Sodium Iodide → 4-(3-Oxo-2-propionylpentyl)benzonitrile

HRID 970024Notes

Reaction equation

HRID 970024 reaction equation
[H-].[Na+].[CH3:3][CH2:4][C:5](=[O:11])[CH2:6][C:7](=[O:10])[CH2:8][CH3:9].[I-].[Na+].[C:14]([C:16]1[CH:23]=[CH:22][C:19]([CH2:20]Br)=[CH:18][CH:17]=1)#[N:15]>CC(=O)CC.C(OCC)C>[O:10]=[C:7]([CH2:8][CH3:9])[CH:6]([C:5](=[O:11])[CH2:4][CH3:3])[CH2:20][C:19]1[CH:22]=[CH:23][C:16]([C:14]#[N:15])=[CH:17][CH:18]=1

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 24758Sodium hydrideHCID 819233,5-HeptanedioneHCID 869964-(Bromomethyl)benzonitrile

Product 1

HCID 590181954-(3-Oxo-2-propionylpentyl)benzonitrileYield 58%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6569Methyl Ethyl KetoneSolvent2×

Procedure

Sodium hydride (60% dispersion in oil, 3.43 g, 86 mmol) was added to a solution of 3,5-heptanedione (10 g, 78 mmol), in 2-butanone (200 ml), under nitrogen. A slight exotherm was observed during gas evolution. Sodium iodide (11.7 g, 78 mmol) was then added, followed by 4-cyanobenzyl bromide (15.29 g, 78 mmol) in 2-butanone (20 ml) and a precipitate was formed. The reaction mixture was heated at reflux for 16 hours. It was then filtered to remove the precipitate and concentrated under reduced pressure. The residue was stirred in dichloromethane (100 ml) and solid sodium bromide was removed by filtration. The dichloromethane filtrate was then washed with water (100 ml) and brine (100 ml). The organic layer was collected, dried over magnesium sulphate and concentrated under reduced pressure to give an orange solid. This was slurried in diethyl ether and filtered off to provide the title compound (11.01 g, 58%) as a pale yellow solid. 1H-NMR (400 MHz, CDCl3): δ=0.98 (t, 6H), 2.29-2.35 (m, 2H), 2.42-2.52 (m, 2H), 3.19 (d, 2H), 3.97 (t, 1H), 7.25 (d, 2H), 7.56 (d, 2H); LRMS: APCl−: m/z 242 [M−H].

Workup

  1. customa precipitate was formed
  2. temperatureThe reaction mixture was heated
  3. temperatureat reflux for 16 hours
  4. filtrationIt was then filtered
  5. customto remove the precipitate
  6. concentrationconcentrated under reduced pressure
  7. customsolid sodium bromide was removed by filtration
  8. washThe dichloromethane filtrate was then washed with water (100 ml) and brine (100 ml)
  9. customThe organic layer was collected
  10. dry with materialdried over magnesium sulphate
  11. concentrationconcentrated under reduced pressure
  12. customto give an orange solid
  13. filtrationfiltered off

Sources & evidence

ORD record
ord-07407a2446dd46a5a2b217e72ea1ed6c
Source dataset
uspto-grants-2007_12
Patent number
US07309712B2

Reaction notes

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