Water → HCID 86626072, compound

HRID 390587Notes

Reaction equation

HRID 390587 reaction equation
[CH2:1]([O:3]/[C:4](=[CH:10]\[C:11]1[CH:16]=[CH:15][C:14](B2OC(C)(C)C(C)(C)O2)=[CH:13][CH:12]=1)/[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH3:2].[CH3:26][NH:27][C:28]1[N:33]=[C:32](Br)[CH:31]=[CH:30][CH:29]=1.[F-].[Cs+].O>COCCOCCOC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(OCC)(=O)C>[CH2:1]([O:3]/[C:4](=[CH:10]\[C:11]1[CH:12]=[CH:13][C:14]([C:32]2[CH:31]=[CH:30][CH:29]=[C:28]([NH:27][CH3:26])[N:33]=2)=[CH:15][CH:16]=1)/[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH3:2]

Participants

8

Reactant 4

HCID 962WaterHCID 25953Cesium fluorideHCID 134703156-bromo-N-methylpyridin-2-amineHCID 86626073HCID 86626073, compound

Product 1

HCID 86626072HCID 86626072, compoundYield 76.6%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8150DiglymeSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

1.0 g (2.9 mmol) of ethyl (Z)-2-ethoxy-3-[4-(4,4,5,5-tetramethyl[1.3]dioxaborolan-2-yl)phenyl]acrylate, 0.4 g (2.4 mmol) of 6-methylamino-2-bromopyridine and 1.1 g (7.2 mmol) of caesium fluoride are dissolved in 60 mL of diethylene glycol dimethyl ether. After bubbling nitrogen through the reaction mixture for 20 minutes, 0.1 g (0.15 mmol) of dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium is added. The reaction mixture is heated at 80° C. for 18 hours with vigorous stirring. After cooling, the reaction is worked up by addition of 60 mL of water and extraction with ethyl acetate. The organic phases are combined, washed with saturated aqueous sodium chloride solution and then dried over magnesium sulfate. After filtration, the solvents are evaporated off. The crude product obtained is purified by chromatography on a column of silica eluted with a 90/10 heptane/ethyl acetate mixture to give 0.6 g (76%) of ethyl (Z)-2-ethoxy-3-[4-(6-methylaminopyrid-2-yl)phenyl]acrylate.

Workup

  1. customAfter bubbling nitrogen through the reaction mixture for 20 minutes
  2. temperatureAfter cooling
  3. washwashed with saturated aqueous sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. filtrationAfter filtration
  6. customthe solvents are evaporated off
  7. customThe crude product obtained
  8. customis purified by chromatography on a column of silica
  9. washeluted with a 90/10 heptane/ethyl acetate mixture

Sources & evidence

ORD record
ord-5c44d422ad654f2d83632f33b4849ee6
Source dataset
uspto-grants-2013_02
Patent number
US08383652B2

Reaction notes

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