Methyl formate → HCID 68873141, compound

HRID 2105837Notes

Reaction equation

HRID 2105837 reaction equation
BrC1[C:3](OCC)=[CH:4][C:5]([N:10]([CH3:12])[CH3:11])=[C:6](C=1)[C:7]#[N:8].C[O-].[Na+].[CH:19]([O:21][CH3:22])=[O:20].O1[CH2:28][CH2:27][O:26][CH2:25][CH2:24]1>>[CH3:22][O:21][C:19](=[O:20])[C:24]1[CH:3]=[CH:4][C:5]([N:10]([CH3:12])[CH3:11])=[C:6]([C:7]#[N:8])[C:25]=1[O:26][CH2:27][CH3:28]

Participants

5

Reactant 4

HCID 7865Methyl formateHCID 312751,4-DioxaneHCID 10942334Sodium MethoxideHCID 68871844HCID 68871844, compound

Product 1

HCID 68873141HCID 68873141, compoundYield 12%

Conditions

Temperature
60 °C

Procedure

To a solution of 5-bromo-2-dimethylamino-4-ethoxy-benzonitrile (1.95 g, 7.3 mmol) in 7.25 mL of dioxane was added sodium methoxide (581 mg, 10.77 mmol), methyl formate (1.85 mL, 30 mmol), and trans-dichlorobis(triphenylphosphine) palladium(II) (281 mg, 0.4 mmol). The mixture was agitated by bubbling nitrogen gas through the solution. To the opening of the vial is affixed a balloon. The reaction was cautiously warmed to 60° C. as gas evolution can cause a froth to enter the balloon. The reaction mixture was stirred for 20 h at 65° C. It was diluted with dioxane and stirred for an additional 5 min. The warm solution was filtered through Celite, and the filtrate was concentrated in vacuo. Purification of the crude residue by flash column chromatography (silica gel, eluting with a gradient of ethyl acetate in hexanes) gave cyano-4-dimethylamino-2-ethoxy-benzoic acid methyl ester (218 mg, 12%).

Workup

  1. customby bubbling nitrogen gas through the solution
  2. stirringThe reaction mixture was stirred for 20 h at 65° C
  3. additionIt was diluted with dioxane
  4. stirringstirred for an additional 5 min
  5. filtrationThe warm solution was filtered through Celite
  6. concentrationthe filtrate was concentrated in vacuo
  7. customPurification of the crude residue by flash column chromatography (silica gel
  8. washeluting with a gradient of ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-03a8eac56e4f47a79667df6c73550674
Source dataset
uspto-grants-2009_08
Patent number
US07579368B2

Reaction notes

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