Dimethyl Sulfate → HCID 59447591, compound

HRID 1518286Notes

Reaction equation

HRID 1518286 reaction equation
[CH2:1]([O:8][C:9]1[CH:21]=[CH:20][C:12]([C:13]([CH:15]([C:18]#[N:19])[C:16]#[N:17])=[O:14])=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:22](=O)(O)[O-].[Na+].S(OC)(OC)(=O)=O>O1CCOCC1.O>[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]([C:13]([O:14][CH3:22])=[C:15]([C:18]#[N:19])[C:16]#[N:17])=[CH:20][CH:21]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 6497Dimethyl SulfateHCID 516892Sodium BicarbonateHCID 221697854-Benzyloxybenzoylmalononitrile

Product 1

HCID 59447591HCID 59447591, compoundYield 79.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

Compound 31B (3.7 g, 13.39 mmol) was dissolved in 1,4-dioxane (30 mL) and water (5 mL). To this solution was added to sodium bicarbonate (9.0 g, 107 mmol) portionwise to control the gas formation. To the resulting suspension was added dimethyl sulfate (8.96 mL, 94 mmol). The reaction was heated under reflux for 2 hours. The reaction mixture was concentrated, and partitioned between water and EtOAc. The aqueous layer was extracted with additional EtOAc. The combined organic layers were washed with brine, dried (MgSO4), filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel eluting with 7:3/hexanes: EtOAc to provide 3.1 g of the desired product: 1H NMR (DMSO-d6): δ 7.64-7.68 (m, 2H), 7.34-7.69 (m, 5H), 7.22-7.26 (m, 2H), 5.22 (s, 2H), 3.92 (s, 3H). MS (DCI(+)): m/z 308 (M+NH4).

Workup

  1. temperatureThe reaction was heated
  2. temperatureunder reflux for 2 hours
  3. concentrationThe reaction mixture was concentrated
  4. custompartitioned between water and EtOAc
  5. extractionThe aqueous layer was extracted with additional EtOAc
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by flash column chromatography on silica gel eluting with 7:3/hexanes

Sources & evidence

ORD record
ord-ce3ca0697eca4c82b0fde11bbb39add1
Source dataset
uspto-grants-2012_07
Patent number
US08232273B2

Reaction notes

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