Diphenylmethylidenehydrazine → HCID 86653529, compound

HRID 871679Notes

Reaction equation

HRID 871679 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][C:7]=1[CH3:8].[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: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]=[CH:6][C:7]=2[CH3:8])[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

6

Reactant 4

HCID 79304DiphenylmethylidenehydrazineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 8176303-Bromo-4-methylpyridineHCID 23676156Sodium t-butoxide

Product 1

HCID 86653529HCID 86653529, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

3-Bromo-4-methyl-pyridine (1.0 g, 5.81 mmol) in 5 mL dry toluene was treated with benzophenone hydrazone (1.25 g, 6.39 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (335 mg, 0.58 mmol), and sodium tert-butoxide (840 mg, 8.72 mmol). The mixture was degassed with argon for 15 minutes. Added Pd(II)(OAc)2 (130 mg, 0.58 mmol) and stirred at 90° C. for 14 hours. Extracted using EtOAc/H2O (3×200 mL EtOAc, 1×100 mL H2O, 1×100 mL brine). Dried using Na2SO4 and then purified by flash chromatography (silica, 10-50% EtOAc/Hexane) to afford 3-(2-(diphenylmethylene)hydrazinyl)-4-methylpyridine (1.00 g, 3.48 mmol, 60%). 1H NMR (300 MHz, DMSO-d6) δ 8.79 (s, 1H), 7.97 (d, 1H), 7.67-7.52 (m, 6H), 7.45-7.36 (m, 5H), 7.06 (d, 1H), 1.91 (s, 3H); LC-MS (ESI) m/z 488 (M+H)+.

Workup

  1. customThe mixture was degassed with argon for 15 minutes
  2. extractionExtracted
  3. customDried
  4. custompurified by flash chromatography (silica, 10-50% EtOAc/Hexane)

Sources & evidence

ORD record
ord-5f4271febccf428b9726c5b752309cdd
Source dataset
uspto-grants-2015_03
Patent number
US08969587B2

Reaction notes

Loading…