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

HRID 1687232Notes

Reaction equation

HRID 1687232 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-0d4da4d25d574fa2aee615a0ae7f3204
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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