Ethylene Glycol → tert-Butyl 4-(4-aminophenyl)piperazine-1-carboxylate

HRID 245001Notes

Reaction equation

HRID 245001 reaction equation
I[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[C:9]([O:13][C:14]([N:16]1[CH2:21][CH2:20][NH:19][CH2:18][CH2:17]1)=[O:15])([CH3:12])([CH3:11])[CH3:10].P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(O)CO>CC(O)C.[Cu](I)I>[C:9]([O:13][C:14]([N:16]1[CH2:21][CH2:20][N:19]([C:2]2[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=2)[CH2:18][CH2:17]1)=[O:15])([CH3:12])([CH3:10])[CH3:11]

Participants

7

Reactant 4

HCID 174Ethylene GlycolHCID 108934-IodoanilineHCID 62657Potassium Phosphate, TribasicHCID 143452tert-Butyl piperazine-1-carboxylate

Product 1

HCID 11011301tert-Butyl 4-(4-aminophenyl)piperazine-1-carboxylateYield 43.3%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 3776IsopropanolSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-iodoaniline (0.654 g, 3 mmol), piperazine-1-carboxylic acid tert-butyl ester (0.67 g, 3.6 mmol), potassium phosphate (1.272 g, 6 mmol), ethylene glycol (0.33 ml) and copper iodide (0.03 g, 0.15 mmol) in 2-propanol (3 ml) was placed under argon in a sealed-tube and heated to 80° C. for 30 hours. After being cooled to room temperature, the medium was washed with water (50 ml) and extracted with ethyl acetate (100 ml). The organic layer was dried over MgSO4, concentrated and chromatographed (dichloromethane:acetone, 70:30) to yield 43a (0.36 g, 1.3 mmol, 43%) as a yellow powder.

Workup

  1. customwas placed under argon in a sealed-tube
  2. temperatureAfter being cooled to room temperature
  3. washthe medium was washed with water (50 ml)
  4. extractionextracted with ethyl acetate (100 ml)
  5. dry with materialThe organic layer was dried over MgSO4
  6. concentrationconcentrated
  7. customchromatographed (dichloromethane:acetone, 70:30)

Sources & evidence

ORD record
ord-21cc155a42d14e5c9f54ed5339bb73ba
Source dataset
uspto-grants-2014_02
Patent number
US08658681B2

Reaction notes

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