Tetrahydrofuran → 4-(4-Cyanophenyl)-2-methyl-3-butyne-2-ol

HRID 393121Notes

Reaction equation

HRID 393121 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].O1CCCC1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([C:13]#[C:12][C:11]([OH:15])([CH3:14])[CH3:10])=[CH:3][CH:4]=1)#[N:7]

Participants

8

Reactant 3

HCID 8028TetrahydrofuranHCID 82582-Methyl-3-butyn-2-olHCID 12162Benzonitrile, 4-bromo-

Product 1

HCID 28221554-(4-Cyanophenyl)-2-methyl-3-butyne-2-olYield 105.3%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

50 g (274.7 mmol) 4-bromobenzonitrile, 46.2 g (550 mmol) 3-methyl-1-butyne-3-ol, 0.97 g (1.38 mmol) bis(triphenylphosphine) dichloropalladium, 0.26 g (1.38 mmol) copper iodide and 2 g (7.6 mmol) triphenyl phosphine were added in a nitrogen stream, and 100 ml tetrahydrofuran (THF) and 20 ml triethylamine were added thereto, and the mixture was reacted at 80 ° C. for 15 hours. The reaction solution was concentrated and partitioned by adding 300 ml ethyl acetate and 300 ml water, and the organic layer was washed twice with 100 ml water and dried over magnesium sulfate anhydride. The solvent was distilled away, and about 250 ml heptane was added to the residual paste and stirred for a while, and the precipitated crystals were filtered to give 53.6 g crystals.

Workup

  1. additionwere added
  2. customthe mixture was reacted at 80 ° C. for 15 hours
  3. concentrationThe reaction solution was concentrated
  4. custompartitioned
  5. additionby adding 300 ml ethyl acetate and 300 ml water
  6. washthe organic layer was washed twice with 100 ml water
  7. dry with materialdried over magnesium sulfate anhydride
  8. distillationThe solvent was distilled away
  9. additionabout 250 ml heptane was added to the residual paste
  10. filtrationthe precipitated crystals were filtered

Sources & evidence

ORD record
ord-cea7688ee1f644e1ac8126a418684503
Source dataset
uspto-grants-2004_10
Patent number
US06805920B2

Reaction notes

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