Carbon Dioxide → (2S,5R)-1-allyl-2,5-dimethylpiperazine

HRID 538274

Reaktionsgleichung

Reaktionsgleichung von HRID 538274
[CH2:1]([N:4]1[C@H:9]([CH3:10])[CH2:8][N:7](C(OCC)=O)[C@@H:6]([CH3:16])[CH2:5]1)[CH:2]=[CH2:3].[OH-].[K+].C(=O)=O.C1(C)C=CC=CC=1>C(O)C>[CH2:1]([N:4]1[CH2:5][C@@H:6]([CH3:16])[NH:7][CH2:8][C@@H:9]1[CH3:10])[CH:2]=[CH2:3]

Komponenten

6

Edukt 4

HCID 280Carbon DioxideHCID 1140TolueneHCID 14797Potassium HydroxideHCID 10823138Ethyl trans-4-allyl-2,5-dimethyl-1-piperazinecarboxylate

Produkt 1

HCID 11291191(2S,5R)-1-allyl-2,5-dimethylpiperazineAusbeute 69 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

Ethyl trans-4-allyl-2,5-dimethyl-1-piperazinecarboxylate (630 g, 2.78 mol) was added to a solution of 87% potassium hydroxide pellets (2970 g, 46 mol) in 4300 mL of 95% ethanol and heated at reflux for 1.5 hours. Carbon dioxide evolution was observed for the first 0.5 l hour of heating. The reaction was cooled below reflux temperature and 2000 mL of toluene was carefully added. Ethanol was removed by azeotropic distillation at 105 C, while adding an additional 4000 mL of toluene to the reaction flask during the course of the distillation. After collection of 9000 mL of distillate, the reaction was cooled to 100 C and 1000 mL of toluene was carefully added. The solution was slowly cooled to 5 C and maintained at 5 C for 30 minutes. The solution was filtered, and the filter cake was washed with an additional 1500 mL of toluene. The filtrate was washed with 1000 mL of water, dried over magnesium sulfate, and the solvent was removed to give 296 g (69%) of trans-1-allyl-2,5-dimethylpiperazine as a dark liquid. NMR (300 MHz, DMSO-d6): δ 0.87 (d, J=6.3 Hz, 3H); 0.92 (d, J=6.3 Hz, 3H); 1.63 (t, J=11 Hz, 1H); 2.05 (m, 1H); 2.30 (t, J=11 Hz, 1H); 2.6-2.8 (m, 4H); 3.33 (dd, J1=5 Hz, J2=14 Hz, 1H); 5.09 (d, J=8.7 Hz, 1H); 5.13 (d, J=14 Hz, 1H) 5.8 (m, 1H).

Aufarbeitung

  1. temperatureheated
  2. temperatureat reflux for 1.5 hours
  3. temperatureof heating
  4. temperatureThe reaction was cooled
  5. additionwas carefully added
  6. customEthanol was removed by azeotropic distillation at 105 C
  7. additionwhile adding an additional 4000 mL of toluene to the reaction flask
  8. distillationduring the course of the distillation
  9. distillationAfter collection of 9000 mL of distillate
  10. temperaturethe reaction was cooled to 100 C and 1000 mL of toluene
  11. additionwas carefully added
  12. temperatureThe solution was slowly cooled to 5 C
  13. temperaturemaintained at 5 C for 30 minutes
  14. filtrationThe solution was filtered
  15. washthe filter cake was washed with an additional 1500 mL of toluene
  16. washThe filtrate was washed with 1000 mL of water
  17. dry with materialdried over magnesium sulfate
  18. customthe solvent was removed

Quellen und Nachweise

ORD-Eintrag
ord-425a82a6561a4da7b5b065e1ae1af41b
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08865721B2

Verknüpfte Notizen

Wird geladen…