Diphenylamine → 9,9-Diethyl-2-diphenylaminofluorene

HRID 720016ノート

反応式

HRID 720016 の反応式
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]([CH2:17][CH3:18])([CH2:15][CH3:16])[C:4]=2[CH:3]=1.[C:19]1([NH:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C(OCC)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH2:15]([C:5]1([CH2:17][CH3:18])[C:4]2[CH:3]=[C:2]([N:25]([C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[CH:14]=[CH:13][C:12]=2[C:11]2[C:6]1=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH3:16]

参加物

8

反応物 3

HCID 11487DiphenylamineHCID 121238752-Bromo-9,9-diethylfluoreneHCID 23676156Sodium t-butoxide

生成物 1

HCID 219021849,9-Diethyl-2-diphenylaminofluorene収率 98.3%

試薬・触媒・溶媒 4

HCID 634876Binap, (A+-)-触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒

実験手順

A mixture of 2-bromo-9,9-diethylfluorene (2.44 g, 8.10 mmol), diphenylamine (1.43 g, 8.5 mmol), tris(dibenzylideneacetone)dipalladium (0.018 g, 0.25 mmol %), rac-BINAP (0.037 g, 0.75 mmol %), and sodium t-butoxide (1.08 g, 11.34 mmol) in dry toluene (100 ml) was heated at the refluxing temperature of the solvent for 8–10 h under an atmospheric pressure of nitrogen. After cooling the reaction mixture to room temperature, it was diluted with diethylether (60 ml), washed with brine (40 ml) and water. Organic layer was dried over sodium sulfate and concentrated in vacuuo. The crude product was purified by column chromatography (silica gel, hexane-toluene/9:1 as eluent, Rf=0.6 on thin layer chromatography using hexane-toluene/4:1 as eluent) to give 9,9-diethyl-2-diphenylaminofluorene (3.1 g) as a white amorphous low melting solid in a yield of 98%.

後処理

  1. temperaturewas heated at the refluxing temperature of the solvent for 8–10 h under an atmospheric pressure of nitrogen
  2. washwashed with brine (40 ml) and water
  3. dry with materialOrganic layer was dried over sodium sulfate
  4. concentrationconcentrated in vacuuo
  5. customThe crude product was purified by column chromatography (silica gel, hexane-toluene/9:1 as eluent, Rf=0.6 on thin layer chromatography using hexane-toluene/4:1 as eluent)

出典と根拠

ORDレコード
ord-f7d24ea3c75e4670aa8f3f3dfc39c945
出典データセット
uspto-grants-2006_11
特許番号
US07132572B2

反応ノート

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