Ethanol → Methyl 2-ethoxy-5-nitrobenzoate

HRID 1096582Notes

Reaction equation

HRID 1096582 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[C:15]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:16]=1.CCO.C(OC(N=NC(OC(C)C)=O)=O)(C)C>C1COCC1>[CH2:15]([O:1][C:2]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])[CH3:16]

Participants

6

Reactant 4

HCID 702EthanolHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 87041Methyl 5-nitrosalicylate

Product 1

HCID 43449037Methyl 2-ethoxy-5-nitrobenzoateYield 90.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Methyl 2-hydroxy-5-nitrobenzoate (11.82 g, 60 mmol), triphenylphosphine (17.29 g, 66 mmol) and EtOH (3.03 g, 3.85 ml, 66 mmol) were taken up in THF (150 ml) and cooled in ice. Di-isopropyl-azodicarboxylate (8.31 g, 10 ml, 66 mmol) was added carefully, and the reaction was stirred at RT for 1 hr. The reaction was concentrated in vacuo, and the residue was triturated with EtOAc (50 ml). The solid thus formed was collected by filtration, washed with MTBE and dried in vacuo to give 12.2 g of crude methyl 2-ethoxy-5-nitrobenzoate. The filtrate was evaporated in vacuo, and the resulting residue was triturated with EtOAc (25 ml). The resulting solid was collected by filtration, washed with MTBE and dried in vacuo to give 6.31 g of a second crop of crude methyl 2-ethoxy-5-nitrobenzoate. The combined portions of methyl 2-ethoxy-5-nitrobenzoate were taken up in hot IPA (50 ml) and cooled to RT. The resulting solid was collected by filtration, washed with MTBE and dried in vacuo to give pure methyl 2-ethoxy-5-nitrobenzoate (5.49 g, 40.5%) as a yellow solid.

Workup

  1. temperaturecooled in ice
  2. concentrationThe reaction was concentrated in vacuo
  3. customthe residue was triturated with EtOAc (50 ml)
  4. customThe solid thus formed
  5. filtrationwas collected by filtration
  6. washwashed with MTBE
  7. customdried in vacuo

Sources & evidence

ORD record
ord-4fcfef290db34923bc252349e44a57a8
Source dataset
uspto-grants-2012_03
Patent number
US08138357B2

Reaction notes

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