Stannane, tributyl(1-ethoxyethenyl)- → HCID 86689176, compound

HRID 1752508Notes

Reaction equation

HRID 1752508 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10]([Cl:11])=[CH:9][C:8](Br)=[CH:7][N:6]=1)=[O:4].C([Sn](CCCC)(CCCC)[C:18]([O:20][CH2:21][CH3:22])=[CH2:19])CCC>O1CCOCC1.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>[CH3:1][O:2][C:3]([C:5]1[C:10]([Cl:11])=[CH:9][C:8]([C:18]([O:20][CH2:21][CH3:22])=[CH2:19])=[CH:7][N:6]=1)=[O:4]

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 46311201Methyl 5-bromo-3-chloropyridine-2-carboxylate

Product 1

HCID 86689176HCID 86689176, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 5-bromo-3-chloro-pyridine-2-carboxylic acid methyl ester [1458-18-0] (376 mg, 1.5 mmol) in dioxane (3.7 ml) was added tributyl-(1-ethoxy-vinyl)-stannane [97674-02-7] (596 mg, 1.65 mmol), the solution was degassed and flushed with nitrogen (3×), Pd(PPh3)4 (87 mg, 0.075 mmol) was added, after degassing and flushing with nitrogen the mixture was heated to reflux for 4 h. The reaction mixture was diluted with EtOAc and treated with 10% aq. KF, the precipitate was filtered off and the layers were separated. The aq. Phase was extracted with EtOAc, the combined organic layers were washed with sat. aq. NaCl, dried with MgSO4, filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (cyclohexane/EtOAc 12:1 to 6/1) to provide the title compound as yellow solid.

Workup

  1. customthe solution was degassed
  2. additionwas added
  3. customafter degassing
  4. customflushing with nitrogen the mixture
  5. temperaturewas heated
  6. temperatureto reflux for 4 h
  7. additionThe reaction mixture was diluted with EtOAc
  8. additiontreated with 10% aq. KF
  9. filtrationthe precipitate was filtered off
  10. customthe layers were separated
  11. extractionThe aq. Phase was extracted with EtOAc
  12. washthe combined organic layers were washed with sat. aq. NaCl
  13. dry with materialdried with MgSO4
  14. filtrationfiltered
  15. concentrationconcentrated under reduced pressure
  16. customThe residue was purified by chromatography on silica gel (cyclohexane/EtOAc 12:1 to 6/1)

Sources & evidence

ORD record
ord-73bbed7c79c9447ba7c192f4ccd4a841
Source dataset
uspto-grants-2015_10
Patent number
US09163011B2

Reaction notes

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