Bromide ion → HCID 67396867, compound

HRID 70502Notes

Reaction equation

HRID 70502 reaction equation
[Br-].Br[C:3]1[CH:4]=[CH:5][C:6]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[N:7][CH:8]=1.O.O1[CH2:19][CH2:18][CH2:17]C1>[Cl-].[Zn+2].[Cl-].Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:17]1([C:3]2[CH:4]=[CH:5][C:6]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[N:7][CH:8]=2)[CH2:18][CH2:19]1

Participants

7

Reactant 4

HCID 259Bromide ionHCID 962WaterHCID 8028Tetrahydrofuran3×HCID 12686158Ethyl 5-bromopicolinate

Product 1

HCID 67396867HCID 67396867, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
0 °C

Procedure

A suspension of zinc chloride (27 g) in tetrahydrofuran (300 mL) was cooled to 0° C. in the presence of a nitrogen gas, and a 1 M solution of cyclopropanemagnesium bromide in tetrahydrofuran (186 mL) was added thereto, followed by stirring at room temperature for 30 minutes. The reaction solution was cooled to 0° C. Dichlorobis(triphenylphosphine)-palladium(II) (3.26 g) and a solution of ethyl 5-bromopyridine-2-carboxylate (21.4 g) in tetrahydrofuran (100 mL) were sequentially added, and the mixture was stirred at 0° C. for 30 minutes and at room temperature for one hour. The reaction solution was poured into water, followed by extraction with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and filtered. The solvent was then evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=4:1→1:1) to give ethyl 5-cyclopropylpyridine-2-carboxylate (15.5 g, 87%) as a pale brown oil.

Workup

  1. temperatureThe reaction solution was cooled to 0° C
  2. stirringthe mixture was stirred at 0° C. for 30 minutes and at room temperature for one hour
  3. extractionfollowed by extraction with ethyl acetate
  4. washThe organic layer was washed with brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customThe solvent was then evaporated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=4:1→1:1)

Sources & evidence

ORD record
ord-e01d7efd5981461e9c5e56bb7c6eb516
Source dataset
uspto-grants-2014_09
Patent number
US08822503B2

Reaction notes

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