Triphenylphosphine → 6-tert-Butyl-2-(3,3-dimethylbut-1-ynyl)nicotinonitrile

HRID 921043Notes

Reaction equation

HRID 921043 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([C:24]#[CH:25])([CH3:23])([CH3:22])[CH3:21].Cl[C:27]1[C:32]([C:33]#[N:34])=[CH:31][CH:30]=[C:29]([C:35]([CH3:38])([CH3:37])[CH3:36])[N:28]=1>CN(C=O)C.C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Cu]I>[C:35]([C:29]1[CH:30]=[CH:31][C:32]([C:33]#[N:34])=[C:27]([C:25]#[C:24][C:20]([CH3:23])([CH3:22])[CH3:21])[N:28]=1)([CH3:38])([CH3:37])[CH3:36]

Participants

8

Reactant 3

HCID 11776TriphenylphosphineHCID 135123,3-Dimethyl-1-butyneHCID 532788766-Tert-butyl-2-chloropyridine-3-carbonitrile

Product 1

HCID 679961326-tert-Butyl-2-(3,3-dimethylbut-1-ynyl)nicotinonitrile

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
65 °C

Procedure

15.7 g (60 mmol) of triphenylphosphine, 6.7 g (30 mmol) of palladium(II) acetate, 5.7 g (30 mmol) of copper(I) iodide and 155.6 g (1.9 mmol) of tert-butylacetylene are added consecutively to a solution of 194.7 g (1 mol) of 2-chloro-3-cyano-6-tert-butylpyridine, S28, in a mixture of 1800 ml of DMF and 1000 ml of triethylamine, and the mixture is stirred at 65° C. for 4 h. After cooling, the precipitated triethylammonium hydrochloride is filtered off with suction, rinsed with 300 ml of DMF. The filtrate is freed from the solvents in vacuo. The oily residue is taken up in 1000 ml of ethyl acetate, the solution is washed five times with 500 ml of water each time and once with 500 ml of saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate. After removal of the ethyl acetate in vacuo, the black oily residue is subjected to bulb-tube distillation (p about 10−2 mbar, T=120-140° C.). Yield: 190.6 g (793 mmol), 79%. Purity: >97% according to 1H-NMR.

Workup

  1. temperatureAfter cooling
  2. filtrationthe precipitated triethylammonium hydrochloride is filtered off with suction
  3. washrinsed with 300 ml of DMF
  4. washthe solution is washed five times with 500 ml of water each time
  5. dry with materialonce with 500 ml of saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate
  6. customAfter removal of the ethyl acetate in vacuo
  7. customthe black oily residue is subjected to bulb-tube
  8. distillationdistillation (p about 10−2 mbar, T=120-140° C.)

Sources & evidence

ORD record
ord-b3e4663cf4e64da6973ce953a1d862b1
Source dataset
uspto-grants-2016_03
Patent number
US09273080B2

Reaction notes

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