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

HRID 247635Notes

Reaction equation

HRID 247635 reaction equation
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.C(OCC)C.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]

Participants

8

Reactant 4

HCID 6410tert-Butyl hydroperoxideHCID 14798Sodium Hydroxide2×HCID 6992610Dibutyl D-tartrateHCID 542146164-(2',5'-Dimethoxy-3',4',6'-trimethylphenyl)-2-methyl-2-butenol

Product 1

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

Reagents, catalysts & solvents 3

HCID 11026Titanium isopropoxideCatalystHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×

Procedure

0.594 ml of titanium tetraisopropoxide was dissolved in 10 ml of dry methylene chloride. Thereupon, 524 mg of dibutyl D-tartrate were added dropwise at -20° C. and the mixture was left to stand at -20° C. for 10 minutes. 197 mg of 4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2-methyl-2-butenol were then added and subsequently a further 180 mg of tert.butyl hydroperoxide (80%) were added dropwise (as a solution in 0.5 ml of methylene chloride). The thus-obtained yellow solution was 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 were then separated, the aqueous phase was washed twice with methylene chloride, the organic phases were dried over sodium sulphate and concentrated. The colourless oil obtained was dissolved in 20 ml of ethyl ether and stirred with 5 ml of 1N sodium hydroxide solution for 1 hour. The phases were again separated, the aqueous phase was washed twice with ethyl ether, the organic phases were dried over sodium sulphate and concentrated. There were obtained 188 mg (98%) of (2R,3R)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2,3-epoxy-2-methylbutanol.

Workup

  1. waitthe mixture was left
  2. waitThe thus-obtained yellow solution was left
  3. waitto stand at -20° C. for 4 to 5 days
  4. waitleft
  5. customThe phases were then separated
  6. washthe aqueous phase was washed twice with methylene chloride
  7. dry with materialthe organic phases were dried over sodium sulphate
  8. concentrationconcentrated
  9. customThe colourless oil obtained
  10. customThe phases were again separated
  11. washthe aqueous phase was washed twice with ethyl ether
  12. dry with materialthe organic phases were dried over sodium sulphate
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-60d80088032f4a68a2aacbc59f880feb
Source dataset
uspto-grants-1987_11
Patent number
US04709055

Reaction notes

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