(Z)-Benzaldehyde oxime → Ethyl 4-hydroxy-1,1-dimethyl-2-oxo-5-(trifluoromethyl)-naphthalene-3-carboxylate

HRID 1868692Notes

Reaction equation

HRID 1868692 reaction equation
C(=N[OH:9])C1C=CC=CC=1.[H-].[Na+].C(O[C:15](=[O:36])[C:16]([C:19]1[CH:24]=[CH:23][CH:22]=[C:21]([C:25]([F:28])([F:27])[F:26])[C:20]=1[C:29]#[C:30][C:31]([O:33][CH2:34][CH3:35])=[O:32])([CH3:18])[CH3:17])C>CN(C=O)C.O1CCOCC1>[OH:9][C:29]1[C:20]2[C:19](=[CH:24][CH:23]=[CH:22][C:21]=2[C:25]([F:27])([F:28])[F:26])[C:16]([CH3:17])([CH3:18])[C:15](=[O:36])[C:30]=1[C:31]([O:33][CH2:34][CH3:35])=[O:32]

Participants

6

Reactant 3

HCID 12143(Z)-Benzaldehyde oximeHCID 24758Sodium hydrideHCID 67099719Ethyl 3-(2-(1-ethoxy-2-methyl-1-oxopropan-2-yl)-6-(trifluoromethyl)phenyl)propiolate

Product 1

HCID 67099721Ethyl 4-hydroxy-1,1-dimethyl-2-oxo-5-(trifluoromethyl)-naphthalene-3-carboxylateYield 19.8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 312751,4-DioxaneSolvent

Procedure

Benzaldehyde oxime (112 mg, 0.92 mmol) in 6 mL dry DMF under argon, was added via syringe to a suspension of NaH (22 mg, 0.92 mmol) in dry dioxane (6 mL) under argon at room temperature. The mixture was stirred for 30 minutes, and ethyl 3-(2-(1-ethoxy-2-methyl-1-oxopropan-2-yl)-6-(trifluoromethyl)phenyl)propiolate (275 mg, 0.77 mmol) was added as a solution in dry DMF (6 mL) via syringe. The reaction was stirred at room temperature for 11 hours. The dioxane was removed under vacuum, and the remaining DMF was partitioned between EtOAc and water. The layers were separated, and the organic layer was washed with twice with water and once with brine. The combined aqueous extracts were back extracted twice with EtOAc, and these organic layers were added to the organic layer already obtained. The combined extracts were dried over MgSO4, concentrated under vacuum, and the resulting residue was purified by column chromatography to give the product as a light yellow oil (50 mg). MS (m/z)=329 (M+H)+

Workup

  1. stirringThe reaction was stirred at room temperature for 11 hours
  2. customThe dioxane was removed under vacuum
  3. customthe remaining DMF was partitioned between EtOAc and water
  4. customThe layers were separated
  5. washthe organic layer was washed with twice with water
  6. extractionThe combined aqueous extracts were back extracted twice with EtOAc
  7. additionthese organic layers were added to the organic layer
  8. customalready obtained
  9. dry with materialThe combined extracts were dried over MgSO4
  10. concentrationconcentrated under vacuum
  11. customthe resulting residue was purified by column chromatography

Sources & evidence

ORD record
ord-03612926a23240b3b3947846b795010c
Source dataset
uspto-grants-2009_12
Patent number
US07635715B2

Reaction notes

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