Dimethyl Sulfate → Salicylic acid, 4-nitro-, methyl ester

HRID 1040925Notes

Reaction equation

HRID 1040925 reaction equation
[OH:1][C:2]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].S(OC)(O[CH3:18])(=O)=O.C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[CH3:18][O:5][C:4](=[O:6])[C:3]1[CH:7]=[CH:8][C:9]([N+:11]([O-:13])=[O:12])=[CH:10][C:2]=1[OH:1]

Participants

5

Reactant 3

HCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 692664-Nitrosalicylic acid

Product 1

HCID 139539Salicylic acid, 4-nitro-, methyl esterYield 98.9%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of 2-hydroxy-4-nitrobenzoic acid (8.0 g, 0.0424 mol) in acetone (240 mL) and dimethyl sulfate (4.48 mL, 0.047 mol) was added potassium carbonate (5.85 g, 0.044 mol), stirred for 24 hrs. and evaporated. To the residue was added ethyl acetate and 2 N HCl (pH 3). The ethyl acetate extract was washed, dried (MgSO4) and evaporated to give 2-hydroxy-4-nitro-benzoic acid methyl ester (8.27 g) as a yellow solid; 1H-NMR (DMSO-d6) δ 11.62 (s, 1H), 9.74 (s, 1H), 8.76 (d, 2H), 8.70-2 (d, 2H), 8.29 (s, 1H), 8.11 (s, 1H), 7.71-7 (m, 2H), 7.55 (m, 2H), 8.33-5 (d, 1H), 7.15-9 (t, 1H), 4.27 (s, 2H), 2.80 (s, 3H); LC/MS (ESI+): 228 (M+2Na)

Workup

  1. customand evaporated
  2. additionTo the residue was added ethyl acetate and 2 N HCl (pH 3)
  3. extractionThe ethyl acetate extract
  4. washwas washed
  5. dry with materialdried (MgSO4)
  6. customevaporated

Sources & evidence

ORD record
ord-883f9ac455d54eec8c32c382a2cbcab4
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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