Nitromethane → HCID 45096327, compound

HRID 1796824Notes

Reaction equation

HRID 1796824 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]([C:9]#[N:10])=[CH:5][CH:6]([CH3:8])[CH3:7].[N+]([CH3:15])([O-])=O>C(#N)C>[CH3:1][O:2][C:3]([C:4]1([C:9]#[N:10])[CH2:15][CH:5]1[CH:6]([CH3:8])[CH3:7])=[O:11]

Participants

4

Reactant 2

HCID 6375NitromethaneHCID 53793275Methyl 2-cyano-4-methylpent-2-enoate

Product 1

HCID 45096327HCID 45096327, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 2-cyano-4-methyl-pent-2-enoic acid methyl ester (10.5 g, 68.3 mmol) in dry acetonitrile (60 mL) was added nitromethane (5.5 mL, 103 mmol) and a portionwise addition of alumina-supported potassium flouride (40% wt, 22 g). The reaction mixture was stirred under reflux for 2 hours and cooled to room temperature. The solid was removed by filtration through a short pad of celite and washed with acetonitrile. Excess of solvent was removed in vacuo and the residue was re-dissolved in ether. The ether layer was washed with water, brine, dried over sodium sulfate (Na2SO4) and concentrated in vacuo. The crude product was purified by flash column chromatography using hexanes/EtOAc (8:2) as an eluent to afford 1-cyano-2-isopropyl-cyclopropanecarboxylic acid methyl ester (7.7 g, 68%) as colorless oil: 1H NMR (300 MHz, CDCl3) δ 1.13 (t, J=7.2 Hz, 6H), 1.39–1.45 (m, 2H), 1.65–1.74 (m, 1H), 1.81 (dd, J=4.4, 8.9 Hz, 1H), 3.81 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 19.6, 21.8, 21.9, 25.3, 31.2, 39.3, 53.7, 117.6, 168.7.

Workup

  1. additiona portionwise addition of alumina-supported potassium flouride (40% wt
  2. temperatureunder reflux for 2 hours
  3. customThe solid was removed by filtration through a short pad of celite
  4. washwashed with acetonitrile
  5. customExcess of solvent was removed in vacuo
  6. dissolutionthe residue was re-dissolved in ether
  7. washThe ether layer was washed with water, brine
  8. dry with materialdried over sodium sulfate (Na2SO4)
  9. concentrationconcentrated in vacuo
  10. customThe crude product was purified by flash column chromatography

Sources & evidence

ORD record
ord-b64c92bddee74a4caf1cb5afb38abe8d
Source dataset
uspto-grants-2006_04
Patent number
US07030267B2

Reaction notes

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