Methanol → 3-(Benzyloxy)-4-nitrobenzenecarboxylic acid

HRID 1505830Notes

Reaction equation

HRID 1505830 reaction equation
C[O:2][C:3](=[O:21])[C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[C:6]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:5]=1.CO.[OH-].[Na+].C(Cl)Cl>C1COCC1>[CH2:14]([O:13][C:6]1[CH:5]=[C:4]([CH:9]=[CH:8][C:7]=1[N+:10]([O-:12])=[O:11])[C:3]([OH:21])=[O:2])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 4

HCID 887Methanol2×HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 15054012Methyl 3-(benzyloxy)-4-nitrobenzoate

Product 1

HCID 225040433-(Benzyloxy)-4-nitrobenzenecarboxylic acidYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

Cmpd 2 (1.53 g, 1.0 eq) was dissolved in THF (52.8 mL) and MeOH (26.4 mL) in a round bottom flask, followed by addition of 2N NaOH (13.2 mL, 5.0 eq). The reaction was heated at 60° C. for 3 hours, occasionally opening the flask to release pressure. The reaction was monitored by TLC (5% MeOH:95% DCM). The resulting mixture was concentrated, and the residue was dissolved in water and acidified to pH=2-3 with 1N HCl. The acidic solution was extracted with AcOEt 3×, dried over Na2SO4, filtered and concentrated to afford Cmpd 3 as a light yellowish solid (1.25 g, 96% yield). Analytic: 1H NMR (DMSO d6, 500 mHz): δ 7.99 (d, 1H), 7.87 (s, 1H), 7.66 (dd, 1H), 7.46-7.40 (m, 4H), 7.33 (m, 1H), 5.39 (s, 2H). LCMS (C18, 2-98% CH3CN in 0.1% TFA/H2O over 6 min); Calculated mass for C14H11NO5 (M+H)+274.06. found by LC-MS 274.

Workup

  1. concentrationThe resulting mixture was concentrated
  2. dissolutionthe residue was dissolved in water
  3. extractionThe acidic solution was extracted with AcOEt 3×
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-6a8a73336e264d76b7fdfbc87c2e8368
Source dataset
uspto-grants-2015_12
Patent number
US09217022B2

Reaction notes

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