Diphenylmethylidenehydrazine → HCID 11300678, compound

HRID 631664Notes

Reaction equation

HRID 631664 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-06a428d90e9f4094aebd4e7018a064ff
Source dataset
uspto-grants-2016_04
Patent number
US09320739B2

Reaction notes

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