3-Bromopyridine → 3-(Diethylboryl)pyridine

HRID 1441075Notes

Reaction equation

HRID 1441075 reaction equation
C([Li])CCC.Br[C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1.[CH2:13]([B:15]([CH2:18][CH3:19])OC)[CH3:14]>CCOCC.O1CCCC1.C(OC(=O)C)C>[CH2:13]([B:15]([CH2:18][CH3:19])[C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1)[CH3:14]

Participants

7

Reactant 3

HCID 122863-BromopyridineHCID 522516DiethylmethoxyboraneHCID 178418339Butyllithium

Product 1

HCID 6428513-(Diethylboryl)pyridine

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-40 °C

Procedure

n-Butyllithium (25.6 ml of a 2.5M solution in hexanes, 64 mmol) was added as a rapid stream of droplets to a solution of 3-bromopyridine (10.04 g, 64 mmol) in ether (200 ml) at -40° C., under nitrogen. The addition was carried out over 5 minutes and the reaction temperature was maintained below -40° C. throughout. The reaction was stirred at -40° C. for 20 minutes and then cooled to -70° C. whereupon diethylmethoxyborane in tetrahydrofuran (64.0 ml of a 1M solution, 64 mmol) was added as a rapid stream of droplets over 5 minutes. The reaction temperature was maintained below -63° C. throughout this addiition. The reaction was then allowed to warm slowly to room temperature whereupon it was diluted with ethylacetate and washed with brine. The organic layer was dried (Na2SO4) and the solvent removed under reduced pressure to give the crude product. This was purified by column chromatography on silica gel, eluting with dichloromethane to afford, after combination and evaporation of the appropriate fractions, the title compound as a yellow crystalline solid (7.3 g). Found: C,73.40; H,9.53; N,8.92; C9H14NB requires: C,73.52; H,9.60; N,9.53%.

Workup

  1. additionThe addition
  2. temperaturethe reaction temperature was maintained below -40° C. throughout
  3. additionwas added as a rapid stream of droplets over 5 minutes
  4. temperatureThe reaction temperature was maintained below -63° C. throughout this addiition
  5. temperatureto warm slowly to room temperature whereupon it
  6. washwashed with brine
  7. dry with materialThe organic layer was dried (Na2SO4)
  8. customthe solvent removed under reduced pressure

Sources & evidence

ORD record
ord-d91be0c52df648e4a4eaf9a3843e1c8f
Source dataset
uspto-grants-1996_03
Patent number
US05502065

Reaction notes

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