Hexane → p-Toluenesulfonate

HRID 605417Notes

Reaction equation

HRID 605417 reaction equation
[C:1]1([C@H:7]([N:9]=[C:10]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:11]([F:14])([F:13])[F:12])[CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([BH3-])#N.[Na+].O.[C:26]1([CH3:36])[CH:31]=[CH:30][C:29]([S:32]([OH:35])(=[O:34])=[O:33])=[CH:28][CH:27]=1.CCCCCC>C1COCC1.CC(O)C>[F:12][C:11]([F:13])([F:14])[C@@H:10]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[NH:9][C@@H:7]([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH3:8].[S:32]([C:29]1[CH:30]=[CH:31][C:26]([CH3:36])=[CH:27][CH:28]=1)([O-:35])(=[O:34])=[O:33]

Participants

8

Reactant 4

HCID 8058HexaneHCID 521998p-Toluenesulfonic acid monohydrateHCID 5003444Sodium cyanoborohydrideHCID 11323391HCID 11323391, compound

Product 2

HCID 85570p-ToluenesulfonateYield 146.8%HCID 67041172HCID 67041172, compound

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

The product of Example 447A (11.1 g, 40 mmol) in THF (60 mL) was treated with a solution of sodium cyanoborohydride (5.3 g, 80 mmol) in THF (30 mL) dropwise at 5° C. over 15 minutes, then 5° C. for 3 hours and at room temperature for 3 days. The reaction was quenched with 1N HCl (to pH 1) and stirred at room temperature for 3 hours, adjusted to pH 11 with K2CO3, and then extracted with ethyl acetate (100 mL). The organic layer was washed with water (3×50 mL) and brine, dried over MgSO4, concentrated and dried at room temperature in vacuum to give crude product (10.2 g) as colorless liquid. The obtained crude product was diluted with i-PrOH (71 mL), treated with p-toluenesulfonic acid monohydrate (7.05g, 37 mmol), and then the mixture was heated to reflux. n-Hexane (71 mL) was added to the hot solution, and then the solution was cooled to room temperature gradually and stirred at room temperature for 2 hours. The resulting crystal was collected by filtration, washed with a mixture of i-PrOH and n-hexane (1:1), and dried at 40° C. overnight in vacuum to give the title compound as tosylate (colorless crystal, 9.3 g): yield 52% from 2,2,2-trifluoroacetophenone

Workup

  1. waitat room temperature for 3 days
  2. customThe reaction was quenched with 1N HCl (to pH 1)
  3. extractionextracted with ethyl acetate (100 mL)
  4. washThe organic layer was washed with water (3×50 mL) and brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customdried at room temperature in vacuum
  8. customto give crude product (10.2 g) as colorless liquid
  9. customThe obtained crude product
  10. temperaturethe mixture was heated to reflux
  11. temperaturethe solution was cooled to room temperature gradually
  12. stirringstirred at room temperature for 2 hours
  13. filtrationThe resulting crystal was collected by filtration
  14. washwashed with a mixture of i-PrOH and n-hexane (1:1)
  15. customdried at 40° C. overnight in vacuum

Sources & evidence

ORD record
ord-d6060c5778464c74acf9dc7ab7733ba6
Source dataset
uspto-grants-2011_03
Patent number
US07910595B2

Reaction notes

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