Sulfuric Acid → Methyl 3-hydroxy-4-methoxy-2-nitrobenzoate

HRID 2381054Notes

Reaction equation

HRID 2381054 reaction equation
S(=O)(=O)(O)O.[OH:6][C:7]1[CH:8]=[C:9]([CH:14]=[CH:15][C:16]=1[O:17][CH3:18])[C:10]([O:12][CH3:13])=[O:11].[N+:19]([O-])([O:21]C(C)C)=[O:20]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.ClCCl>[OH:6][C:7]1[C:8]([N+:19]([O-:21])=[O:20])=[C:9]([CH:14]=[CH:15][C:16]=1[O:17][CH3:18])[C:10]([O:12][CH3:13])=[O:11]

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 15575Isopropyl nitrateHCID 4056967Methyl 3-hydroxy-4-methoxybenzoate

Product 1

HCID 59268115Methyl 3-hydroxy-4-methoxy-2-nitrobenzoate

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 6344DichloromethaneSolvent

Procedure

Sulfuric acid (3.0 mL, 56 mmol) was added dropwise over 2 min to a solution of methyl 3-hydroxy-4-methoxybenzoate (3.64 g, 20 mmol), tetrabutylammonium hydrogensulfate (340 mg, 1.0 mmol), isopropyl nitrate (5.0 mL, 50 mmol), and dichloromethane (40 mL) at 0° C. The reaction was allowed to warm to rt, maintained for 45 min, and then quenched with ice water (100 mL). This mixture was extracted with dichloromethane (250 mL×2). The combined extracts were dried, filtered, concentrated, and purified by silica gel chromatography (4:1→3:7; hexanes:ethyl acetate) to give methyl 3-hydroxy-4-methoxy-2-nitrobenzoate: MS (ESI): 228.4.

Workup

  1. temperaturemaintained for 45 min
  2. customquenched with ice water (100 mL)
  3. extractionThis mixture was extracted with dichloromethane (250 mL×2)
  4. customThe combined extracts were dried
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified by silica gel chromatography (4:1→3:7; hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-899b6b822b6f42efb42011ad5307c699
Source dataset
uspto-grants-2012_09
Patent number
US08258154B2

Reaction notes

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