1,2-Dichloroethane → 1,4,7,10-Tetraazacyclododecane

HRID 1274414Notes

Reaction equation

HRID 1274414 reaction equation
[NH2:1][CH2:2][CH2:3][NH:4][CH2:5][CH2:6][NH:7][CH2:8][CH2:9][NH2:10].[CH:11]([CH:13]=O)=O.O.ClCCCl.O.NN.[OH-].[K+]>CO.CN(C)C=O>[NH:4]1[CH2:5][CH2:6][NH:7][CH2:8][CH2:9][NH:10][CH2:13][CH2:11][NH:1][CH2:2][CH2:3]1

Participants

9

Reactant 6

HCID 111,2-DichloroethaneHCID 962WaterHCID 5565TriethylenetetramineHCID 7860GlyoxalHCID 14797Potassium HydroxideHCID 24654Hydrazine hydrate (1:1)

Product 1

HCID 649631,4,7,10-Tetraazacyclododecane

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Procedure

50 g of triethylenetetramine (0.342 mol) is dissolved in 1 ml of methanol and mixed at room temperature with 39 ml of 40% glyoxal in water (0.342 mol). After 20 hours of stirring, the solvent is distilled off in a vacuum, and an orange-colored oil is obtained, which then is taken up in 400 ml of dimethylformamide and mixed with 81.2 ml (101.5 g=1.026 mol) of 1,2-dichloroethane. After 8 hours of stirring at 40° C., it is concentrated by evaporation in a vacuum, the residue is taken up in 400 ml of ethanol and acidified to pH=3-4 with 37% aqueous hydrochloric acid. 166 ml (171 g=3.42 mol) of hydrazine hydrate is added to this reaction solution at room temperature, and it is heated under reflux for 30 hours. The reaction solution is set at pH=13 with solid potassium hydroxide. The reaction solution is subsequently concentrated by evaporation in a vacuum, taken up once more in 100 ml of ethanol, and the solvent is removed again in a vacuum. The residue is mixed with 25 g of activated carbon and 150 ml of formaldehyde diethylacetal, and it is heated under reflux for some time before the hot solution is filtered through a membrane. After the solution is cooled, the product is isolated by filtration.

Workup

  1. distillationthe solvent is distilled off in a vacuum
  2. customan orange-colored oil is obtained
  3. stirringAfter 8 hours of stirring at 40° C.
  4. concentrationit is concentrated by evaporation in a vacuum
  5. temperatureit is heated
  6. temperatureunder reflux for 30 hours
  7. concentrationThe reaction solution is subsequently concentrated by evaporation in a vacuum
  8. customthe solvent is removed again in a vacuum
  9. additionThe residue is mixed with 25 g of activated carbon and 150 ml of formaldehyde diethylacetal, and it
  10. temperatureis heated
  11. temperatureunder reflux for some time before the hot solution
  12. filtrationis filtered through a membrane
  13. temperatureAfter the solution is cooled
  14. customthe product is isolated by filtration

Sources & evidence

ORD record
ord-2832f8b2e1de4f21a336af49485cf785
Source dataset
uspto-grants-2000_12
Patent number
US06156890

Reaction notes

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