Nitric Acid → Benzyl 5-(benzyloxy)-4-methoxy-2-nitrobenzoate

HRID 61640Notes

Reaction equation

HRID 61640 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:22]=[CH:23][C:24]=1[O:25][CH3:26])[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+:27]([O-])([OH:29])=[O:28].[OH-].[Na+].C([O-])(O)=O.[Na+]>CC(OC(C)=O)=O>[CH2:1]([O:8][C:9]1[C:24]([O:25][CH3:26])=[CH:23][C:22]([N+:27]([O-:29])=[O:28])=[C:11]([CH:10]=1)[C:12]([O:14][CH2:15][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 14798Sodium Hydroxide2×HCID 516892Sodium BicarbonateHCID 22070447Benzyl 3-(benzyloxy)-4-methoxybenzoate

Product 1

HCID 59362000Benzyl 5-(benzyloxy)-4-methoxy-2-nitrobenzoateYield 93%

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Procedure

To a solution of benzyl 3-(benzyloxy)-4-methoxybenzoate (6.32 g, 18.1 mmol) in Ac2O (62 mL) cooled to −10° C. under an atmosphere of N2 was added fuming HNO3 (1.5 mL, 37.1 mmol) in one portion. Stirring was continued at −10° C. for 10 minutes, then at RT for 3 hours. The reaction mixture was carefully poured into ice-water and the pH adjusted to ca. pH=5 with 5N NaOH, sat. NaHCO3 and 0.5 NaOH. The mixture was extracted with CH2Cl2 (3×200 mL). The combined organics were dried (Na2SO4), filtered and concentrated in vacuo. The residue was azeotroped with heptane to give benzyl 5-(benzyloxy)-4-methoxy-2-nitrobenzoate as red colored oil (6.55 g, 16.7 mmol, 93%).

Workup

  1. waitat RT for 3 hours
  2. extractionThe mixture was extracted with CH2Cl2 (3×200 mL)
  3. dry with materialThe combined organics were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was azeotroped with heptane

Sources & evidence

ORD record
ord-d8b566cb3796403ca89b43a01101efa7
Source dataset
uspto-grants-2016_09
Patent number
US09440961B2

Reaction notes

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