1-Hexyne → HCID 15859215, compound

HRID 583314Notes

Reaction equation

HRID 583314 reaction equation
[CH3:1][O:2][C:3](=[O:31])[C:4]1[CH:9]=[C:8](Br)[CH:7]=[C:6]([CH3:11])[C:5]=1[N:12]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[S:13]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)(=[O:15])=[O:14].[CH:32]#[C:33][CH2:34][CH2:35][CH2:36][CH3:37]>CN(C=O)C.C(N(CC)CC)C.CCOCC.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[CH3:1][O:2][C:3](=[O:31])[C:4]1[CH:9]=[C:8]([C:32]#[C:33][CH2:34][CH2:35][CH2:36][CH3:37])[CH:7]=[C:6]([CH3:11])[C:5]=1[N:12]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[S:13]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)(=[O:15])=[O:14]

Participants

8

Reactant 2

HCID 127321-Hexyne2×HCID 70052828HCID 70052828, compound

Product 1

HCID 15859215HCID 15859215, compoundYield 61%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

To a solution of 0.324 g (0.643 mmol) of the product of Example 11 in 2.0 mL of DMF and 2.0 mL of triethylamine was added 0.088 mL (0.771 mmol) of 1-hexyne, 9 mg (0.013 mmol) of bis(triphenylphosphine)palladium(II)dichloride and 1.2 mg of copper(I)iodide. The reaction mixture was then heated to 65 degrees for 5 h and an additional 0.22 mL of 1-hexyne was added to the reaction. The motion was then heated to zeflux for 6 h and then cooled to room tempemaure and diluted with ether. The organics were washed with water and brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was chromatographed on silica eluting with EtOAc-Hex (1:10) to provide 0.198 g (61%) of the desired product as a yellow oil. Electrospray Mass Spec: 506.3 (M+H)+.

Workup

  1. temperatureThe reaction mixture was then heated to 65 degrees for 5 h
  2. temperatureThe motion was then heated to zeflux for 6 h
  3. temperaturecooled to room tempemaure
  4. washThe organics were washed with water and brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was chromatographed on silica eluting with EtOAc-Hex (1:10)

Sources & evidence

ORD record
ord-f6d858244b1e4a92b98bfb017f27046e
Source dataset
uspto-grants-1999_07
Patent number
US05929097

Reaction notes

Loading…