Phosphoric Acid → 2,2-Dimethyl-5-phenyl-4H-(1,3)benzodioxin-4-one

HRID 865918Notes

Reaction equation

HRID 865918 reaction equation
[CH3:1][C:2]1([CH3:21])[O:7][C:6]2[CH:8]=[CH:9][CH:10]=[C:11](OS(C(F)(F)F)(=O)=O)[C:5]=2[C:4](=[O:20])[O:3]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:30]1(B(OC(C)C)OC(C)C)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.P(=O)(O)(O)O>CN(C)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.O>[CH3:1][C:2]1([CH3:21])[O:7][C:6]2[CH:8]=[CH:9][CH:10]=[C:11]([C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[C:5]=2[C:4](=[O:20])[O:3]1

Participants

8

Reactant 4

HCID 1004Phosphoric AcidHCID 62657Potassium Phosphate, TribasicHCID 569210Bis(1-methylethyl) B-phenylboronateHCID 108927482,2-Dimethyl-4-oxo-4H-benzo[D][1,3]dioxin-5-YL trifluoromethanesulfonate

Product 1

HCID 152794362,2-Dimethyl-5-phenyl-4H-(1,3)benzodioxin-4-oneYield 57%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

0.23 g (0.2 mmol) of tetrakistriphenylphosphinepalladium is added under nitrogen to a solution of 2.93 g (9 mmol) of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzodioxin-4-one in 50 ml of dimethylformamide, the mixture is stirred for a few minutes and 2.97 g (14 mmol) of potassium phosphate and 2.04 g (9.9 mmol) of diisopropyl phenylboronate are then added. The mixture is heated to 100° C. until conversion is complete (about 16 h). After cooling, the reaction solution is poured into a mixture of 250 ml of water and 6 g of orthophosphoric acid and extracted three times with methyl tert-butyl ether, and the combined organic phases are washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. 2.6 g of a dark oil remain, which is chromatographed on silica gel using toluene/acetone. 1.3 g (57%) of a colorless solid are obtained, m.p. 158°-163° C. (recrystallized from hexane).

Workup

  1. custom(about 16 h)
  2. temperatureAfter cooling
  3. extractionextracted three times with methyl tert-butyl ether
  4. washthe combined organic phases are washed with water and saturated sodium chloride solution
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated
  7. customwhich is chromatographed on silica gel

Sources & evidence

ORD record
ord-4a87ec803e4d4eb5a464335b3e38176e
Source dataset
uspto-grants-1996_10
Patent number
US05569640

Reaction notes

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