Chloride → 5-Bromo-2-cyclopropylpyridine

HRID 268936Notes

Reaction equation

HRID 268936 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1.[Cl-].C([O-])(O)=O.[Na+].[CH2:15]1[CH2:19]OC[CH2:16]1>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>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([CH:16]2[CH2:15][CH2:19]2)=[N:3][CH:4]=1

Participants

6

Reactant 4

HCID 312ChlorideHCID 8028TetrahydrofuranHCID 693532,5-DibromopyridineHCID 516892Sodium Bicarbonate

Product 1

HCID 223177225-Bromo-2-cyclopropylpyridineYield 103%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
70 °C

Procedure

To a solution 2,5-dibromopyridine [CAS 624-28-2, commercially available] (5 g, 21 mmol) and Pd(PPh3)4 (244 mg, 1 mol %) in THF (25 mL) was added cycloropylzinc chloride (0.4M in THF, 53 mL, 26 mmol), and the mixture was stirred under argon atmosphere at 70° C. for 3 h. Cooled to 23° C., poured into sat. NaHCO3-solution, extracted with ether, washed with brine, dried over Na2SO4. Removal of the solvent in vacuum left a brown oil, which was purified by silica gel chromatography with heptane-EtOAc (9:1) to give the title compound as a colorless liquid (4.3 g, 103%). MS (EI) 197 [(M)+] and 199 [(M+2)+].

Workup

  1. temperatureCooled to 23° C.
  2. extractionextracted with ether
  3. washwashed with brine
  4. dry with materialdried over Na2SO4
  5. customRemoval of the solvent in vacuum
  6. waitleft a brown oil, which
  7. customwas purified by silica gel chromatography with heptane-EtOAc (9:1)

Sources & evidence

ORD record
ord-bee1101fbdec46028f8ef07002e52531
Source dataset
uspto-grants-2008_11
Patent number
US07446113B2

Reaction notes

Loading…