Cesium carbonate → Methyl 3-{6-[(diphenylmethylene)amino]pyridazin-4-yl}benzoate

HRID 407074Notes

Reaction equation

HRID 407074 reaction equation
Cl[C:2]1[N:7]=[N:6][CH:5]=[C:4]([C:8]2[CH:9]=[C:10]([CH:15]=[CH:16][CH:17]=2)[C:11]([O:13][CH3:14])=[O:12])[CH:3]=1.[C:18](=[NH:31])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:19]1([C:18](=[N:31][C:2]2[N:7]=[N:6][CH:5]=[C:4]([C:8]3[CH:9]=[C:10]([CH:15]=[CH:16][CH:17]=3)[C:11]([O:13][CH3:14])=[O:12])[CH:3]=2)[C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 86667186Methyl 3-(6-chloropyridazin-4-yl)benzoate

Product 1

HCID 86667185Methyl 3-{6-[(diphenylmethylene)amino]pyridazin-4-yl}benzoateYield 69.6%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of methyl 3-(6-chloropyridazin-4-yl)benzoate (0.21 g, 0.84 mmol), benzophenone imine (260 μL, 1.5 mmol), (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (26 mg, 0.042 mmol), cesium carbonate (0.55 g, 1.7 mmol) and palladium acetate (9.5 mg, 0.042 mmol) in 1,4-dioxane (3 mL) was vacuum and refilled with nitrogen for 3 times. The reaction was stirred at 110° C. overnight. After cooling it was diluted with ethyl acetate. The organic solution was washed with water and brine, dried over Na2SO4. After filtration the filtrate was concentrated under reduced pressure. The residue was purified by flash chromatography on a silica gel column with ethyl acetate in methylene chloride (0-20%) to afford the desired product (0.23 g). LCMS (M+H)+: m/z=394.2

Workup

  1. additionrefilled with nitrogen for 3 times
  2. temperatureAfter cooling it
  3. washThe organic solution was washed with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationAfter filtration the filtrate
  6. concentrationwas concentrated under reduced pressure
  7. customThe residue was purified by flash chromatography on a silica gel column with ethyl acetate in methylene chloride (0-20%)

Sources & evidence

ORD record
ord-bc17eb2769874d5aaed9652464303362
Source dataset
uspto-grants-2014_06
Patent number
US08754114B2

Reaction notes

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