Benzocaine → Ethyl 4-((3-aminophenyl)amino)benzoate

HRID 1354977Notes

Reaction equation

HRID 1354977 reaction equation
[NH2:1][C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].Br[C:20]1[CH:21]=[C:22]([CH:24]=[CH:25][CH:26]=1)[NH2:23]>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]>[NH2:23][C:22]1[CH:21]=[C:20]([NH:1][C:2]2[CH:3]=[CH:4][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:11][CH:12]=2)[CH:26]=[CH:25][CH:24]=1

Participants

5

Reactant 3

HCID 2337BenzocaineHCID 11430Potassium CarbonateHCID 115623-Bromoaniline

Product 1

HCID 21106132Ethyl 4-((3-aminophenyl)amino)benzoateYield 80.4%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

An oven-dried resealable schlenk tube containing a stir bar was charged with Pd2(dba)3 (4.6 mg, 0.005 mmol), 2-ditbutylphosphino-2′,4′,6′-triisopropylbiphenyl (17.0 mg, 0.04 mmol), ethyl 4-aminobenzoate (125 mg, 0.75 mmol) and K2CO3 (173 mg, 1.25 mmol). The tube was capped with a rubber septum, evacuated and backfilled with argon. 3-Bromoaniline (56 μL, 0.5 mmol) and tbutanol (1 mL) were added through the septum via syringe. The septum was replaced with a Teflon screw cap. The schlenk tube was sealed and put into a pre-heated oil bath at 80° C. The reaction mixture was stirred for 11 h, allowed to cool down to room temperature and filtered through celite with ethyl acetate. The filtrate was concentrated under reduced pressure. Chromatography on silica gel column with 4:1 hexane:ethyl acetate gave 103 mg (80%) of the title compound as a pale yellow oil.

Workup

  1. additionAn oven-dried resealable schlenk tube containing a stir bar
  2. customThe tube was capped with a rubber septum
  3. customevacuated
  4. customscrew cap
  5. customThe schlenk tube was sealed
  6. customput into a pre-heated oil bath at 80° C
  7. filtrationfiltered through celite with ethyl acetate
  8. concentrationThe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-8701cd6c6c1a41afa7ee7824b3af22b0
Source dataset
uspto-grants-2007_05
Patent number
US07223879B2

Reaction notes

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