Hydrochloric Acid → 5-(Benzyloxy)-4,4-dimethyl-3-oxopentanenitrile

HRID 2069117Notes

Reaction equation

HRID 2069117 reaction equation
[H-].[Na+].[CH2:3]([O:10][CH2:11][C:12]([CH3:18])([CH3:17])[C:13]([O:15]C)=O)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[C:19](#[N:21])[CH3:20].Cl>C1(C)C=CC=CC=1>[CH2:3]([O:10][CH2:11][C:12]([CH3:18])([CH3:17])[C:13](=[O:15])[CH2:20][C:19]#[N:21])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6342AcetonitrileHCID 24758Sodium hydrideHCID 59267989Methyl 3-(benzyloxy)-2,2-dimethylpropanoate

Product 1

HCID 585647415-(Benzyloxy)-4,4-dimethyl-3-oxopentanenitrileYield 120.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a suspension of sodium hydride (1.62 g of a 60% w/w dispersion in mineral oil, 40.5 mmol) in toluene (20 mL) at reflux was added a solution of methyl 3-(benzyloxy)-2,2-dimethylpropanoate [Eur. J. Org. Chem., 2007 (6) 934-942] (6.00 g, 27.0 mmol) and acetonitrile (2.12 ml, 40.5 mmol) in toluene, dropwise over 1 hr. The reaction mixture was heated for a further 5 hr at reflux then cooled to RT. The mixture was acidified to pH 4 with aqueous hydrochloric acid (1M) and extracted with EtOAc. The organic extract was washed with water and with brine then dried (MgSO4) and evaporated in vacuo to afford 5-(benzyloxy)-4,4-dimethyl-3-oxopentanenitrile as a yellow oil (7.50 g, 96%): m/z 232 (M+H)+ (ES+), which was used without purification in the next step.

Workup

  1. temperatureat reflux
  2. temperatureThe reaction mixture was heated for a further 5 hr
  3. temperatureat reflux
  4. extractionextracted with EtOAc
  5. extractionThe organic extract
  6. washwas washed with water and with brine
  7. dry with materialthen dried (MgSO4)
  8. customevaporated in vacuo

Sources & evidence

ORD record
ord-ff11871b1c184625be27e8a958e2814e
Source dataset
uspto-grants-2012_10
Patent number
US08299074B2

Reaction notes

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