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

HRID 538256

反応式

HRID 538256 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
100 °C

実験手順

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 0.5-1 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).

後処理

  1. temperatureheated
  2. temperatureat reflux for 1.5 hours
  3. customwas observed for the first 0.5-1 hour
  4. temperatureof heating
  5. temperatureThe reaction was cooled
  6. additionwas carefully added
  7. customEthanol was removed by azeotropic distillation at 105° C.
  8. additionwhile adding an additional 4000 mL of toluene to the reaction flask
  9. distillationduring the course of the distillation
  10. distillationAfter collection of 9000 mL of distillate
  11. addition1000 mL of toluene was 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

出典と根拠

ORDレコード
ord-c0a9519371d340e7893a7db35723d440
出典データセット
uspto-grants-2014_10
特許番号
US08865721B2

関連ノート

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