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tert-Butyl hydroperoxide → (2R,3R)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2,3-epoxy-2-methylbutanol

HRID 1789599
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HRID 1789599 반응식
C([C@H]([C@@H](C(OCCCC)=O)O)O)(OCCCC)=[O:2].[CH3:19][O:20][C:21]1[C:26]([CH3:27])=[C:25]([CH3:28])[C:24]([O:29][CH3:30])=[C:23]([CH3:31])[C:22]=1[CH2:32][CH:33]=[C:34]([CH3:37])[CH2:35][OH:36].C(OO)(C)(C)C.[OH-].[Na+]>C(Cl)Cl.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[CH3:19][O:20][C:21]1[C:26]([CH3:27])=[C:25]([CH3:28])[C:24]([O:29][CH3:30])=[C:23]([CH3:31])[C:22]=1[CH2:32][C@H:33]1[O:2][C@:34]1([CH3:37])[CH2:35][OH:36]
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참가 물질

7

반응물 4

HCID 6410tert-Butyl hydroperoxideHCID 14798Sodium HydroxideHCID 6992610Dibutyl D-tartrateHCID 542146164-(2',5'-Dimethoxy-3',4',6'-trimethylphenyl)-2-methyl-2-butenol

생성물 1

HCID 18602181(2R,3R)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2,3-epoxy-2-methylbutanol수율 98%

시약·촉매·용매 2

HCID 11026
Titanium isopropoxide
촉매
HCID 6344Dichloromethane용매2회

실험 절차

0.594 ml of titanium tetraisopropoxide is dissolved in 10 ml of dry methylene chloride. Thereupon, 524 ml of dibutyl D-tartrate are added dropwise at -20° C. and the mixture is left to stand at -20° C. for 10 minutes. 197 mg of 4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2-methyl-2-butenol are then added and subsequently 180 mg of tert.butyl hydroperoxide (80%) are added dropwise (as a solution in 0.5 ml of methylene chloride). The thus-obtained yellow solution is left to stand at -20° C. for 4 to 5 days, then treated with 5 ml of 1N sodium hydroxide solution, left to warm to room temperature and stirred for 1 hour. The phases are then separated, and the aqueous phase is washed twice with methylene chloride. The combined organic phases are subsequently dried over anhydrous sodium sulphate and concentrated. The thus-obtained colourless oil is dissolved in 20 ml of diethyl ether and stirred with 5 ml of 1N sodium hydroxide solution for 1 hour. The phases are again separated, the aqueous phase is washed twice with diethyl ether and the organic phases are dried over anhydrous sodium sulphate and concentrated. There are obtained 188 mg (98%) of (2R,3R)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2,3-epoxy-2-methylbutanol, [α]D20 +18.2° (c=2% in CHCl3).

후처리

  1. waitthe mixture is left
  2. waitThe thus-obtained yellow solution is left
  3. waitto stand at -20° C. for 4 to 5 days
  4. waitleft
  5. customThe phases are then separated
  6. washthe aqueous phase is washed twice with methylene chloride
  7. dry with materialThe combined organic phases are subsequently dried over anhydrous sodium sulphate
  8. concentrationconcentrated
  9. dissolutionThe thus-obtained colourless oil is dissolved in 20 ml of diethyl ether
  10. stirringstirred with 5 ml of 1N sodium hydroxide solution for 1 hour
  11. customThe phases are again separated
  12. washthe aqueous phase is washed twice with diethyl ether
  13. dry with materialthe organic phases are dried over anhydrous sodium sulphate
  14. concentrationconcentrated

출처 및 근거

ORD 기록
ord-fd24838512664f5e9442ce1f96d1f3cb
출처 데이터셋
uspto-grants-1987_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US04689427

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