Aniline → 4-(Phenylamino)benzoic acid

BINAP (0.1 g, 0.16 mmol) and Pd(OAc)2 (0.014 g, 0.06 mmol) were mixed in toluene (10 mL) and this first solution was purged with argon for 15 minutes. Phenylamine (0.3 gm, 3.22 mmol), 4-bromo-benzoic acid (0.776 g, 3.89 mmol) and Cs2CO3 (3.14 gm, 9.66 mmol) were mixed in toluene (20 mL) and this second solution was purged with argon for 15 minutes. The first solution was added to the second solution, and the resulting mixture was heated to reflux overnight. Additional BINAP (0.1 g, 0.16 mmol) and Pd(OAc)2 (0.014 g, 0.06 mmol) were then added and the mixture heated to reflux for a further 6 hours. The toluene was removed and the residue was acidified with 10% HCl. The product was extracted with EtOAc and washed with brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure to afford 950 mg crude product. Purification by column chromatography (using silica gel of mesh size of 60-120 and 30:70 EtOAc:Hexane as the eluent) afforded 300 mg (43% yield) of 4-Phenylamino-benzoic acid.

1. customthis first solution was purged with argon for 15 minutes
2. customthis second solution was purged with argon for 15 minutes
3. additionThe first solution was added to the second solution
4. temperaturethe resulting mixture was heated
5. temperatureto reflux overnight
6. temperaturethe mixture heated
7. temperatureto reflux for a further 6 hours
8. customThe toluene was removed
9. extractionThe product was extracted with EtOAc
10. washwashed with brine
11. dry with materialThe organic layer was dried over Na2SO4
12. concentrationconcentrated under reduced pressure
13. customto afford 950 mg crude product
14. customPurification by column chromatography (

ORD record

ord-dc046030edfb4e27a6f42fdd749b9a4f

Source dataset

uspto-grants-2010_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07842696B2