Dimethyl malonate → HCID 86637416, compound

HRID 1924788Notes

Reaction equation

HRID 1924788 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].[H-].[Na+].[Cl:12][C:13]1[CH:14]=[C:15]([C:20](=[O:22])[CH3:21])[CH:16]=[N:17][C:18]=1Cl>CS(C)=O>[C:20]([C:15]1[CH:14]=[C:13]([Cl:12])[C:18]([CH:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4])=[N:17][CH:16]=1)(=[O:22])[CH3:21]

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 101980061-(5,6-Dichloropyridin-3-yl)ethan-1-one

Product 1

HCID 86637416HCID 86637416, compoundYield 32.2%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

Dimethyl malonate (4.69 g, 35.5 mmol) was dissolved in DMSO (24.0 ml). This solution was added 70% NaH (1.33 g, 33.2 mmol) at 0° C. The resulting mixture was warmed up to room temperature, then stirred at the same temperature for 40 min. To this solution was added 1-(5,6-dichloropyridin-3-yl)ethanone (Tetrahedron 1992, 48, 9233-9236, 4.50 g, 23.7 mmol) at room temperature, then the resulting mixture was stirred at 100° C. for 4 hours. The mixture was partitioned between Et2O and water. The organic layer was washed with water and brine, dried over Na2SO4, then concentrated to give a brown syrup. The crude material was purified by SiO2 column chromatography (100 g, EtOAc/hexane (1/2)) to give the title compound (2.18 g, 32%) as a yellow oil. 1H NMR (300 MHz, CDCl3) δ 2.64 (3H, s), 3.83 (6H, s), 5.31 (1H, s), 8.26 (1H, s), 9.02 (1H, s).

Workup

  1. stirringthe resulting mixture was stirred at 100° C. for 4 hours
  2. customThe mixture was partitioned between Et2O and water
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated
  6. customto give a brown syrup
  7. customThe crude material was purified by SiO2 column chromatography (100 g, EtOAc/hexane (1/2))

Sources & evidence

ORD record
ord-8f7cca1180454d0ca8ec9391119bb3d5
Source dataset
uspto-grants-2012_05
Patent number
US08178558B2

Reaction notes

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