Diphenylmethylidenehydrazine → HCID 86619672, compound

HRID 2042120Notes

Reaction equation

HRID 2042120 reaction equation
[C:1]1([C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[N:8][NH2:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:17]1[CH:18]=[C:19]2[C:24](=[CH:25][CH:26]=1)[N:23]=[CH:22][CH:21]=[N:20]2.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.CCOCC.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]1([C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[N:8][NH:9][C:17]2[CH:18]=[C:19]3[C:24](=[CH:25][CH:26]=2)[N:23]=[CH:22][CH:21]=[N:20]3)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

9

Reactant 3

HCID 79304DiphenylmethylidenehydrazineHCID 6109396-BromoquinoxalineHCID 23676156Sodium t-butoxide

Product 1

HCID 86619672HCID 86619672, compoundYield 20.3%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 962WaterSolventHCID 1140TolueneSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
100 °C

Procedure

In toluene (8 mL) was placed 1-(diphenylmethylene)hydrazine (1.00 g, 5.10 mmol), palladium acetate (10.4 mg, 0.0464 mmol) and 2-(diphenylphosphino)-1-(2-(diphenylphosphino)naphthalen-1-yl)naphthalene (44 mg, 0.0696 mmol) and the reaction was stirred at 100° C. under Ar for 5 min and then cooled to RT. To this dark purple solution was added 6-bromoquinoxaline (970 mg, 4.64 mmol), sodium t-butoxide (624 mg, 6.50 mmol) and toluene (2 mL). The reaction was placed under Ar and warmed to 100° C. for 5 hrs, cooled to RT and stirred overnight. The reaction was diluted with ether (50 mL) and water (30 mL) and filtered through a Celite pad. The pad was washed with ether (20 mL) and water (20 mL). The combined organic layers were washed with brine (50 mL), dried (Na2SO4), concentrated in vacuo and purified by chromatography (ethyl acetate/hexanes) to give 1-(diphenylmethylene)-2-(quinoxalin-6-yl)hydrazine (305 mg, 20% yield) as a bright yellow foam. 1H NMR (300 MHz, DMSO-d6) δ 7.35-7.41 (m, 5H), 7.51-7.53 (m, 2H), 7.58-7.65 (m, 3H), 7.75 (s, 1H), 7.89 (s, 2H), 8.61 (s, 1H), 8.74 (s, 1H), 9.60 (s, 1H); MS (ESI) m/z: 325.0 (M+H+).

Workup

  1. temperaturecooled to RT
  2. temperaturewarmed to 100° C. for 5 hrs
  3. temperaturecooled to RT
  4. stirringstirred overnight
  5. filtrationfiltered through a Celite pad
  6. washThe pad was washed with ether (20 mL) and water (20 mL)
  7. washThe combined organic layers were washed with brine (50 mL)
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated in vacuo
  10. custompurified by chromatography (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-5155f98f78e241f2ac8daac602a1f10b
Source dataset
uspto-grants-2013_11
Patent number
US08586565B2

Reaction notes

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