluoro-benzo[1,3]dioxole-5-carboxylic Acid Methyl EsterYield 16%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent

Procedure

1.9 g of 7-(5,5-Dimethyl-[1,3,2]dioxaborinan-2-yl)-2,2-difluoro-benzo[1,3]dioxole-5-carboxylic acid methyl ester (example YY, step 4), 1.5 g of 4-bromo-2-chloro-1-methoxybenzene, 152 mg of triphenylphosphine, 65 mg of palladium(II) acetate, and 2.4 g of K2CO3 were stirred in 30 ml of DMF and 3 ml of water under an argon atmosphere at 100° C. for 4 h. 200 ml of water were then added and the mixture was extracted three times using 100 ml of EA each. The organic layer was then dried using MgSO4 and evaporated. Chromatography on silica gel using EA/HEP 1:5 yielded 330 mg of the title compound, colorless oil. Rf (EA/HEP 1:5)=0.29

Workup

  1. extractionthe mixture was extracted three times
  2. customThe organic layer was then dried
  3. customevaporated

Sources & evidence

ORD record
ord-ee6bcfbdde9d46e694d6ee756da4c9be
Source dataset
uspto-grants-2015_04
Patent number
US09018383B2

Reaction notes

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