p-Toluenesulfonic acid → Cis-4-(p-toluenesulfonyloxy)-2-[(1E,3E)-4-[4-(trifluoromethyl)phenyl]-1,3-butadien-1-yl]-1,3-dioxane

HRID 379959Notes

Reaction equation

HRID 379959 reaction equation
[C:1]1([CH3:16])[CH:6]=[CH:5][C:4]([S:7]([O:10][CH:11]([CH2:14]O)CO)(=[O:9])=[O:8])=[CH:3][CH:2]=1.[F:17][C:18]([F:32])([F:31])[C:19]1[CH:24]=[CH:23][C:22](/[CH:25]=[CH:26]/[CH:27]=[CH:28]/[CH:29]=[O:30])=[CH:21][CH:20]=1.C1(C)C=CC(S(O)(=O)=O)=CC=1.[C:44](=O)([O-])[OH:45].[Na+]>C(Cl)Cl>[C:1]1([CH3:16])[CH:2]=[CH:3][C:4]([S:7]([O:10][C@H:11]2[CH2:14][CH2:44][O:45][C@@H:29](/[CH:28]=[CH:27]/[CH:26]=[CH:25]/[C:22]3[CH:21]=[CH:20][C:19]([C:18]([F:31])([F:32])[F:17])=[CH:24][CH:23]=3)[O:30]2)(=[O:8])=[O:9])=[CH:5][CH:6]=1

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 516892Sodium BicarbonateHCID 103772501,3-Dihydroxypropan-2-yl 4-methylbenzenesulfonateHCID 10609261(2E,4E)-5-(4-(trifluoromethyl)phenyl)penta-2,4-dienal

Product 1

HCID 86583791Cis-4-(p-toluenesulfonyloxy)-2-[(1E,3E)-4-[4-(trifluoromethyl)phenyl]-1,3-butadien-1-yl]-1,3-dioxaneYield 29%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

In 4.5 ml of methylene chloride were dissolved 200 mg (0.81 mmol) of 2-(p-toluenesulfonyloxy)-1,3-propanediol and 206 mg (0.91 mmol) of (2E,4E)-5-[4-(trifluoromethyl)phenyl]-2,4-pentadienal, and 15 mg of p-toluenesulfonic acid and 0.8 g of molecular sieves 4A were added to the solution, followed by stirring of the resulting mixture at 0° C. for 1 hour. An aqueous sodium hydrogencarbonate solution was added to the reaction mixture and the mixture was stirred for 10 minutes. Then, the molecular sieves were removed by filtration and the filtrate was extracted with methylene chloride. The oil obtained by evaporation of the solvent was separated by preparative thin layer chromatography of silica gel (developing solvent: 20% ethyl acetate-hexane) to obtain 107 mg (yield: 29%) of a trans isomer having less polarity and 153 mg (yield: 42%) of a cis isomer having higher polarity as an oil, respectively.

Workup

  1. additionwere added to the solution
  2. stirringthe mixture was stirred for 10 minutes
  3. customThen, the molecular sieves were removed by filtration
  4. extractionthe filtrate was extracted with methylene chloride
  5. customThe oil obtained by evaporation of the solvent
  6. customwas separated by preparative thin layer chromatography of silica gel (developing solvent: 20% ethyl acetate-hexane)
  7. customto obtain 107 mg (yield: 29%) of a trans isomer

Sources & evidence

ORD record
ord-cc06adf4a107456e8c02b59f42b8ab7a
Source dataset
uspto-grants-2001_10
Patent number
US06300357B1

Reaction notes

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