Sodium Hydroxide → HCID 68585344, compound

HRID 17352Notes

Reaction equation

HRID 17352 reaction equation
[Cl-].[NH4+:2].C[Al](C)C.[C:7]([C:9]1[C:14]2[N:15]=[C:16]([C:18]([CH3:25])([CH3:24])[C:19]([O:21]CC)=O)[O:17][C:13]=2[C:12]([F:26])=[C:11]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:10]=1[CH3:33])#[N:8].[OH-].[Na+]>C1C=CC=CC=1.C(OCC)(=O)C.CCCCCC>[C:7]([C:9]1[C:14]2[N:15]=[C:16]([C:18]([CH3:24])([CH3:25])[C:19]([NH2:2])=[O:21])[O:17][C:13]=2[C:12]([F:26])=[C:11]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:10]=1[CH3:33])#[N:8]

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 25517Ammonium Chloride2×HCID 16682925Trimethylaluminum2×HCID 68586363HCID 68586363, compound

Product 1

HCID 68585344HCID 68585344, compoundYield 38.2%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolvent3×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Ammonium chloride (73 mg, 1.36 mmol) was suspended in benzene (3.3 ml), and under nitrogen atmosphere, trimethylaluminium (1.03 M n-hexane solution) was dropwise added with keeping at 5° C. or lower, followed by stirring at room temperature for 2 hours. A benzene (1.6 ml) solution of ethyl 2-(4-cyano-7-fluoro-5-methyl-6-phenyl-1,3-benzoxazol-2-yl)-2-methylpropanoate (I-95) (166 mg, 0.45 mmol) was added, followed by stirring at 50° C. for 17 hours. Since the reaction did not finish, separately, the same amount of ammonium chloride (73 mg, 1.36 mmol) was suspended in benzene (3.3 ml), trimethylaluminium (1.03 M n-hexane solution was dropwise added with keeping at 5° C. or lower, followed by stirring at room temperature for 2 hours to prepare a solution, which was added to the original reaction solution, followed by stirring at 50° C. for 19 hours. Though the reaction did not finish, this was cooled to room temperature, fractionated with ethyl acetate and aqueous 1 N sodium hydroxide solution, and the organic layer was washed with saturated brine. The obtained organic layer was dried over anhydrous sodium sulfate, the solvent was evaporated away under reduced pressure. The resulting residue was subjected to preparative TLC, eluted with a mixed solvent of chloroform/methanol (10:1, v/v) to obtain the entitled compound (58 mg, 38%) as a yellow amorphous solid.

Workup

  1. customwith keeping at 5° C.
  2. stirringby stirring at 50° C. for 17 hours
  3. customwith keeping at 5° C.
  4. stirringby stirring at room temperature for 2 hours
  5. customto prepare a solution, which
  6. additionwas added to the original reaction solution
  7. stirringby stirring at 50° C. for 19 hours
  8. temperaturethis was cooled to room temperature
  9. washthe organic layer was washed with saturated brine
  10. dry with materialThe obtained organic layer was dried over anhydrous sodium sulfate
  11. customthe solvent was evaporated away under reduced pressure
  12. washeluted with a mixed solvent of chloroform/methanol (10:1

Sources & evidence

ORD record
ord-9bd4583cfacf47e3a892b1be26ab47e8
Source dataset
uspto-grants-2010_06
Patent number
US07737166B2

Reaction notes

Loading…