Hexane → HCID 70014587, compound

HRID 430478Notes

Reaction equation

HRID 430478 reaction equation
[H-].[Na+].[N+:3]([C:6]1[CH:7]=[C:8]([C:12](=[O:19])[CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH:9]=[CH:10][CH:11]=1)([O-:5])=[O:4].[CH2:20](Br)[CH:21]=[CH:22][CH3:23].CCCCCC>C1COCC1>[CH2:20]([CH:13]([C:12](=[O:19])[C:8]1[CH:9]=[CH:10][CH:11]=[C:6]([N+:3]([O-:5])=[O:4])[CH:7]=1)[C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH:21]=[CH:22][CH3:23]

Participants

6

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 104078Ethyl 3-(m-nitrophenyl)-3-oxopropionateHCID 1224142-Butene, 1-bromo-

Product 1

HCID 70014587HCID 70014587, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A 60% dispersion of NaH in mineral oil (917 mg, 22.9 mmol) was added over 20 min to a solution of ethyl 3-nitro-β-oxobenzenepropanoate (5.00 g, 21.1 mmol) in THF (50 mL) at such a rate to maintain a gentle reflux. The mixture was stirred at 25° for 30 min and a solution of crotyl bromide (2.95 g, 21.9 mmol) in THF (15 mL) was added over 50 min. The reaction mixture was stirred at 25° for 45 min and then heated at reflux for 16 h. Hexane (100 mL) was added to the cooled mixture. The resulting suspension was filtered and the filtrate was concentrated under reduced pressure. The residue was dissolved in EtOAc and the resulting solution was washed with aqueous 10% citric acid (2×), aqueous saturated NaHCO3 (2×) and brine then was dried (MgSO4) and concentrated under reduced pressure. The residue was purified by flash chromatography (40-63μ silica gel, hexane:EtOAc, 9:1) to afford ethyl α-(2-butenyl)-3-nitro-β-oxobenzenepropanoate (4.60 g, 75% yield):

Workup

  1. temperatureto maintain a gentle reflux
  2. stirringThe reaction mixture was stirred at 25° for 45 min
  3. temperatureheated
  4. temperatureat reflux for 16 h
  5. filtrationThe resulting suspension was filtered
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. dissolutionThe residue was dissolved in EtOAc
  8. washthe resulting solution was washed with aqueous 10% citric acid (2×), aqueous saturated NaHCO3 (2×) and brine
  9. dry with materialthen was dried (MgSO4)
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by flash chromatography (40-63μ silica gel, hexane:EtOAc, 9:1)

Sources & evidence

ORD record
ord-9daf679ff96d4331a151bc6477df223f
Source dataset
uspto-grants-2001_11
Patent number
US06323202B1

Reaction notes

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