4-Aminobenzoic Acid → 4-(4-Butyl-phenylamino)-benzoic acid

HRID 1354966Notes

Reaction equation

HRID 1354966 reaction equation
[OH-].[K+].[NH2:3][C:4]1[CH:12]=[CH:11][C:7]([C:8]([OH:10])=[O:9])=[CH:6][CH:5]=1.[CH2:13]([C:17]1[CH:22]=[CH:21][C:20](Cl)=[CH:19][CH:18]=1)[CH2:14][CH2:15][CH3:16]>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].CC1C=CC(C(C2C=CC(C)=CC=2)C(=O)C(C)C)=CC=1.CC(O)(C)C>[CH2:13]([C:17]1[CH:22]=[CH:21][C:20]([NH:3][C:4]2[CH:12]=[CH:11][C:7]([C:8]([OH:10])=[O:9])=[CH:6][CH:5]=2)=[CH:19][CH:18]=1)[CH2:14][CH2:15][CH3:16]

Participants

7

Reactant 3

HCID 9784-Aminobenzoic AcidHCID 14797Potassium HydroxideHCID 524314Benzene, 1-butyl-4-chloro-

Product 1

HCID 112886654-(4-Butyl-phenylamino)-benzoic acidYield 92.1%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 120407443-Methyl-1,1-bis(4-methylphenyl)-2-butanoneCatalystHCID 6386tert-ButanolSolvent2×

Conditions

Temperature
100 °C

Procedure

An oven-dried resealable Schlenk flask was evacuated and backfilled with argon. The flask was charged with Pd2 dba3 (9.2 mg, 0.01 mmol, 2 mol % Pd), Ligand 1 (19 mg, 0.04 mmol, 4 mol %), pulverized KOH (168 mg, 3.0 mmol), and 4-amino-benzoic acid (165 mg, 1.2 mmol). The flask was evacuated and backfilled with argon (3×) and then capped with a rubber septum. To the flask was added t-BuOH (2.0 mL), 4-n-butylchlorobenzene (168 mg, 1.0 mmol) and t-BuOH (0.5 mL). The septum was replaced with a Teflon screwcap, the flask was sealed, and the mixture was heated to 100° C. with stirring until the starting aryl chloride was consumed by GC analysis (3 h). The reaction was cooled to room temperature, diluted with 5% aq. NaOH and extracted with Et2O. The aqueous layer was cooled to 0° C. and acidified with HCl (12.0 M) until pH ˜4. The aqueous layer was extracted with Et2O, dried over anh. MgSO4, filtered, and concentrated under reduced pressure to give crude product (248 mg). The product was purified by re-crystallizing in hot hexanes/chloroform to give faint brown platelets (209 mg, 78%).

Workup

  1. customAn oven-dried resealable Schlenk flask was evacuated
  2. customThe flask was evacuated
  3. customcapped with a rubber septum
  4. customthe flask was sealed
  5. customwas consumed by GC analysis (3 h)
  6. temperatureThe reaction was cooled to room temperature
  7. additiondiluted with 5% aq. NaOH
  8. extractionextracted with Et2O
  9. temperatureThe aqueous layer was cooled to 0° C.
  10. extractionThe aqueous layer was extracted with Et2O
  11. dry with materialdried over anh. MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-ff7c2d0badca4d598d83ce0841b36257
Source dataset
uspto-grants-2007_05
Patent number
US07223879B2

Reaction notes

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