4-Bromomethyl-3-nitrobenzoic acid → 4-Hydroxymethyl-3-nitrobenzoic acid

HRID 1678099Notes

Reaction equation

HRID 1678099 reaction equation
Br[CH2:2][C:3]1[CH:11]=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[CH:5][C:4]=1[N+:12]([O-:14])=[O:13].C([O-])(O)=[O:16].[Na+].C(Cl)(Cl)Cl.CO.CCOC(C)=O>CC#N>[OH:16][CH2:2][C:3]1[CH:11]=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[CH:5][C:4]=1[N+:12]([O-:14])=[O:13]

Participants

5

Reactant 3

HCID 1323864-Bromomethyl-3-nitrobenzoic acidHCID 516892Sodium BicarbonateHCID 21956348HCID 21956348, compound

Product 1

HCID 15018924-Hydroxymethyl-3-nitrobenzoic acidYield 80%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

In a round-bottom flask provided with reflux system, 4.5 g (17.3 mmols) of 4-bromomethyl-3-nitrobenzoic acid were placed, and an aqueous NaHCO3 saturated solution is added (135 mL). The reaction was stirred and allowed to stand at 90-95° C. The progress of the reaction was monitored by thin layer chromatography (TLC) (chloroform/MeOH/AcOEt, 100:50:0.1, v/v) or by HPLC of an acidified aliquot in a linear gradient 0-100% MeCN in 15 minutes in a Symmetry C18 column (150×4.6 mm×5 μm, 100 Å, Waters) retention time for the final product: 7.12 min; retention time for the initial product: 10.39 min. The reaction was completed in 30 minutes. The solution obtained was hot filtered and the reaction was quenched with HCl (12N) to a pH between 1-2 and was extracted with AcOEt (3×100 mL), the different organic fractions were combined, washed with a satured NaCl aqueous solution and dried over MgSO4 anh. The AcOEt was evaporated in vacuo. The product was obtained as a pale yellow solid in a 80% yield. The product has been characterized by HPLC (tr) 7.12 min (linear gradient 0-100% in 15 minutes), HPLC-MS (196 Da) and Rf=0.3 by TLC (Chloroform/MeOH/AcOEt, 100:50:0.1, v/v), NMR-1H 400 MHz in CD3OD: Signals: 2H: singlet 4.98 ppm, 1H: doublet, 7.96 ppm (J: 21 Hz), 1H: doublet of doublets, 8.26 ppm (4 Hz, 20 Hz), 1H: doublet, 8.56 ppm (4 Hz).

Workup

  1. customIn a round-bottom flask provided
  2. customto stand at 90-95° C

Sources & evidence

ORD record
ord-2cb229424e464409a16e4fe2a0637407
Source dataset
uspto-grants-2011_08
Patent number
US08008492B2

Reaction notes

Loading…