Benzophenone imine → HCID 15479546, compound

HRID 365509Notes

Reaction equation

HRID 365509 reaction equation
CC(C)([O-])C.[Na+].Br[C:8]1[CH:9]=[C:10]2[C:15](=[CH:16][CH:17]=1)[N:14]([CH:18]([CH3:20])[CH3:19])[C:13](=[O:21])[CH2:12][C:11]2([CH3:23])[CH3:22].C(=[NH:37])(C1C=CC=CC=1)C1C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH:18]([N:14]1[C:15]2[C:10](=[CH:9][C:8]([NH2:37])=[CH:17][CH:16]=2)[C:11]([CH3:23])([CH3:22])[CH2:12][C:13]1=[O:21])([CH3:20])[CH3:19]

Participants

6

Reactant 3

HCID 136809Benzophenone imineHCID 10732680HCID 10732680, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 15479546HCID 15479546, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

A 25 mL round bottom flask was connected to a reflux condenser and the apparatus flame-dried under high vacuum. The vacuum was broken by the addition of dry argon, and the flask was allowed to cool to room temperature. The flask was charged with 0.135 g (1.4 mmol) of powdered sodium t-butoxide, 9.2 mg (0.01 mmol) of tris(dibenzylideneacetone)dipalladium(0) (Pd2 (dba)3), and 19 mg (0.03 mmol) of (S)-(-)-2,2'-bis(diphenylphosphino)1,1'-binaphthyl (BINAP), and the apparatus was evacuated and filled with dry argon 3 times. A solution of 6-bromo-1-isopropyl-4,4-dimethyl-2-oxo-1,2,3,4-tetrahydroquinoline (0.296 mg, 1 mmol) available as described in U.S. Pat. No. 5,399,56, and benzophenone imine (0.218 g, 1.2 mmol) in 4 mL of dry toluene was added. The flask was immersed in an oil bath and heated to 80° C. until all of the starting material had been consumed as judged by thin layer chromatography (TLC) analysis. The solution was cooled to room temperature and diluted with 40 mL of ether. The mixture was filtered and concentrated in vacuo. The residue was dissolved in tetrahydrofuran (THF, 0.3 M) and 2.0 M HCl was added. The solution was stirred for 20 minutes at room temperature and partitioned between 0.5 M HCl and 2:1 hexane/ethyl acetate. The aqueous layer was made basic with 1 M NaOH and the product extracted with methylene chloride, dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel using 33% ethyl acetate in hexanes, to produce the title compound.

Workup

  1. customA 25 mL round bottom flask was connected to a reflux condenser
  2. customthe apparatus flame-dried under high vacuum
  3. additionThe vacuum was broken by the addition of dry argon
  4. customthe apparatus was evacuated
  5. additionfilled with dry argon 3 times
  6. customThe flask was immersed in an oil bath
  7. temperatureheated to 80° C. until all of the starting material
  8. customhad been consumed
  9. temperatureThe solution was cooled to room temperature
  10. additiondiluted with 40 mL of ether
  11. filtrationThe mixture was filtered
  12. concentrationconcentrated in vacuo
  13. dissolutionThe residue was dissolved in tetrahydrofuran (THF, 0.3 M)
  14. addition2.0 M HCl was added
  15. custompartitioned between 0.5 M HCl and 2:1 hexane/ethyl acetate
  16. extractionthe product extracted with methylene chloride
  17. dry with materialdried over Na2SO4
  18. concentrationconcentrated in vacuo
  19. customThe residue was purified by flash chromatography on silica gel using 33% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-cef4ef7836a34ac099c5c089ade413a4
Source dataset
uspto-grants-2000_10
Patent number
US06127382

Reaction notes

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