4-Toluenesulfonyl chloride → bicyclo[2.2.2]oct-1-ylmethyl 4-methylbenzene-1-sulfonate

HRID 1600988Notes

Reaction equation

HRID 1600988 reaction equation
[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7](Cl)(=[O:9])=[O:8])=[CH:3][CH:2]=1.[C:12]12([CH2:20][OH:21])[CH2:19][CH2:18][CH:15]([CH2:16][CH2:17]1)[CH2:14][CH2:13]2.C(N(CC)CC)C.C(=O)([O-])O.[Na+]>C(#N)C>[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7]([O:21][CH2:20][C:12]23[CH2:19][CH2:18][CH:15]([CH2:16][CH2:17]2)[CH2:14][CH2:13]3)(=[O:9])=[O:8])=[CH:3][CH:2]=1

Participants

6

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 516892Sodium BicarbonateHCID 13245694{bicyclo[2.2.2]octan-1-yl}methanol

Product 1

HCID 280185bicyclo[2.2.2]oct-1-ylmethyl 4-methylbenzene-1-sulfonateYield 28.6%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Solid para-toluenesulfonyl chloride (0.449 g) was added to a solution of bicyclo-[2,2,2]oct-1-ylmethanol (300 mg) and triethylamine (0.45 ml) in anhydrous acetonitrile (6 ml) under nitrogen. The mixture was stirred at room temperature for 16 hours then heated at reflux for 18 hours, poured into saturated aqueous sodium hydrogen carbonate solution and extracted with ether. The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography over silica eluting with ether:hexane (1:9) and further purified by preparative normal-phase HPLC on a Dynamax™ Silica column with hexane:ethyl acetate gradient elution to give the sub-title compound as an oil (0.180 g).

Workup

  1. temperaturethen heated
  2. temperatureat reflux for 18 hours
  3. extractionextracted with ether
  4. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography over silica eluting with ether:hexane (1:9)
  8. customfurther purified by preparative normal-phase HPLC on a Dynamax™ Silica column with hexane
  9. washethyl acetate gradient elution

Sources & evidence

ORD record
ord-a6709b4244e94ee1af5917c64c681f12
Source dataset
uspto-grants-1999_11
Patent number
US05977105

Reaction notes

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