Water → HCID 86720224, compound

HRID 625155Notes

Reaction equation

HRID 625155 reaction equation
[H-].[Na+].[Br:3][C:4]1[C:5]([CH3:11])=[C:6]([CH:9]=[O:10])[NH:7][CH:8]=1.[C:12]1([CH3:22])[CH:17]=[CH:16][C:15]([S:18](Cl)(=[O:20])=[O:19])=[CH:14][CH:13]=1.O>C1COCC1.C(OCC)(=O)C>[Br:3][C:4]1[C:5]([CH3:11])=[C:6]([CH:9]=[O:10])[N:7]([S:18]([C:15]2[CH:16]=[CH:17][C:12]([CH3:22])=[CH:13][CH:14]=2)(=[O:20])=[O:19])[CH:8]=1

Participants

7

Reactant 4

HCID 962WaterHCID 73974-Toluenesulfonyl chlorideHCID 24758Sodium hydrideHCID 86112953HCID 86112953, compound

Product 1

HCID 86720224HCID 86720224, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Following a general procedure,50 a stirred suspension of 60% NaH (2.5 g, 62 mmol) in dry THF (42 mL, distilled) was cooled to 0° C. under argon. The mixture was treated portionwise with 3 (7.78 g, 41.4 mmol). The mixture was stirred for 30 min at 0° C. before treating all at once with p-toluenesulfonyl chloride (8.00 g, 41.4 mmol). The reaction mixture was stirred at room temperature for 3 h, whereupon water (100 mL) was slowly added to quench the reaction. Ethyl acetate (100 mL) was added, and the organic layer was separated. The organic layer was washed with brine, dried (Na2SO4), and concentrated to a solid. The solid was dried under high vacuum for 2 h. The crude solid material was dissolved in 100 mL hexanes/ethyl acetate (5:1) by refluxing in a hot water bath. Upon allowing the solution to cool to room temperature the product crystallized. The mixture was cooled overnight at −10° C. to promote additional crystallization. The mixture was vacuum-filtered, and the resulting light brown crystals were dried under high vacuum (9.73 g, 69%): mp 152-155° C.; 1H NMR δ 2.29 (s, 3H), 2.43 (s, 3H), 7.34 (d, J=8.5 Hz, 2H), 7.55 (s, 1H), 7.76 (d, J=8.5 Hz, 2H), 10.14 (s, 1H); 13C NMR δ 2.1, 22.0, 106.2, 126.8, 127.6, 129.1, 130.6, 135.2, 136.4, 146.5, 180.1; Anal. Calcd for C13H12BrNO3S: C, 45.63; H, 3.53; N, 4.09. Found: C, 45.71; H, 3.44; N, 4.11.

Workup

  1. additionwas slowly added
  2. customto quench
  3. customthe reaction
  4. customthe organic layer was separated
  5. washThe organic layer was washed with brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated to a solid
  8. customThe solid was dried under high vacuum for 2 h
  9. dissolutionThe crude solid material was dissolved in 100 mL hexanes/ethyl acetate (5:1)
  10. temperatureby refluxing in a hot water bath
  11. temperatureto cool to room temperature the product
  12. customcrystallized
  13. temperatureThe mixture was cooled overnight at −10° C.
  14. customcrystallization
  15. filtrationThe mixture was vacuum-filtered
  16. customthe resulting light brown crystals were dried under high vacuum (9.73 g, 69%)

Sources & evidence

ORD record
ord-502d25be4d094547b3309279c468ee7c
Source dataset
uspto-grants-2016_04
Patent number
US09303165B2

Reaction notes

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