Diphenylamine → 4-(Diphenylamino)benz[a]anthracene

HRID 877294

反応式

HRID 877294 の反応式
ClP(C(C)(C)C)C(C)(C)C.Br[C:12]1[C:17]2=[CH:18][CH:19]=[C:20]3[C:29]([CH:28]=[C:27]4[C:22]([CH:23]=[CH:24][CH:25]=[CH:26]4)=[CH:21]3)=[C:16]2[CH:15]=[CH:14][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:17]3=[CH:18][CH:19]=[C:20]4[C:29]([CH:28]=[C:27]5[C:22]([CH:23]=[CH:24][CH:25]=[CH:26]5)=[CH:21]4)=[C:16]3[CH:15]=[CH:14][CH:13]=2)[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=1

参加物

8

反応物 4

HCID 11487DiphenylamineHCID 139566Di-tert-butylchlorophosphineHCID 182324Benz(a)anthracene, 4-bromo-HCID 23676156Sodium t-butoxide

生成物 1

HCID 594127924-(Diphenylamino)benz[a]anthracene

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 1140Toluene溶媒

反応条件

温度
60 °C

実験手順

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 15.4 g (50 mmol) of 4-bromobenz[a]anthracene, 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. Recrystallisation five times from dioxane (about 8 ml/g); sublimation (p=5×10−5 mbar, T=280° C.). Yield: 12.7 g (32 mmol), 64.1%, purity 99.9% (HPLC), Tg=74.7° C.

後処理

  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. customRecrystallisation five times from dioxane (about 8 ml/g)
  10. customsublimation (p=5×10−5 mbar, T=280° C.)

出典と根拠

ORDレコード
ord-3d424e238af145848f7273db027f9b8e
出典データセット
uspto-grants-2015_03
特許番号
US08986852B2

関連ノート

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