Nitromethane → HCID 45357900, compound

HRID 1297235Notes

Reaction equation

HRID 1297235 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]([C:10]#[N:11])=[CH:5][CH2:6][CH:7]([CH3:9])[CH3:8].[N+]([CH3:16])([O-])=O>C(#N)C>[CH3:1][O:2][C:3]([C:4]1([C:10]#[N:11])[CH2:16][CH:5]1[CH2:6][CH:7]([CH3:9])[CH3:8])=[O:12]

Participants

4

Reactant 2

HCID 6375NitromethaneHCID 53427408Methyl 2-cyano-5-methylhex-2-enoate

Product 1

HCID 45357900HCID 45357900, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 2-cyano-5 methyl-hex-2-enoic acid methyl ester (20.2 g, 121 mmol) in dry acetonitrile (110 mL) was added nitromethane (9.8 mL, 181 mmol) and a portionwise addition of alumina-supported potassium flouride (40% wt, 39.3 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 (Na2SO4) and concentrated in vacuo. The crude product was purified by flash column chromatography using hexanes/EtOAc (8:2) as an eluent to give 15 g (69%) of 1-cyano-2-isobutyl-cyclopropanecarboxylic acid methyl ester as colorless oil: 1H NMR (300 MHz, CDCl3) δ 0.98 (d, J=2.9 Hz, 3H), 1.00 (d, J=3.0 Hz, 3H), 1.35-1.42 (m, 2H), 1.65 (m, 1H), 1.79-1.94 (m, 3H), 3.81 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 19.3, 22.3, 22.4, 25.5, 27.9, 30.1, 39.0, 53.4, 117.3, 168.5.

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 (Na2SO4)
  9. concentrationconcentrated in vacuo
  10. customThe crude product was purified by flash column chromatography

Sources & evidence

ORD record
ord-7ef20c4909b34b5681d38bc5d83fcb60
Source dataset
uspto-grants-2007_07
Patent number
US07250433B2

Reaction notes

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