Iodobenzene → N2-methyl-N3-phenylpyridine-2,3-diamine

HRID 333562Notes

Reaction equation

HRID 333562 reaction equation
[CH3:1][NH:2][C:3]1[C:8]([NH2:9])=[CH:7][CH:6]=[CH:5][N:4]=1.I[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.CC([O-])(C)C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC=C3C=2C(C2C4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C=CC=2)=CC=C3)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].C1(C)C=CC=CC=1>[CH3:1][NH:2][C:3]1[C:8]([NH:9][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:7][CH:6]=[CH:5][N:4]=1

Participants

7

Reactant 4

HCID 11575IodobenzeneHCID 99390178,8'-Bis(diphenylphosphino)-1,1'-binaphthaleneHCID 123436692-N-methylpyridine-2,3-diamineHCID 23676156Sodium t-butoxide

Product 1

HCID 68205838N2-methyl-N3-phenylpyridine-2,3-diamine

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

N2-methylpyridine-2,3-diamine (11.95 g, 97 mmol), iodobenzene (16.22 ml, 146 mmol), sodium 2-methylpropan-2-olate (13.99 g, 146 mmol), 8,8′-bis(diphenylphosphino)-1,1′-binaphthalene (BINAP) (60.4 g, 97 mmol) with toluene (400 mL) were added to a three necked 1 L round bottom flask. The reaction was degassed with N2 for 20 minutes. Pd2(dba)3 (1.777 g, 1.941 mmol) was added and the reaction mixture was refluxed for 20 h. The reaction mixture was concentrated to dryness. Residue was dissolved in EtOAc. It was not clear solution, but a suspension was obtained and then filtered through a silica gel plug. The desired product was concentrated and recrystallized from DCM/hexanes providing a yield of 6.45 g, 33.3%.

Workup

  1. customThe reaction was degassed with N2 for 20 minutes
  2. temperaturethe reaction mixture was refluxed for 20 h
  3. concentrationThe reaction mixture was concentrated to dryness
  4. dissolutionResidue was dissolved in EtOAc
  5. customa suspension was obtained
  6. filtrationfiltered through a silica gel plug
  7. concentrationThe desired product was concentrated
  8. customrecrystallized from DCM/hexanes providing a yield of 6.45 g, 33.3%

Sources & evidence

ORD record
ord-ece73c7210ac4131bad4f9c6528c419a
Source dataset
uspto-grants-2014_11
Patent number
US08883322B2

Reaction notes

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