4-Toluenesulfonyl chloride → HCID 58633250, compound

HRID 2368788Notes

Reaction equation

HRID 2368788 reaction equation
[Cl-].[Li+].C([Mg]Cl)=C.[S:7](Cl)([C:10]1[CH:16]=[CH:15][C:13]([CH3:14])=[CH:12][CH:11]=1)(=[O:9])=[O:8].[CH3:18][C@@H:19]([OH:23])[CH2:20][CH:21]=[CH2:22]>C1COCC1.[Cu]Cl>[C:13]1([CH3:14])[CH:15]=[CH:16][C:10]([S:7]([O:23][C@@H:19]([CH2:20][CH:21]=[CH2:22])[CH3:18])(=[O:9])=[O:8])=[CH:11][CH:12]=1

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 433294Lithium ChlorideHCID 6999724(2R)-pent-4-en-2-olHCID 178461836HCID 178461836, compound

Product 1

HCID 58633250HCID 58633250, compound

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

Copper(I) chloride (3.24 g, 32.4 mmol) and lithium chloride (2.75 g, 64.8 mmol) were dissolved in THF (0.64 L) and cooled to 0° C. Vinyl magnesium chloride (1.87 kg, 3.56 mol, 16.5% in THF) was added slowly, maintaining the temperature below 5° C. The mixture was cooled to −20° C. A cooled solution of R-propylene oxide (0.19 kg, 3.24 mol) in THF (0.41 L) was added slowly, maintaining the temperature below −10° C. The reaction mixture was stirred until more than 98.5% of the epoxide had been consumed (using GC). The mixture was added slowly to a cooled solution of TsCl (0.67 kg, 3.43 mol) in THF (1.72 L). The mixture was heated to ambient temperature and stirred until more than 98% of the 4-penten-2(R)-ol had been consumed (using GC). The reaction mixture was transferred to a cool mixture of water (2.28 L) and MTBE (1.54 L). Hydrochloric acid (65.5 g) was added until a slightly acidic pH was obtained. The phases were separated and the aqueous phase was washed with MTBE. The combined organic phases were washed with aqueous sodium chloride solution and the organic phase was distilled to remove MTBE, to yield (R)-4-penten-2-yl p-toluenesulfonate in a THF solution.

Workup

  1. temperaturemaintaining the temperature below 5° C
  2. temperatureThe mixture was cooled to −20° C
  3. temperaturemaintaining the temperature below −10° C
  4. customhad been consumed (using GC)
  5. temperatureThe mixture was heated to ambient temperature
  6. customhad been consumed (using GC)
  7. additionThe reaction mixture was transferred to a cool mixture of water (2.28 L) and MTBE (1.54 L)
  8. additionHydrochloric acid (65.5 g) was added until a slightly acidic pH
  9. customwas obtained
  10. customThe phases were separated
  11. washthe aqueous phase was washed with MTBE
  12. washThe combined organic phases were washed with aqueous sodium chloride solution
  13. distillationthe organic phase was distilled
  14. customto remove MTBE

Sources & evidence

ORD record
ord-81f0a7c56b234a1ca8ae4cad3ecfd225
Source dataset
uspto-grants-2014_04
Patent number
US08703802B2

Reaction notes

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