Benzophenone imine → N-(diphenylmethylidene)-3-[1-(4-methoxybenzyl)-4-pyridin-4-yl-1H-pyrazol-3-yl]aniline

HRID 45835Notes

Reaction equation

HRID 45835 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2[C:12]([C:13]3[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=3)=[CH:11][N:10]([CH2:19][C:20]3[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=3)[N:9]=2)[CH:5]=[CH:6][CH:7]=1.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.CC(C)([O-])C.[Na+].[C:80](=[NH:93])([C:87]1[CH:92]=[CH:91][CH:90]=[CH:89][CH:88]=1)[C:81]1[CH:86]=[CH:85][CH:84]=[CH:83][CH:82]=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]>[C:87]1([C:80]([C:81]2[CH:82]=[CH:83][CH:84]=[CH:85][CH:86]=2)=[N:93][C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([C:8]3[C:12]([C:13]4[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=4)=[CH:11][N:10]([CH2:19][C:20]4[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=4)[N:9]=3)[CH:3]=2)[CH:88]=[CH:89][CH:90]=[CH:91][CH:92]=1

Participants

7

Reactant 4

HCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 671844264-[3-(3-bromophenyl)-1-(4-methoxybenzyl)-1H-pyrazol-4-yl]pyridine

Product 1

HCID 86654334N-(diphenylmethylidene)-3-[1-(4-methoxybenzyl)-4-pyridin-4-yl-1H-pyrazol-3-yl]anilineYield 65%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

1.9 g (4.5 mmol) of 4-[3-(3-bromophenyl)-1-(4-methoxybenzyl)-1H-pyrazol-4-yl]pyridine were dissolved in 60 ml of dry toluene under nitrogen atmosphere and 366 mg (0.4 mmol) of tris(dibenzylidene-acetone)dipalladium(0), 498 mg (0.8 mmol) of racemic 2,2′-bis(diphenylphosphino)-1,1′-binaphtalene, 562 mg (5.85 mmol) of sodium tertbutoxide and 975 L (5.85 mmol) of benzophenonimine were added to the solution successively. The mixture was refluxed for 3 hours. After cooling to room temperature the reaction mixture was filtered over a celite pad and the solvent evaporated. The residue was redissolved with ethylacetate and washed with water. The organic layer was dried over Na2SO4 and evaporated again to dryness. The crude was purified by chromatography on a silica gel column eluted by dichloromethane-methanol 95/5, affording 1.5 g (65% yield) of the title compound.

Workup

  1. temperatureThe mixture was refluxed for 3 hours
  2. filtrationwas filtered over a celite pad
  3. customthe solvent evaporated
  4. dissolutionThe residue was redissolved with ethylacetate
  5. washwashed with water
  6. dry with materialThe organic layer was dried over Na2SO4
  7. customevaporated again to dryness
  8. customThe crude was purified by chromatography on a silica gel column
  9. washeluted by dichloromethane-methanol 95/5

Sources & evidence

ORD record
ord-fda0bcab19264152a18d36f4b8570818
Source dataset
uspto-grants-2013_09
Patent number
US08541575B2

Reaction notes

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