3-Butyn-1-OL → 4-[4-(Trifluoromethyl)phenyl]but-3-YN-1-OL

HRID 852357Notes

Reaction equation

HRID 852357 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][CH:3]=1.[CH2:12]([OH:16])[CH2:13][C:14]#[CH:15]>N1CCCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[F:9][C:8]([F:11])([F:10])[C:5]1[CH:6]=[CH:7][C:2]([C:15]#[C:14][CH2:13][CH2:12][OH:16])=[CH:3][CH:4]=1

Participants

6

Reactant 2

HCID 135663-Butyn-1-OL2×HCID 67993Benzene, 1-iodo-4-(trifluoromethyl)-

Product 1

HCID 608016064-[4-(Trifluoromethyl)phenyl]but-3-YN-1-OLYield 93.7%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8082PiperidineSolvent

Conditions

Temperature
50 °C

Procedure

The synthesis was performed following a procedure of Stara, Irena G.; Stary, Ivo; Kollarovic, Adrian; Teply, Filip; Saman, David; Fiedler, Pavel, Coupling reactions of halobenzenes with alkynes. The synthesis of phenylacetylenes and symmetrical or unsymmetrical 1,2-diphenylacetylenes, Collect. Czech. Chem. Commun. (1999), 64(4), 649-672. To a degassed (argon) solution of 5.0 g (17.83 mmol) 1-iodo-4-trifluoromethyl-benzene in 65 ml piperidine was added 1.03 g (0.89 mmol) Pd(PPh3)4 and 0.17 g (0.89 mmol) CuI. The reaction mixture was stirred at 50° C. for 10 min, then 2.03 ml (26.75 mmol) of but-3-yn-1-ol were added dropwise within 1 h. During the addition of but-3-yn-1-ol the oil bath was slowly heated to 80° C. starting after 30 min. The reaction mixture was stirred at this temperature for 3 h and then extracted with chilled aqueous 10% KHSO4/Et2O (three times). The organic phases were washed with aqueous 10% NaCl, dried (Na2SO4) and evaporated. Purification by flash-chromatography on silica gel (n-heptane/EtOAc 9:1 to 4:1) yielded 3.58 g of the title compound as a yellow solid.

Workup

  1. customsymmetrical or unsymmetrical 1,2-diphenylacetylenes, Collect
  2. temperaturewas slowly heated to 80° C.
  3. waitstarting after 30 min
  4. stirringThe reaction mixture was stirred at this temperature for 3 h
  5. extractionextracted with chilled aqueous 10% KHSO4/Et2O (three times)
  6. washThe organic phases were washed with aqueous 10% NaCl
  7. dry with materialdried (Na2SO4)
  8. customevaporated
  9. customPurification by flash-chromatography on silica gel (n-heptane/EtOAc 9:1 to 4:1)

Sources & evidence

ORD record
ord-08f0fb69dbab48579ff2fd4ed6778146
Source dataset
uspto-grants-2007_08
Patent number
US07253192B2

Reaction notes

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