Benzophenone imine → HCID 68832310, compound

HRID 714861Notes

Reaction equation

HRID 714861 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:14]#[N:15])[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)=[CH:4][CH:3]=1.C1(C(C2C=CC=CC=2)=[NH:23])C=CC=CC=1.CC([O-])(C)C.[Na+]>C1(C)C=CC=CC=1.C(OCC)(=O)C.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].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[NH2:23][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:14]#[N:15])[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)=[CH:4][CH:3]=1

Participants

8

Reactant 3

HCID 136809Benzophenone imineHCID 23676156Sodium t-butoxideHCID 431190214-(4-bromophenyl)tetrahydro-2H-Pyran-4-carbonitrile

Product 1

HCID 68832310HCID 68832310, compoundYield 70.4%

Reagents, catalysts & solvents 4

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 4-(4-bromophenyl)tetrahydro-2H-pyran-4-carbonitrile (1.7 g) obtained in Step A of Example 150, diphenylmethanimine (1.4 g), tris(dibenzylideneacetone)dipalladium(0) (88 mg) and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (130 mg) in toluene (50 mL) was added sodium 2-methylpropan-2-olate (920 mg) under nitrogen atmosphere, and the mixture was stirred at 90° C. for 10 hr. The reaction mixture was diluted with ethyl acetate, and the insoluble substance was removed by filtration through Celite. The filtrate was concentrated, and to a solution of the residue in methanol (10 mL) were added hydroxylamine hydrochloride (440 mg) and sodium acetate (530 mg). The mixture was stirred at room temperature for 30 min, and 0.1 M aqueous sodium hydroxide solution and ethyl acetate were added thereto. The solvent was evaporated under reduced pressure, and the reaction mixture was poured into water, and extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate) to give the title compound (910 mg).

Workup

  1. customthe insoluble substance was removed by filtration through Celite
  2. concentrationThe filtrate was concentrated
  3. additionto a solution of the residue in methanol (10 mL) were added hydroxylamine hydrochloride (440 mg) and sodium acetate (530 mg)
  4. stirringThe mixture was stirred at room temperature for 30 min
  5. addition0.1 M aqueous sodium hydroxide solution and ethyl acetate were added
  6. customThe solvent was evaporated under reduced pressure
  7. additionthe reaction mixture was poured into water
  8. extractionextracted with ethyl acetate
  9. washThe obtained organic layer was washed with saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customthe solvent was evaporated under reduced pressure
  12. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-7bf86d1ef85d46e6b2e782b7c753b771
Source dataset
uspto-grants-2015_11
Patent number
US09187453B2

Reaction notes

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