Diphenylmethylidenehydrazine → HCID 11300678, compound

HRID 871713Notes

Reaction equation

HRID 871713 reaction equation
Br[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([CH3:8])[CH:3]=1.[C:9](=[N:22][NH2:23])([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:10]1([C:9]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[N:22][NH:23][C:7]2[CH:2]=[CH:3][C:4]([CH3:8])=[N:5][CH:6]=2)[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

7

Reactant 4

HCID 79304DiphenylmethylidenehydrazineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 27628354-Bromo-2-methylpyridineHCID 23676156Sodium t-butoxide

Product 1

HCID 11300678HCID 11300678, compoundYield 95.8%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of 4-bromo-2-methylpyridine (0.7 ml, 5.81 mmol) in anhydrous toluene, previously degassed with Ar, were added benzophenone hydrazone (1.25 g, 6.4 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (336 mg, 0.58 mmol), palladium (II) acetate (130 mg, 0.581 mmol), and sodium tert-butoxide (838 mg, 8.72 mmol). The reaction mixture was sealed and stirred at 85° C. overnight, then filtered through celite, washed with DCM and concentrated under reduced pressure. The residue was taken in EtOAc, washed with water, extracted, and the organics were combined and dried (MgSO4). The crude was purified by silica gel chromatography (hexane/ethyl acetate 10-100%) to afford 5-(2-(diphenylmethylene)hydrazinyl)-2-methylpyridine (1.6 g, 95%). 1H NMR (300 MHz, CDCl3) δ 2.47 (s, 3H), 6.76 (d, J=2 Hz, 1H), 6.83 (s, 1H), 7.31-7.36 (m, 5H), 7.53-7.63 (m, 6H), 8.20 (d, J=6 Hz, 1H); LC-MS (ESI) m/z 288 (M+H)+.

Workup

  1. customThe reaction mixture was sealed
  2. filtrationfiltered through celite
  3. washwashed with DCM
  4. concentrationconcentrated under reduced pressure
  5. washwashed with water
  6. extractionextracted
  7. dry with materialdried (MgSO4)
  8. customThe crude was purified by silica gel chromatography (hexane/ethyl acetate 10-100%)

Sources & evidence

ORD record
ord-46cb822b6dea452c84746b116f9cf063
Source dataset
uspto-grants-2015_03
Patent number
US08969587B2

Reaction notes

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