Citric Acid → HCID 67342201, compound

HRID 1673551Notes

Reaction equation

HRID 1673551 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1)([O-:3])=[O:2].[H-].[Na+].C(P(C(C)(C)C)C1C=CC=CC=1C1C(C(C)C)=CC(C(C)C)=CC=1C(C)C)(C)(C)C.[C:43]([NH:51][C:52]1[CH:64]=[C:63](Br)[CH:62]=[CH:61][C:53]=1[C:54]([O:56][C:57]([CH3:60])([CH3:59])[CH3:58])=[O:55])(=[O:50])[C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1.F[B-](F)(F)F.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C.C1(C)C=CC=CC=1>[C:43]([NH:51][C:52]1[CH:64]=[C:63]([O:10][C:7]2[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=2)[CH:62]=[CH:61][C:53]=1[C:54]([O:56][C:57]([CH3:59])([CH3:60])[CH3:58])=[O:55])(=[O:50])[C:44]1[CH:45]=[CH:46][CH:47]=[CH:48][CH:49]=1

Participants

11

Reactant 6

HCID 311Citric AcidHCID 9804-NitrophenolHCID 24758Sodium hydrideHCID 11618717Di-tert-butyl(2',4',6'-tris(propan-2-yl)-(1,1'-biphenyl)-2-yl)phosphaneHCID 44558591Tri-t-butylphosphine fluoroborateHCID 67343005Tert-butyl 2-(benzamido)-4-bromobenzoate

Product 1

HCID 67342201HCID 67342201, compoundYield 27.8%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

31 mg of 4-nitrophenol was added to 1.0 mL of toluene suspension containing of 8.9 mg of 60% sodium hydride at room temperature, and the resulting mixture was heated to reflux under nitrogen atmosphere for 15 minutes. After the reaction mixture was cooled to room temperature, 0.5 mL of toluene solution containing 3.8 mg of 2-(di-tert-butylphosphino)-2′,4′,6′-triisopropylbiphenyl, 1.3 mg of palladium acetate and 56 mg of tert-butyl 2-(benzamido)-4-bromobenzoate were added and the resulting mixture was heated to reflux under nitrogen atmosphere for 3 hours. After the reaction mixture was cooled to room temperature, 1.3 mg of tri-tert-butylphosphine tetrafluoroborate and 4.1 mg of tris(dibenzylideneacetone)dipalladium(0) were added and the resulting mixture was heated to reflux under nitrogen atmosphere for 4 hours. After the reaction mixture was cooled to room temperature, 10% citric acid aqueous solution and ethyl acetate were added and insoluble were removed by filtration. The organic layer was separated and dried over anhydrous magnesium sulfate after washed with a saturated sodium chloride aqueous solution, and the solvent was evaporated under reduced pressure. The obtained residue was purified with silica gel column chromatography [PSQ100B (spherical) manufactured by Fuji Silysia chemical Ltd., eluent; hexane:ethyl acetate=10:1] to obtain 18 mg of tert-butyl 2-(benzamido)-4-(4-nitrophenoxy)benzoate as white solid.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux under nitrogen atmosphere for 15 minutes
  3. additionwere added
  4. temperaturethe resulting mixture was heated
  5. temperatureto reflux under nitrogen atmosphere for 3 hours
  6. temperatureAfter the reaction mixture was cooled to room temperature
  7. temperaturethe resulting mixture was heated
  8. temperatureto reflux under nitrogen atmosphere for 4 hours
  9. temperatureAfter the reaction mixture was cooled to room temperature
  10. custominsoluble were removed by filtration
  11. customThe organic layer was separated
  12. dry with materialdried over anhydrous magnesium sulfate
  13. washafter washed with a saturated sodium chloride aqueous solution
  14. customthe solvent was evaporated under reduced pressure
  15. customThe obtained residue was purified with silica gel column chromatography [PSQ100B (spherical) manufactured by Fuji Silysia chemical Ltd., eluent; hexane:ethyl acetate=10:1]

Sources & evidence

ORD record
ord-a7030351bc174803ac2f35dee0bb1f2b
Source dataset
uspto-grants-2011_08
Patent number
US07999132B2

Reaction notes

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