Diphenylmethylidenehydrazine → HCID 58385365, compound

HRID 631675Notes

Reaction equation

HRID 631675 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([F:8])[CH:7]=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>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:2]2[CH:3]=[N:4][CH:5]=[C:6]([F:8])[CH:7]=2)[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

6

Reactant 3

HCID 79304DiphenylmethylidenehydrazineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 8202063-Bromo-5-fluoropyridine

Product 1

HCID 58385365HCID 58385365, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

To a stirred and degassed solution of 3-bromo-5-fluoropyridine (1 g, 5.68 mmol), benzophenone hydrazone (1.23 g, 6.25 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (329 mg, 0.57 mmol) in anhydrous toluene (15 mL) at rt under an argon atmosphere, was added palladium acetate (128 mg, 0.57 mmol). The vessel was sealed and heated at 85° C. for 15 h. The reaction mixture was cooled to rt and partitioned between ethyl acetate and water. The organic layer was separated and washed with water, then brine, then dried over magnesium sulfate and filtered. Concentration under reduced pressure gave a brown solid which was purified via silica gel column chromatography (eluting with a gradient of 12% ethyl acetate in hexanes to 100% ethyl acetate) to afford 3-(2-(diphenylmethylene)hydrazinyl)-5-fluoropyridine (1.35 g, 82%) as a yellow solid. 1H NMR (300 MHz, DMSO-d6) δ 9.41 (s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.30-7.65 (m, 11H); LC-MS (ESI) m/z 292 (M+H)+.

Workup

  1. customThe vessel was sealed
  2. temperatureThe reaction mixture was cooled to rt
  3. custompartitioned between ethyl acetate and water
  4. customThe organic layer was separated
  5. washwashed with water
  6. dry with materialbrine, then dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationConcentration under reduced pressure
  9. customgave a brown solid which
  10. customwas purified via silica gel column chromatography (
  11. washeluting with a gradient of 12% ethyl acetate in hexanes to 100% ethyl acetate)

Sources & evidence

ORD record
ord-5d6c6fe954974058a7d5b8de4947193d
Source dataset
uspto-grants-2016_04
Patent number
US09320739B2

Reaction notes

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