4-Toluenesulfonyl chloride → HCID 178447926, compound

HRID 1941719Notes

Reaction equation

HRID 1941719 reaction equation
[CH2:1]([Li])[CH2:2]CC.[C:6]1([CH3:16])[CH:11]=[CH:10][C:9](S(Cl)(=O)=O)=[CH:8][CH:7]=1.[CH2:17]1[CH2:21][O:20][CH2:19]C1>>[CH2:16]([C@H:6]1[CH2:11][CH2:10][C@H:9]([CH:21]2[CH2:17][CH2:19][O:20]2)[CH2:8][CH2:7]1)[CH2:1][CH3:2]

Participants

4

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8028Tetrahydrofuran2×HCID 178418339Butyllithium2×

Product 1

HCID 178447926HCID 178447926, compoundYield 70%

Procedure

THF (1,000 ml) was added to 1-(trans-4-propyl-cyclohexyl)-propane-1,3-diol(4) (229.3 g) prepared in the third step in a reaction vessel under an atmosphere of nitrogen. n-Butyllithium (1.63 M in n-hexane; 702 ml) was added dropwise to the mixture at around −5° C. After 30 minutes of stirring, p-toluenesulfonyl chloride (218.2 g) in a THF (1,000 ml) solution was added dropwise. After the reaction mixture had been stirred for 30 minutes, n-butyllithium (1.63 M in n-hexane; 702 ml) was added dropwise at around −5° C., and then the reaction mixture was heated slowly up to the reflux temperature. After the evolution of gas had ceased, the reaction mixture was cooled to room temperature, and quenched with a saturated aqueous solution of ammonium chloride, and then water (1,000 ml) was added to give two layers. The water layer was extracted with toluene (500 ml) three times, and the combined organic layer was washed with water and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was treated with silica gel chromatography (silica gel: 200 g, eluent: heptane/ethyl acetate=90/10 by volume) and distilled under reduced pressure (71 to 74° C., 3 mmHg) to give 2-(trans-4-propyl-cyclohexyl)-oxetane (5) (145 g) in 70% yield.

Workup

  1. customprepared in the third step in a reaction vessel under an atmosphere of nitrogen
  2. stirringAfter the reaction mixture had been stirred for 30 minutes
  3. temperaturethe reaction mixture was heated slowly up to the reflux temperature
  4. customquenched with a saturated aqueous solution of ammonium chloride
  5. additionwater (1,000 ml) was added
  6. customto give two layers
  7. extractionThe water layer was extracted with toluene (500 ml) three times
  8. washthe combined organic layer was washed with water
  9. dry with materialdried over anhydrous magnesium sulfate
  10. distillationThe solvent was distilled off under reduced pressure
  11. additionThe residue was treated with silica gel chromatography (silica gel: 200 g, eluent: heptane/ethyl acetate=90/10 by volume)
  12. distillationdistilled under reduced pressure (71 to 74° C., 3 mmHg)

Sources & evidence

ORD record
ord-6c4646b2f1394d2291e04e34aa144a7b
Source dataset
uspto-grants-2013_03
Patent number
US08389073B2

Reaction notes

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