Citric Acid → Tert-butyl 2-(benzamido)-4-(2,4-dichlorophenoxy)benzoate

HRID 1673563

반응식

HRID 1673563 반응식
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[OH:9].[H-].[Na+].[C:12]([NH:20][C:21]1[CH:33]=[C:32](Br)[CH:31]=[CH:30][C:22]=1[C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])(=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.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(O)(=O)CC(CC(O)=O)(C(O)=O)O>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:12]([NH:20][C:21]1[CH:33]=[C:32]([O:9][C:3]2[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=2[Cl:1])[CH:31]=[CH:30][C:22]=1[C:23]([O:25][C:26]([CH3:28])([CH3:29])[CH3:27])=[O:24])(=[O:19])[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

참가 물질

9

반응물 5

HCID 311Citric AcidHCID 84492,4-Dichlorophenol2회HCID 24758Sodium hydride2회HCID 11618717Di-tert-butyl(2',4',6'-tris(propan-2-yl)-(1,1'-biphenyl)-2-yl)phosphaneHCID 67343005HCID 67343005, 화합물

생성물 1

HCID 67342198Tert-butyl 2-(benzamido)-4-(2,4-dichlorophenoxy)benzoate

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매2회HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

실험 절차

91 mg of 2,4-dichlorophenol was added to 2.1 mL of toluene suspension containing 22 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, 70 mg of tert-butyl 2-(benzamido)-4-bromobenzoate, 4.7 mg of 2-(di-tert-butylphosphine)-2′,4′,6′-triisopropylbiphenyl and 6.8 mg of tris(dibenzylideneacetone)dipalladium(0) were added and the resulting mixture was heated to reflux under nitrogen atmosphere for 6 hours. After the reaction mixture was cooled to room temperature, 61 mg of 2,4-dichlorophenol, 15 mg of 60% sodium hydride, 4.7 mg of 2-(di-tert-butylphosphino)-2′, 4′,6′-triisopropylbiphenyl and 6.8 mg of tris(dibenzylideneacetone)dipalladium(0) were added and the resulting mixture was heated to reflux under nitrogen atmosphere for 10 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=20:1] to obtain tert-butyl 2-(benzamido)-4-(2,4-dichlorophenoxy)benzoate.

후처리

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux under nitrogen atmosphere for 15 minutes
  3. temperaturethe resulting mixture was heated
  4. temperatureto reflux under nitrogen atmosphere for 6 hours
  5. temperatureAfter the reaction mixture was cooled to room temperature
  6. temperaturethe resulting mixture was heated
  7. temperatureto reflux under nitrogen atmosphere for 10 hours
  8. temperatureAfter the reaction mixture was cooled to room temperature
  9. custominsoluble were removed by filtration
  10. customThe organic layer was separated
  11. dry with materialdried over anhydrous magnesium sulfate
  12. washafter washed with a saturated, sodium chloride aqueous solution
  13. customthe solvent was evaporated under reduced pressure
  14. customThe obtained residue was purified with silica gel column chromatography [PSQ100B (spherical) manufactured by Fuji Silysia Chemical Ltd., eluent; hexane; ethyl acetate=20:1]

출처 및 근거

ORD 기록
ord-190cf9f47dee4958835978e181a26b08
출처 데이터셋
uspto-grants-2011_08
특허 번호
US07999132B2

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