Chlorotrimethylsilane → HCID 12769232、化合物

HRID 621157ノート

反応式

HRID 621157 の反応式
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]

参加物

8

反応物 5

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 13661p-Toluenesulfonyl azideHCID 12769229HCID 12769229、化合物HCID 178418339Butyllithium

生成物 1

HCID 12769232HCID 12769232、化合物

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒3 回HCID 8058Hexane溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-a51437db75d94014ace9879f407c1842
出典データセット
uspto-grants-1989_04
特許番号
US04822788

反応ノート

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