Diphenylamine → 9,9-Diethyl-2-diphenylaminofluorene

HRID 720016노트

반응식

HRID 720016 반응식
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]

참가 물질

8

반응물 3

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

생성물 1

HCID 219021849,9-Diethyl-2-diphenylaminofluorene수율 98.3%

시약·촉매·용매 4

HCID 634876Binap, (A+-)-촉매HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 1140Toluene용매HCID 3283Diethyl Ether용매

실험 절차

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%.

후처리

  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)

출처 및 근거

ORD 기록
ord-f7d24ea3c75e4670aa8f3f3dfc39c945
출처 데이터셋
uspto-grants-2006_11
특허 번호
US07132572B2

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