Triphenylphosphine → HCID 18442161, compound

HRID 458496Notes

Reaction equation

HRID 458496 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:9]2[O:10][C:11]([C:14]3[CH:19]=[CH:18][C:17]([O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[CH:16][CH:15]=3)=[N:12][N:13]=2)[CH:5]=[C:6](Br)[CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:48][Si:49]([C:52]#[CH:53])([CH3:51])[CH3:50]>CCN(CC)CC.CO.[Cu]I.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:48][Si:49]([CH3:51])([CH3:50])[C:52]1[C:3]([C:2]#[CH:7])=[C:4]([C:9]2[O:10][C:11]([C:14]3[CH:19]=[CH:18][C:17]([O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[CH:16][CH:15]=3)=[N:12][N:13]=2)[CH:5]=[C:6]([Si:49]([CH3:51])([CH3:50])[CH3:48])[CH:53]=1

Participants

8

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 21982087HCID 21982087, compound

Product 1

HCID 18442161HCID 18442161, compoundYield 11.8%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 887MethanolSolventHCID 8471TriethylamineSolvent

Procedure

To an ice-cold mixture of 2-(3,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (11.47 g, 24.4 mmol), triphenylphosphine (0.1816 g, 0.692 mmol), copper (I) iodide (0.062 g, 0.326 mmol) and palladium (II) acetate (0.0594 g, 0.265 mmol) in 100 mL Et3N was added trimethylsilyl acetylene (6.0 g, 61.1 mmol). The mixture was stirred in the ice bath for 30 minutes. The ice bath was removed and after a further 30 minutes warming to room temperature the mixture was heated at reflux for 20 hours. The cooled reaction mixture was slurried in 150 mL methanol. The insoluble material was filtered off and dissolved in chloroform. Precipitation with hexane and evaporation to dryness of the hexane solution gave 2-(3,5-bis-trimethylsilanylethynylphenyl)-5-(4-octyloxyphenyl)-[1,3,4]oxadiazole (1.5 g, 11% yield). The methanol soluble filtrate was evaporated to dryness and dissolved in 250 mL chloroform. About 1.5 L of hexane was added. Filtration gave a dark solid material (3.5 g). Evaporation to dryness of the filtrate gave a further crop of 2-(3,5-bis-trimethylsilanylethynyl-phenyl)-5-(4-octyloxyphenyl)-[1,3,4]oxadiazole (3.5 g, 34% yield in total).

Workup

  1. customThe ice bath was removed and after a further 30 minutes
  2. temperaturewas heated
  3. temperatureat reflux for 20 hours
  4. customThe cooled reaction mixture
  5. filtrationThe insoluble material was filtered off
  6. dissolutiondissolved in chloroform
  7. customPrecipitation
  8. customwith hexane and evaporation to dryness of the hexane solution

Sources & evidence

ORD record
ord-ff977965b78c4cfca180ff8fc5ccacbd
Source dataset
uspto-grants-2007_03
Patent number
US07192657B2

Reaction notes

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