Chlorotrimethylsilane → HCID 12769232, 화합물

HRID 621065노트

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HRID 621065 반응식
C([Li])CCC.C(NC(C)C)(C)C.[CH3:13][C:14]1([CH3:23])[O:21][CH2:20][CH2:19][CH:18]2[N:15]1[C:16](=[O:22])[CH2:17]2.C1(C)C=CC(S([N:33]=[N+:34]=[N-:35])(=O)=O)=CC=1.C[Si](Cl)(C)C>CCCCCC.O1CCCC1>[CH3:13][C:14]1([CH3:23])[O:21][CH2:20][CH2:19][CH:18]2[N:15]1[C:16](=[O:22])[CH:17]2[N:33]=[N+:34]=[N-:35]

참가 물질

8

반응물 5

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 13661p-Toluenesulfonyl azideHCID 12769229HCID 12769229, 화합물HCID 178418339Butyllithium

생성물 1

HCID 12769232HCID 12769232, 화합물

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매3회HCID 8058Hexane용매

실험 절차

In a nitrogen stream under stirring, 50 ml of dry tetrahydrofuran is cooled to -78° C. and, then, 20 ml of a solution of 15% n-butyllithium in n-hexane is added thereto. After dropwise addition of 3.66 ml of diisopropylamine, the mixture is stirred at -78° C. for 15 minutes. A solution of 3.1 g of 2,2-dimethyl-1-aza-3-oxabicyclo[4.2.0]octan-8-one in 15 ml of dry tetrahydrofuran is added dropwise and the mixture is stirred at -78° C. for one hour. Then, a solution of 4.34 g of p-toluenesulfonyl azide in 15 ml of dry tetrahydrofuran is added dropwise and the mixture is stirred at -50° C. to -60° C. for 1.5 hours. To this mixture 5.1 ml of trimethylsilyl chloride is added dropwise and the reaction mixture is heated under reflux for 5 hours. After cooling, the insolubles are filtered off and the filtrate is concentrated under reduced pressure. The residue is shaken with water and ethyl acetate and the ethyl acetate layer is separated, washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The solvent is then distilled off and the residue is purified by silica gel column chromatography to give 2,2-dimethyl-7-azido-1-aza-3-oxabicyclo[4.2.0]octan-8-one as a 1:4 mixture of cis- and trans-isomers.

후처리

  1. stirringthe mixture is stirred at -78° C. for 15 minutes
  2. stirringthe mixture is stirred at -78° C. for one hour
  3. stirringthe mixture is stirred at -50° C. to -60° C. for 1.5 hours
  4. temperaturethe reaction mixture is heated
  5. temperatureunder reflux for 5 hours
  6. temperatureAfter cooling
  7. filtrationthe insolubles are filtered off
  8. concentrationthe filtrate is concentrated under reduced pressure
  9. stirringThe residue is shaken with water and ethyl acetate
  10. customthe ethyl acetate layer is separated
  11. washwashed with water
  12. dry with materialdried over anhydrous sodium sulfate
  13. concentrationconcentrated under reduced pressure
  14. distillationThe solvent is then distilled off
  15. customthe residue is purified by silica gel column chromatography

출처 및 근거

ORD 기록
ord-7e6a232601554ad29cc14a95b49e961d
출처 데이터셋
uspto-grants-1989_04
특허 번호
US04822790

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