Ammonia → 1-(2,2-Dimethylpropanoyl)-4-(1,1-dimethylprop-2-yn-1-yl)piperazine

HRID 1454989Notes

Reaction equation

HRID 1454989 reaction equation
C(O[C:5]([CH3:9])([CH3:8])[C:6]#[CH:7])(=O)C.[N:10]1([C:16]([O:18]C(C)(C)C)=O)[CH2:15][CH2:14][NH:13][CH2:12][CH2:11]1.[OH-].[Na+].N>O1CCCC1.C(OCC)(=O)C>[CH3:6][C:5]([CH3:9])([CH3:8])[C:16]([N:10]1[CH2:11][CH2:12][N:13]([C:5]([CH3:8])([CH3:9])[C:6]#[CH:7])[CH2:14][CH2:15]1)=[O:18]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 14798Sodium HydroxideHCID 741441,1-Dimethylprop-2-ynyl acetateHCID 143452tert-Butyl piperazine-1-carboxylate

Product 1

HCID 866102081-(2,2-Dimethylpropanoyl)-4-(1,1-dimethylprop-2-yn-1-yl)piperazineYield 157%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

0.756 g (6 mmol) of 1,1-dimethylprop-2-yn-1-yl acetate (J. Org. Chem. 1994, 59, 2282-4) and 2.235 g (12 mmol) of 1,1-dimethylethyl piperazine-1-carboxylate are dissolved in 9 ml of tetrahydrofuran and then 0.059 g (0.6 mmol) of cuprous chloride is added. The mixture is heated at reflux for 3 hours. After cooling to ambient temperature, 100 ml of ethyl acetate, 10 ml of 1N aqueous sodium hydroxide and 2 ml of 30% ammonia are added. The organic phase is separated off and washed with 2 times 10 ml of water and then with 10 ml of saturated aqueous sodium chloride solution. It is dried over sodium sulphate and evaporated. The product is purified by chromatography on silica gel, eluting with an 85/15 then 75/25 and 65/35 mixture of cyclohexane and ethyl acetate, to give 1.19 g (4.71 mmol) of product in the form of a pale yellow solid.

Workup

  1. temperatureThe mixture is heated
  2. temperatureat reflux for 3 hours
  3. customThe organic phase is separated off
  4. washwashed with 2 times 10 ml of water
  5. dry with materialIt is dried over sodium sulphate
  6. customevaporated
  7. customThe product is purified by chromatography on silica gel
  8. washeluting with an 85/15
  9. addition75/25 and 65/35 mixture of cyclohexane and ethyl acetate

Sources & evidence

ORD record
ord-5023dc0f1d6741cca9dd0dad900340d6
Source dataset
uspto-grants-2009_01
Patent number
US07482346B2

Reaction notes

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