Sodium Carbonate → Benzoic acid, 3-nitro-5-(4-pyridinyl)-, methyl ester

Temperature

90 °C

To a suspension of 3-bromo-5-nitrobenzoic acid 45.1.A (10.0 g, 40.7 mmol, available from Apollo) and pyridin-4-ylboronic acid (7.40 g, 60.9 mmol) in toluene (100 mL) was added 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (3.3 g, 4.07 mmol), and 2M Na2CO3 aqueous (100 mL). The mixture was stirred for 3 hours at 90° C. at which time the mixture was condensed. The residue was dissolved in water (200 mL) and washed with EtOAc (50 mL). The water layer was then condensed, the residue was triturated with methanol (200 mL), and then filtered. Sulfuric acid (5 mL) was then added to the mother liquor and stirred at reflux overnight. The mixture was then concentrated, neutralized with saturated aqueous NaHCO3 (100 mL), and extracted with DCM (2×100 mL). The combined organic layers were then concentrated to afford methyl 3-nitro-5-(pyridin-4-yl)benzoate 45.1.B (5.60 g, 53% yield) which was used in the next step without any further purification.

1. customcondensed
2. washwashed with EtOAc (50 mL)
3. customcondensed
4. customthe residue was triturated with methanol (200 mL)
5. filtrationfiltered
6. additionSulfuric acid (5 mL) was then added to the mother liquor
7. stirringstirred
8. temperatureat reflux overnight
9. concentrationThe mixture was then concentrated
10. extractionextracted with DCM (2×100 mL)
11. concentrationThe combined organic layers were then concentrated

ORD record

ord-5d10788a8d9d41b2bab4d42bb39959f7

Source dataset

uspto-grants-2014_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08785468B2