Water → 1-(1,3-Dioxolo[4,5-B]pyridin-6-YL)-ethanone

HRID 2170039Notes

Reaction equation

HRID 2170039 reaction equation
Br[C:2]1[CH:3]=[C:4]2[O:10][CH2:9][O:8][C:5]2=[N:6][CH:7]=1.C([Sn](CCCC)(CCCC)[C:16]([O:18]CC)=[CH2:17])CCC.O.CCOC(C)=O>CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[O:10]1[C:4]2[C:5](=[N:6][CH:7]=[C:2]([C:16](=[O:18])[CH3:17])[CH:3]=2)[O:8][CH2:9]1

Participants

7

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 125630906-bromo-2H-[1,3]dioxolo[4,5-b]pyridine

Product 1

HCID 125630971-(1,3-Dioxolo[4,5-B]pyridin-6-YL)-ethanone

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
65 °C

Procedure

A round-bottomed flask was charged with 6-Bromo-[1,3]dioxolo[4,5-b]pyridine IM13 (1.74 g, 8.61 mmol) in DMF (25 ml) under N2 and tributyl(1-ethoxyvinyl)tin (3.65 ml, 10.8 mmol) was added. Tetrakistriphenylphosphinepalladium(0) (0.50 g, 0.43 mmol) was added and the solution was stirred at 65° C. overnight. The mixture was added to water and EtOAc and the phases were separated. The org phase was washed with brine, dried (MgSO4) filtered and was rotovaped. The residue was dissolved in THF (100 ml), and a mixture of water (15 ml) and conc. HCl (2.5 ml) was added and the solution was stirred at rt 5 min. The solution was added to brine and sat NaHCO3 solution was added until the solution was slightly alkaline. The org Phase was extracted with EtOAc and the phases were separated. The org phase was washed with brine, dried (MgSO4) filtered and was rotovaped. The residue was redissolved in THF (10 ml) EtOAc (20 ml) and heptanes (20 ml). The mixture was concentrated until 25 ml remained and cooled in ice. A solid precipitated and was collected by filtration. Yield: 0.942 g (66%) of IM21. 1H-NMR (500 MHz, DMSO) δ 8.47 (s, 1H), 8.54 (s, 1H), 6.27 (s, 2H), 2.53 (s, 3H).

Workup

  1. customthe phases were separated
  2. washThe org phase was washed with brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. dissolutionThe residue was dissolved in THF (100 ml)
  6. additiona mixture of water (15 ml) and conc. HCl (2.5 ml)
  7. additionwas added
  8. stirringthe solution was stirred at rt 5 min
  9. additionThe solution was added to brine
  10. additionwas added until the solution
  11. extractionThe org Phase was extracted with EtOAc
  12. customthe phases were separated
  13. washThe org phase was washed with brine
  14. dry with materialdried (MgSO4)
  15. filtrationfiltered
  16. dissolutionThe residue was redissolved in THF (10 ml) EtOAc (20 ml)
  17. concentrationThe mixture was concentrated until 25 ml
  18. temperaturecooled in ice
  19. customA solid precipitated
  20. filtrationwas collected by filtration

Sources & evidence

ORD record
ord-59acf65f3aa745ba9e4d8f6ee639cc66
Source dataset
uspto-grants-2015_06
Patent number
US09050327B2

Reaction notes

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