Ethanol → 1,4-Dimethylpiperazine

HRID 1604898Notes

Reaction equation

HRID 1604898 reaction equation
[NH:1]1[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.C=O.[H][H].[CH2:11](O)[CH3:12]>O.[Ni]>[CH3:6][N:1]1[CH2:12][CH2:11][N:4]([CH3:5])[CH2:3][CH2:2]1.[CH3:11][N:1]1[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.[NH:1]1[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1

Participants

9

Reactant 4

HCID 702Ethanol2×HCID 712FormaldehydeHCID 4837PiperazineHCID 178418361HCID 178418361, compound

Product 3

HCID 4837PiperazineYield 0.5%HCID 78181,4-DimethylpiperazineYield 60.4%HCID 531671-MethylpiperazineYield 38.2%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 962WaterSolvent

Procedure

A solution of 86 g. (1.0 mole) of piperazine in 262 g. ethanol was added with stirring to 130 g. (1.6 moles) of 37% formalin in an appropriate vessel at a temperature of 30°-40°C. maintained with cooling. This slurry, containing 25 wt.% water and 75 wt.% ethanol as solvent, based on solvent weight, was then charged to an autoclave containing 14 g. of a supported nickel catalyst (Harshaw Ni-3266P, Harshaw Chemical Company) and stirred in a hydrogen atmosphere at 91°C. under 50 psig for 5 hours. Analysis of the crude product by gas liquid chromatography, calculating on a water-alcohol free basis, gave 60.4% 1,4-dimethylpiperazine, 38.2% 1-methylpiperazine, and 0.5% piperazine.

Workup

  1. temperaturewith cooling
  2. additionwas then charged to an autoclave
  3. additioncontaining 14 g

Sources & evidence

ORD record
ord-e83c3f4028fa4b7bb366165276d2edd0
Source dataset
uspto-grants-1976_04
Patent number
US03948900

Reaction notes

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