Diphenylamine → 5-(Diphenylamino)benzo[c]phenanthrene

HRID 1470908Notes

Reaction equation

HRID 1470908 reaction equation
ClP(C(C)(C)C)C(C)(C)C.Br[C:12]1[C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][C:24]=2[C:23]2[C:22]3[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=3[CH:16]=[CH:15][C:14]=2[CH:13]=1.[C:30]1([NH:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:37]1([N:36]([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:12]2[C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][C:24]=3[C:23]3[C:22]4[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=4[CH:16]=[CH:15][C:14]=3[CH:13]=2)[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=1

Participants

8

Reactant 4

HCID 11487DiphenylamineHCID 139566Di-tert-butylchlorophosphineHCID 106624825-Bromobenzo[c]phenanthreneHCID 23676156Sodium t-butoxide

Product 1

HCID 585113625-(Diphenylamino)benzo[c]phenanthrene

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

190 μl (1 mmol) of chlorodi-tert-butylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to a suspension of 15.3 g (50 mmol) of 5-bromobenzo[c]phenanthrene, 10.2 g (60 mmol) of diphenylamine and 7.7 g (80 mmol) of sodium tert-butoxide in 500 ml of toluene, and the mixture is subsequently heated under reflux for 5 h. After the mixture has been cooled to 60° C., 500 ml of water are added, the organic phase is separated off, filtered through silica gel, evaporated virtually to dryness at 80° C. in vacuo, and 300 ml of ethanol are then added. After cooling, the solid is filtered off with suction. The product is purified by recrystallisation from dioxane five times (about 8 ml/g). Yield: 12.6 g (32 mmol), 64.1%, purity 99.9% (HPLC).

Workup

  1. temperaturethe mixture is subsequently heated
  2. temperatureunder reflux for 5 h
  3. customthe organic phase is separated off
  4. filtrationfiltered through silica gel
  5. customevaporated virtually to dryness at 80° C. in vacuo, and 300 ml of ethanol
  6. additionare then added
  7. temperatureAfter cooling
  8. filtrationthe solid is filtered off with suction
  9. customThe product is purified by recrystallisation from dioxane five times (about 8 ml/g)

Sources & evidence

ORD record
ord-47e4575dc3a44914ac06ca59f8e0cf9e
Source dataset
uspto-grants-2015_04
Patent number
US09006503B2

Reaction notes

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