Dimethylformamide → Ethyl 3-quinolineacrylate

HRID 1792131Notes

Reaction equation

HRID 1792131 reaction equation
Br[C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[CH:7][CH:6]=2.[C:12]([O:16][CH2:17][CH3:18])(=[O:15])[CH:13]=[CH2:14].C(=O)(O)[O-].[Na+].CN(C)C=O>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C>[N:4]1[C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[CH:11]=[C:2]([CH:14]=[CH:13][C:12]([O:16][CH2:17][CH3:18])=[O:15])[CH:3]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 8821Ethyl AcrylateHCID 214133-Bromoquinoline2×HCID 516892Sodium Bicarbonate

Product 1

HCID 53657281Ethyl 3-quinolineacrylateYield 65%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

The 3-bromoquinoline (300 g, 1.44 mmol), ethyl acrylate (168 g, 1.68 mmol), palladium(II) acetate (32.3 g, 144 mmol), tetrabutylammonium bromide (478 g 1.44 mol), and sodium bicarbonate (483.9 g, 5.76 mol) were combined in a 5-L round-bottom flask with overhead stirring and 3 L dimethyl formamide (anhydrous). The reaction mixture was heated to 90° C. with heating mantle. After 30 minutes, 3-bromoquinoline was not detected by HPLC. The reaction was cooled to room temperature with an ice bath, and 2.65 L of ethyl acetate was added. The organic layer was washed with 1500 mL H2O. The aqueous layer was extracted with 4×1 L of 1:1 toluene/ethyl acetate; the combined organic layers were then washed with 6×1 L brine, then evaporated to give 217.4 g (65% of desired product).

Workup

  1. temperaturewith heating mantle
  2. temperatureThe reaction was cooled to room temperature with an ice bath
  3. washThe organic layer was washed with 1500 mL H2O
  4. extractionThe aqueous layer was extracted with 4×1 L of 1:1 toluene/ethyl acetate
  5. washthe combined organic layers were then washed with 6×1 L brine
  6. customevaporated

Sources & evidence

ORD record
ord-f83c87bc9b8c4febad52cb8f24326a21
Source dataset
uspto-grants-2006_07
Patent number
US07074932B2

Reaction notes

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