Hydrochloric Acid → Oxiranemethanol, 4-methylbenzenesulfonate, (S)-

HRID 1739459Notes

Reaction equation

HRID 1739459 reaction equation
C(=O)([O-])[O-].[K+].[K+].Cl[CH2:8][C@@H:9]([OH:12])[CH2:10][OH:11].C(N(CC)CC)C.[C:20]1([CH3:30])[CH:25]=[CH:24][C:23]([S:26](Cl)(=[O:28])=[O:27])=[CH:22][CH:21]=1.Cl>ClCCCl>[S:26]([C:23]1[CH:24]=[CH:25][C:20]([CH3:30])=[CH:21][CH:22]=1)([O:11][CH2:10][C@H:9]1[O:12][CH2:8]1)(=[O:28])=[O:27]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 148904alpha-Chlorohydrin, (+)-

Product 1

HCID 153296Oxiranemethanol, 4-methylbenzenesulfonate, (S)-Yield 70.3%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

To a suspension of 37.5 g of potassium carbonate (0.27 mol) and 250 ml of 1,2-dichloroethane, was added dropwise at 24-28° C. 20 g of (S)-3-chloro-1,2-propanediol (0.18 mol) (optical purity: 98.9% ee). After finishing the addition, the solution was stirred for 26 hours and cooled. To the reaction solution were added dropwise under stirring at 5-10° C. 20.1 g of triethylamine (0.2 mol) and 0.4 g of N,N-dimethylaminopyridine (0.0033 mol) and 34.5 g of p-toluenesulfonyl chloride (0.18 ml) in order. After finishing the addition the mixture was stirred for 3 hours and the resulting salt was dissolved by adding 150 ml of 3% hydrochloric acid. The organic layer was washed with 150 ml of 1% hydrochloric acid and 150 ml of water. The excess solvent was removed under vacuo. The chemical purity and optical purity at that time were 93.7%, 96.6% ee respectively. The residue was recrystallized from isopropyl alcohol/hexane=1/1 (V/V) to give 28.9 g of (S)-glycidyl tosylate (yield 70%). Chemical purity: 98.3%, optical purity: 97.5% ee

Workup

  1. additionwas added dropwise at 24-28° C
  2. additionthe addition
  3. temperaturecooled
  4. additionTo the reaction solution were added dropwise
  5. stirringunder stirring at 5-10° C
  6. additionthe addition the mixture
  7. stirringwas stirred for 3 hours
  8. dissolutionthe resulting salt was dissolved
  9. washThe organic layer was washed with 150 ml of 1% hydrochloric acid and 150 ml of water
  10. customThe excess solvent was removed under vacuo
  11. customThe residue was recrystallized from isopropyl alcohol/hexane=1/1 (V/V)

Sources & evidence

ORD record
ord-4c83ea34242e4db580ffdde017c2574e
Source dataset
uspto-grants-1999_10
Patent number
US05965753

Reaction notes

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