Sodium Hydroxide → Methyl 3-hydroxy-5-nitrobenzoate

HRID 1515560Notes

Reaction equation

HRID 1515560 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6](B(O)O)[CH:7]=[C:8]([C:10]([O:12][CH3:13])=[O:11])[CH:9]=1)([O-:3])=[O:2].[OH-].[Na+].C(=O)(O)[O-:20].[Na+].OOS([O-])=O.[K+]>O.CC(C)=O>[OH:20][C:6]1[CH:7]=[C:8]([CH:9]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)[C:10]([O:12][CH3:13])=[O:11]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 516892Sodium BicarbonateHCID 27734923-(Methoxycarbonyl)-5-nitrophenylboronic Acid (contains varying amounts of Anhydride)HCID 23707502Potassium hydroxy sulfite

Product 1

HCID 239344Methyl 3-hydroxy-5-nitrobenzoateYield 130.9%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

3-Nitro-5-methoxycarbonylphenylboronic acid (225 mg, 1.0 mmol) was added to a vigorously stirred solution of sodium hydroxide (59 mg, 1.5 mmol) in water (15 mL), followed by sodium bicarbonate (681 mg, 8.1 mmol) and acetone (1 mL). Oxone® (543 mg, 0.88 mmol) was added slowly, keeping the temperature below 8° C. The reaction mixture was stirred 5 min and quenched with sodium bisulfite (600 mg). The reaction mixture was diluted with ethyl acetate and carefully acidified with concentrated hydrochloric acid. The reaction mixture was extracted with ethyl acetate (3×) and the combined organic layers were washed with water and brine and concentrated in vacuo to give 93A (258 mg, 100%) as a yellow solid. 1H NMR (400 MHz, CD3OD) δ ppm 3.95 (s, 3H) 7.74-7.78 (m, 1H) 7.78-7.83 (m, 1 H) 8.23-8.28 (m, 1H); LC/MS 198 (M+H).

Workup

  1. customthe temperature below 8° C
  2. customquenched with sodium bisulfite (600 mg)
  3. additionThe reaction mixture was diluted with ethyl acetate
  4. extractionThe reaction mixture was extracted with ethyl acetate (3×)
  5. washthe combined organic layers were washed with water and brine
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-be9a903d30ed4c0bba60bac3dd88d2a7
Source dataset
uspto-grants-2012_07
Patent number
US08222453B2

Reaction notes

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