1-Hexyne → HCID 11424006, compound

HRID 545325Notes

Reaction equation

HRID 545325 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6].[CH:10]#[C:11][CH2:12][CH2:13][CH2:14][CH3:15]>N1CCCCC1.[Cu]I.[Pd].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.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>[C:10]([C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6])#[C:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

6

Reactant 2

HCID 127321-HexyneHCID 765833-Bromobenzaldehyde

Product 1

HCID 11424006HCID 11424006, compoundYield 87.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8082PiperidineSolvent2×

Conditions

Temperature
60 °C

Procedure

A solution of 10.0 g (54.05 mmol) of 3-bromo-benzaldehyde in 150 ml of piperidine was treated at RT with 1.029 g (5.40 mmol) of copper(I)iodide and 6.246 g (5.40 mmol) of tetrakis-(triphenylphosphine)-palladium and the mixture was then warmed up to 60° C. After 10 min, a solution of 9.30 ml=6.66 g (81.07 mmol) of hex-1-yne in 150 ml of piperidine was added drop by drop during 1 hour. After 30 min, the oil bath temperature was steadily increased to 80° C. The reaction mixture was then stirred at 80° C. for 15 hours and subsequently cooled down to RT. The solvent was evaporated and the residue poured into crashed ice, acidified with HCl (37%) to pH 2-3 and extracted twice with EtOAc; the organic phases were washed with water, dried over magnesium sulfate, filtered and evaporated. The residue was purified by flash column chromatography (n-heptane/EtOAc 1:0 to 97:3) to give 8.78 g (87%) of the title compound as yellow oil. MS: 186.2 (M+).

Workup

  1. waitAfter 30 min
  2. temperaturethe oil bath temperature was steadily increased to 80° C
  3. temperaturesubsequently cooled down to RT
  4. customThe solvent was evaporated
  5. additionthe residue poured
  6. extractionextracted twice with EtOAc
  7. washthe organic phases were washed with water
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated
  11. customThe residue was purified by flash column chromatography (n-heptane/EtOAc 1:0 to 97:3)

Sources & evidence

ORD record
ord-967e1a0031f040539f4e96651194cf6c
Source dataset
uspto-grants-2011_05
Patent number
US07935707B2

Reaction notes

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