Hydrochloric Acid → HCID 68515976, compound

HRID 732793Notes

Reaction equation

HRID 732793 reaction equation
C[O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[C:9]([O:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:21][CH2:22][N:23]3[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24]3)=[CH:16][CH:15]=1)=[C:8]([C:29]1[CH:34]=[CH:33][C:32]([S:35]([N:38]([CH3:40])[CH3:39])(=[O:37])=[O:36])=[CH:31][CH:30]=1)[CH:7]=[CH:6]2.[ClH:41].C(OCC)C.B(Br)(Br)Br>ClCCl>[ClH:41].[OH:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[C:9]([O:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:21][CH2:22][N:23]3[CH2:24][CH2:25][CH2:26][CH2:27][CH2:28]3)=[CH:16][CH:15]=1)=[C:8]([C:29]1[CH:30]=[CH:31][C:32]([S:35]([N:38]([CH3:40])[CH3:39])(=[O:36])=[O:37])=[CH:33][CH:34]=1)[CH:7]=[CH:6]2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 3283Diethyl EtherHCID 25134Boron tribromideHCID 59751439HCID 59751439, compound

Product 1

HCID 68515976HCID 68515976, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

In a round bottom flask place the product of Example 64 (120 mg, 0.214 mmol), dichloromethane (5 mL) and a 1.0 M hydrochloric acid in diethyl ether solution (0.43 mL, 0.43 mmol). Shake this solution at ambient temperature for 2 minutes then evaporate it in vacuo. After drying on vacuum, add dichloromethane (10 mL) and place this solution in an ice bath with stirring. Add a solution of 1.0 M boron tribromide in dichloromethane (0.750 mL, 0.750 mmol) and stir the reaction for 3-4 hours, keeping the temperature between 0° C.-10° C. Quench the reaction over saturated aqueous sodium bicarbonate then extract it into ethyl acetate. Wash the combined extracts with saturated aqueous sodium bicarbonate, water and brine; then dry (sodium sulfate) and evaporate them in vacuo. Purify the crude solid on a Chromatotron (silica gel; 5%-11% MeOH gradient in CH2Cl2; loaded with 7% MeOH/CHCl3). Dissolve the purified material in methanol (5 mL) and add a 1.0 M hydrochloric acid in diethyl ether solution (0.43 mL). Shake the resulting solution for two minutes at room temperature then evaporate it in vacuo to give 96 mg of the title compound (77%). MS (IS+) m/e 547 (M+1−HCl).

Workup

  1. customShake this solution at ambient temperature for 2 minutes then evaporate it in vacuo
  2. customAfter drying on vacuum
  3. additionadd dichloromethane (10 mL) and place this solution in an ice bath
  4. stirringstir
  5. customthe reaction for 3-4 hours
  6. custombetween 0° C.-10° C
  7. customQuench
  8. customthe reaction over saturated aqueous sodium bicarbonate
  9. extractionthen extract it into ethyl acetate
  10. washWash the combined extracts with saturated aqueous sodium bicarbonate, water and brine
  11. dry with materialthen dry (sodium sulfate)
  12. customevaporate them in vacuo
  13. customPurify the crude solid on a Chromatotron (silica gel; 5%-11% MeOH gradient in CH2Cl2; loaded with 7% MeOH/CHCl3)
  14. dissolutionDissolve the purified material in methanol (5 mL)
  15. additionadd a 1.0 M hydrochloric acid in diethyl ether solution (0.43 mL)
  16. customShake the resulting solution for two minutes at room temperature then evaporate it in vacuo

Sources & evidence

ORD record
ord-b342c9cf4cf64a33ad96ec18cc6bac96
Source dataset
uspto-grants-2009_09
Patent number
US07585977B2

Reaction notes

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