2-Methyl-3-butyn-2-ol → 4-(4-Cyanophenyl)-2-methyl-3-butyne-2-ol

HRID 1755616Notes

Reaction equation

HRID 1755616 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[CH3:10][C:11]([OH:15])([CH3:14])[C:12]#[CH:13]>C(N(CC)CC)C.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:10][C:11]([OH:15])([CH3:14])[C:12]#[C:13][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1

Participants

7

Reactant 2

HCID 82582-Methyl-3-butyn-2-olHCID 12162Benzonitrile, 4-bromo-

Product 1

HCID 28221554-(4-Cyanophenyl)-2-methyl-3-butyne-2-olYield 79.6%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

30 g of 4-bromobenzonitrile, 13.4 g of 3-methyl-1-butyn-3-ol, 0.7 g of triphenylphosphine and 0.3 g of bis(triphenylphosphine) palladium(II) chloride were dissolved in 140 ml of triethylamine in nitrogen atmosphere, and 0.1 g of copper(I) iodide was added thereto. This was stirred for one hour at room temperature and then for 5 hours at 90° C. The crystals as precipitated were filtered out and, after triethylamine was removed by distillation, extracted with chloroform. The crystals were washed two times with 10% hydrochloric acid and two times with water, and chloroform was removed by distillation. The residue was distilled under reduced pressure (b.p. 140° to 160° C./5 mmHg) to obtain 23.5 g of 3-methyl-1-(4'-cyanophenyl)-1-butyn-3-ol.

Workup

  1. additionwas added
  2. waitfor 5 hours at 90° C
  3. customThe crystals as precipitated
  4. filtrationwere filtered out
  5. customafter triethylamine was removed by distillation
  6. extractionextracted with chloroform
  7. washThe crystals were washed two times with 10% hydrochloric acid and two times with water, and chloroform
  8. customwas removed by distillation
  9. distillationThe residue was distilled under reduced pressure (b.p. 140° to 160° C./5 mmHg)

Sources & evidence

ORD record
ord-530a34b623284735b466eeea57b0a2ae
Source dataset
uspto-grants-1995_08
Patent number
US05437815

Reaction notes

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