3-Nitrobenzaldehyde → Ethyl 3-(m-nitrophenyl)-3-oxopropionate

HRID 1062675Notes

Reaction equation

HRID 1062675 reaction equation
[Sn](Cl)Cl.[N+](=[CH:6][C:7]([O:9][CH2:10][CH3:11])=[O:8])=[N-].[N+:12]([C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][CH:22]=1)[CH:18]=[O:19])([O-:14])=[O:13]>C(Cl)Cl>[N+:12]([C:15]1[CH:16]=[C:17]([C:18](=[O:19])[CH2:6][C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH:20]=[CH:21][CH:22]=1)([O-:14])=[O:13]

Participants

5

Reactant 3

HCID 74493-NitrobenzaldehydeHCID 12192Ethyl diazoacetateHCID 24479Stannous Chloride2×

Product 1

HCID 104078Ethyl 3-(m-nitrophenyl)-3-oxopropionateYield 32%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of anhydrous tin (II) chloride (2.5 g, 13.2 mmol) in 150 mL of methylene chloride was added ethyl diazoacetate (8.3 g, 72.8 mmol). Then 3-nitrobenzaldehyde (10.0 g, 66.2 mmol) was added as a solid in small portions over 30 min. The resulting suspension was stirred at room temperature for 24 h. Additional tin (II) chloride (2.5 g) was added and the reaction was stirred an additional 24 h. The reaction was concentrated in vacuo, diluted with ethyl acetate, washed with water (2 times) and brine, dried (MgSO4) and concentrated. The residue was purified by flash chromatography (elution with 4:1 hexanes/ethyl acetate) to afford 5 g (32%) of the title compound. 1H NMR (CDCl3) (approximately 12:1 mixture of enol and keto tautomers, data for enol only) δ: 12.6 (s, 1H); 8.60 (t, 1H, J=1.8 Hz); 8.3 (m, 1H); 8.1 (m, 1H); 7.62 (t, 1H, J=7.9 Hz) 5.77 (s, 1H); 4.30 (q, 2H, J=7.2 Hz); 1.35 (t, 3H, J=7.2 Hz).

Workup

  1. stirringthe reaction was stirred an additional 24 h
  2. concentrationThe reaction was concentrated in vacuo
  3. additiondiluted with ethyl acetate
  4. washwashed with water (2 times) and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography (elution with 4:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-23de2f5fb5434dac99a4fccaae5973f2
Source dataset
uspto-grants-2005_11
Patent number
US06962935B2

Reaction notes

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