1-Butyne → HCID 67979408, compound

HRID 539292Notes

Reaction equation

HRID 539292 reaction equation
[CH:1]#[C:2][CH2:3][CH3:4].C(NC(C)C)(C)C.Br[C:13]1[CH:14]=[N:15][CH:16]=[C:17]([Br:19])[CH:18]=1>C(#N)C.CCOC(C)=O>[Br:19][C:17]1[CH:16]=[N:15][CH:14]=[C:13]([C:1]#[C:2][CH2:3][CH3:4])[CH:18]=1

Participants

6

Reactant 3

HCID 78461-Butyne2×HCID 7912DiisopropylamineHCID 693693,5-Dibromopyridine

Product 1

HCID 67979408HCID 67979408, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

But-1-yne (g) was during 5 min gently bubbled through anhydrous acetonitrile cooled in an ice-water bath. The resulting solution contained about 170 mg but-1-yne per mL. The solution of but-1-yne (4.57 mL, 14.36 mmol) and diisopropylamine (3.72 mL, 26.11 mmol) were added sequentially to a mixture of 3,5-dibromopyridine (3.09 g, 13.06 mmol), bis(triphenylphosphine)-palladium(IT) chloride (0.458 g, 0.65 mmol) and CuT (0.249 g, 1.31 mmol) in acetonitrile (15 mL) under an argon atmosphere. The resulting mixture was stirred at r.t. overnight, diluted with EtOAc and passed through a short plug of silica. The solvents were evaporated and the residue was purified by flash chromatography on silica (gradient elution 0-20% EtOAc in heptane) to give 2.40 g of the title compound (87% yield): 1H NMR (500 MHz, DMSO-d6) δ ppm 1.17 (t, 4 H), 2.47 (q, 3 H), 8.11 (t, 1 H), 8.57 (d, 1 H), 8.65 (d, 1 H); MS (ES+) m/z 210 [M+H]F.

Workup

  1. customgently bubbled through anhydrous acetonitrile
  2. temperaturecooled in an ice-water bath
  3. customThe solvents were evaporated
  4. customthe residue was purified by flash chromatography on silica (gradient elution 0-20% EtOAc in heptane)

Sources & evidence

ORD record
ord-2f8df5ea40bb4005a93c9b60c1e89a8d
Source dataset
uspto-grants-2014_10
Patent number
US08865911B2

Reaction notes

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