4-Nitrobenzoic Acid → Methyl [6-(4-nitrobenzoyl)-2H-1,3-benzodioxol-5-yl]acetate

HRID 442662Notes

Reaction equation

HRID 442662 reaction equation
[CH2:1]1[O:9][C:8]2[CH:7]=[CH:6][C:5]([CH2:10][C:11]([O:13][CH3:14])=[O:12])=[CH:4][C:3]=2[O:2]1.[N+:15]([C:18]1[CH:26]=[CH:25][C:21]([C:22](O)=[O:23])=[CH:20][CH:19]=1)([O-:17])=[O:16].O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.C([O-])([O-])=O.[K+].[K+]>C(Cl)CCl.O>[CH2:1]1[O:2][C:3]2[C:8](=[CH:7][C:6]([C:22](=[O:23])[C:21]3[CH:20]=[CH:19][C:18]([N+:15]([O-:17])=[O:16])=[CH:26][CH:25]=3)=[C:5]([CH2:10][C:11]([O:13][CH3:14])=[O:12])[CH:4]=2)[O:9]1

Participants

7

Reactant 4

HCID 61084-Nitrobenzoic AcidHCID 11430Potassium CarbonateHCID 14812Phosphorus oxide (P4O10)HCID 266588Methyl 2-(1,3-dioxaindan-5-yl)acetate

Product 1

HCID 404213Methyl [6-(4-nitrobenzoyl)-2H-1,3-benzodioxol-5-yl]acetateYield 50%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 962WaterSolvent

Procedure

To a solution of methyl 3,4-methylenedioxyphenylacetate (5.4 g, 28 mmol) in ClCH2CH2Cl (100 mL) was added 4-nitrobenzoic acid (7.2 g, 43 mmol) and P2O5 (18 g) at room temperature under argon. The mixture was refluxed for 28 h, cooled to room temperature, then cold water was added slowly. The resulting mixture was carefully neutralized with solid K2CO3, and extracted with 1:1 hexane/EtOAc (2×300 mL). The combined extracts were washed with water and brine, and dried over Na2SO4. The solvent was removed in vacuo and the resulting residue was separated by chromatography (3:1 hexane/EtOAc) to afford the title compound as a yellow solid (4.7 g, 14 mmol, 50%). 1H NMR (CDCl3) 8.32 (d, 2H, J=8.5), 7.92 (d, 2H, J=8.5), 6.85 (s, 1H), 6.81 (s, 1H), 6.07 (s, 2H), 3.88 (s, 2H), 3.63 (s, 3H).

Workup

  1. temperatureThe mixture was refluxed for 28 h
  2. extractionextracted with 1:1 hexane/EtOAc (2×300 mL)
  3. washThe combined extracts were washed with water and brine
  4. dry with materialdried over Na2SO4
  5. customThe solvent was removed in vacuo
  6. customthe resulting residue was separated by chromatography (3:1 hexane/EtOAc)

Sources & evidence

ORD record
ord-e7efa73de63944e1bb9d22e90b559737
Source dataset
uspto-grants-1999_04
Patent number
US05891871

Reaction notes

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