1-Butyne, 3-chloro-3-methyl- → 147539-53-5

HRID 1449736Notes

Reaction equation

HRID 1449736 reaction equation
[CH3:1][C:2]([CH3:13])([O:4][C:5]([N:7]1[CH2:12][CH2:11][NH:10][CH2:9][CH2:8]1)=[O:6])[CH3:3].Cl[C:15]([CH3:19])([CH3:18])[C:16]#[CH:17]>CCOCC.O.[Cu]>[CH3:3][C:2]([CH3:13])([O:4][C:5]([N:7]1[CH2:8][CH2:9][N:10]([C:15]([CH3:19])([CH3:18])[C:16]#[CH:17])[CH2:11][CH2:12]1)=[O:6])[CH3:1]

Participants

6

Reactant 2

HCID 706791-Butyne, 3-chloro-3-methyl-HCID 143452tert-Butyl piperazine-1-carboxylate

Product 1

HCID 21477651147539-53-5

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent3×

Procedure

To a mixture of 1-(1,1-dimethylethoxycarbonyl)piperazine (3.29 g), copper powder (20 mg), cuprous chloride (20 mg), ether (4 ml), and water (1 ml) under nitrogen at 0° is added a solution of 3-chloro-3-methyl-1-butyne in ether (1 ml) in 4 portions over 15 min. The mixture is stirred at 20°-25° for 2 hr, diluted with ether (25 ml) and water (10 ml), and the layers are separated. The aqueous layer is extracted with ether (3×25 ml), and the combined organic layer is washed with saline (25 ml), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a solid which is then chromatographed on silica gel (70-230, 100 g), eluting with ethyl acetate/hexane (25/75). Pooling of fractions giving an Rf =0.48 by TLC (ethyl acetate/hexane, 50/50) and removal of solvent under reduced pressure gives the title compound, mp 105.5°-107°.

Workup

  1. customthe layers are separated
  2. extractionThe aqueous layer is extracted with ether (3×25 ml)
  3. washthe combined organic layer is washed with saline (25 ml)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customto give a solid which
  7. customis then chromatographed on silica gel (70-230, 100 g)
  8. washeluting with ethyl acetate/hexane (25/75)
  9. customPooling of fractions giving an Rf =0.48
  10. customby TLC (ethyl acetate/hexane, 50/50) and removal of solvent under reduced pressure

Sources & evidence

ORD record
ord-40d196346efd464c8f4fc79eb700097b
Source dataset
uspto-grants-1997_02
Patent number
US05599930

Reaction notes

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