Citric Acid → HCID 68959443, compound

HRID 2191702Notes

Reaction equation

HRID 2191702 reaction equation
[NH2:1][C:2]1[CH:14]=[C:13]([CH2:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:12]=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].I[C:24]1[CH:29]=[CH:28][C:27]2[O:30][CH2:31][O:32][C:26]=2[CH:25]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.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>[O:30]1[C:27]2[CH:28]=[CH:29][C:24]([NH:1][C:2]3[CH:14]=[C:13]([CH2:15][CH2:16][C:17]4[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=4)[CH:12]=[CH:11][C:3]=3[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])=[CH:25][C:26]=2[O:32][CH2:31]1

Participants

8

Reactant 4

HCID 311Citric AcidHCID 1386201-Iodo-3,4-methylenedioxybenzeneHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl2×HCID 58508624Tert-butyl 2-amino-4-phenethylbenzoate

Product 1

HCID 68959443HCID 68959443, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

To toluene 3.0 mL solution of tert-butyl 2-amino-4-phenethylbenzoate 0.10 g were added 1-iodo-3,4-methylenedioxybenzene 0.14 g,cesium carbonate 0.22 g, tris(dibenzylideneacetone)dipalladium(0) 3 mg and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 8 mg,and it was stirred at 110° C. for 24 hours. After the reaction mixture was cooled to room temperature, tris(dibenzylideneacetone)dipalladium(0) 3 mg and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 8 mg were added to it, and it was stirred at 110° C. for 24 hours. After the reaction mixture was cooled to room temperature, ethyl acetate and 10% citric acid aqueous solution were added to it. The organic layer was separated and collected,dried over anhydrous magnesium sulfate after washing with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The obtained residue was refined by silica gel column chromatography [Trikonex company, Flash Tube 2008, eluent; hexane:ethyl acetate=4:1] to give tert-butyl 2-((benzo-1,3-dioxol-5-yl)amino)-4-phenethylbenzoate. Trifluoroacetic acid 10 mL was added to the obtained tert-butyl 2-((benzo-1,3-dioxol-5-yl)amino)-4-phenethylbenzoate, and it was stirred at room temperature for 2 hours. The solvent was removed under reduced pressure, and the obtained residue was refined by reversed-phase silica gel column chromatography [eluent; 80-100% acetonitrile/0.1% trifluoroacetic acid aqueous solution] to give 2-((benzo-1,3-dioxol-5-yl)amino)-4-phenethylbenzoic acid 12 mg of white solid.

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. stirringwas stirred at 110° C. for 24 hours
  3. temperatureAfter the reaction mixture was cooled to room temperature
  4. customThe organic layer was separated
  5. washafter washing with saturated sodium chloride aqueous solution
  6. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-b521d15bb739430f881122087c3a18a1
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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