Nitric Acid → 3-Benzofurancarboxylic acid, 5-bromo-2-(4-fluorophenyl)-6-nitro-, ethyl ester

HRID 1776935Notes

Reaction equation

HRID 1776935 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:9][C:8]([C:10]3[CH:15]=[CH:14][C:13]([F:16])=[CH:12][CH:11]=3)=[C:7]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:6]=2[CH:22]=1.[N+:23]([O-])([OH:25])=[O:24]>C(Cl)(Cl)Cl>[Br:1][C:2]1[C:3]([N+:23]([O-:25])=[O:24])=[CH:4][C:5]2[O:9][C:8]([C:10]3[CH:11]=[CH:12][C:13]([F:16])=[CH:14][CH:15]=3)=[C:7]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:6]=2[CH:22]=1

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 67393171HCID 67393171, compound

Product 1

HCID 673936353-Benzofurancarboxylic acid, 5-bromo-2-(4-fluorophenyl)-6-nitro-, ethyl esterYield 66%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of ethyl 5-bromo-2-(4-fluorophenyl)benzofuran-3-carboxylate (50 g, 137.6 mmol) in CHCl3 (500 mL), fuming HNO3 (50 mL) was added dropwise at −15° C. and the mixture was stirred for 0.5 hour. The reaction mixture was poured into ice water and extracted with CH2Cl2. The organic layer was washed with a.q. sat. NaHCO3 and brine, after removed the most of solvent, the resulting residue was crystallized with petroleum ether/dichloromethane=20/1 to provide product of ethyl 5-bromo-2-(4-fluorophenyl)-6-nitrobenzofuran-3-carboxylate (35 g, yield: 66%). 1H-NMR (CDCl3, 400 MHz) δ 8.36 (s, 1H), 8.02˜8.04 (m, 3H), 7.13˜7.18 (m, 2H), 4.36˜4.41 (m, 2H), 1.37 (t, J=4.0 Hz, 3H). MS (M+H)+: 408/410.

Workup

  1. extractionextracted with CH2Cl2
  2. washThe organic layer was washed with a.q
  3. customsat. NaHCO3 and brine, after removed the most of solvent
  4. customthe resulting residue was crystallized with petroleum ether/dichloromethane=20/1

Sources & evidence

ORD record
ord-ddd1e1cacbc245c38fb91cbb89883dab
Source dataset
uspto-grants-2016_02
Patent number
US09265773B2

Reaction notes

Loading…