1,4-Dioxane → Methyl 3-dimethylamino-2-(2,3,4,5-tetrafluorobenzoyl)acrylate

HRID 1708543Notes

Reaction equation

HRID 1708543 reaction equation
O1CCOCC1.[F:7][C:8]1[C:16]([F:17])=[C:15]([F:18])[C:14]([F:19])=[CH:13][C:9]=1[C:10](Cl)=[O:11].[CH3:20][N:21]([CH3:28])[CH:22]=[CH:23][C:24]([O:26][CH3:27])=[O:25]>C(N(CC)CC)C>[CH3:20][N:21]([CH3:28])[CH:22]=[C:23]([C:10](=[O:11])[C:9]1[CH:13]=[C:14]([F:19])[C:15]([F:18])=[C:16]([F:17])[C:8]=1[F:7])[C:24]([O:26][CH3:27])=[O:25]

Participants

5

Reactant 3

HCID 312751,4-Dioxane2×HCID 566587Methyl 3-(dimethylamino)acrylateHCID 27336892,3,4,5-Tetrafluorobenzoyl chloride

Product 1

HCID 53884844Methyl 3-dimethylamino-2-(2,3,4,5-tetrafluorobenzoyl)acrylateYield 50.7%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

To dioxane (80 ml) solution of 2,3,4,5-tetrafluorobenzoyl chloride (21.25 g) was added dioxane (25 ml) solution of methyl 3-dimethylaminoacrylate (12.92 g) with ice-cooling, and triethylamine (14.46 ml) was added thereto with ice-cooling. The mixture was stirred for 30 minutes at the same temperature, then for 3 hours at room temperature, and then for one hour at 50° to 60° C. The mixture was concentrated under reduced pressure, then dissolved in methylene chloride (200 ml), washed with water (200 ml) and brine (100 ml) in order, then dried with sodium sulfate and concentrated under reduced pressure to obtain a syrup product. The syrup product was subjected to column chromatography with silica gel and eluted with a mixed liquid of methanol/methylene chloride (3/97, V/V) to obtain methyl 3-dimethylamino-2-(2,3,4,5-tetrafluorobenzoyl)acrylate (15.47 g) as a syrup product.

Workup

  1. temperaturecooling
  2. temperaturewith ice-cooling
  3. waitfor 3 hours at room temperature
  4. waitfor one hour at 50° to 60° C
  5. concentrationThe mixture was concentrated under reduced pressure
  6. dissolutiondissolved in methylene chloride (200 ml)
  7. washwashed with water (200 ml) and brine (100 ml) in order
  8. dry with materialdried with sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customto obtain a syrup product
  11. washeluted with a mixed liquid of methanol/methylene chloride (3/97, V/V)

Sources & evidence

ORD record
ord-fccdf0d855e94d9ca6306e5392f57271
Source dataset
uspto-grants-1994_10
Patent number
US05359066

Reaction notes

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