Carbazole → 4,4'-Bis(9H-carbazol-9-yl)biphenyl

HRID 16033

反応式

HRID 16033 の反応式
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.Br[C:15]1[CH:20]=[CH:19][C:18]([C:21]2[CH:26]=[CH:25][C:24](Br)=[CH:23][CH:22]=2)=[CH:17][CH:16]=1.[CH3:28][C:29]([CH3:32])([O-])[CH3:30].[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>[CH:10]1[C:11]2[N:12]([C:15]3[CH:20]=[CH:19][C:18]([C:21]4[CH:26]=[CH:25][C:24]([N:12]5[C:11]6[CH:10]=[CH:9][CH:8]=[CH:7][C:32]=6[C:29]6[C:30]5=[CH:2][CH:1]=[CH:13][CH:28]=6)=[CH:23][CH:22]=4)=[CH:17][CH:16]=3)[C:13]3[C:5](=[CH:4][CH:3]=[CH:2][CH:1]=3)[C:6]=2[CH:7]=[CH:8][CH:9]=1

参加物

7

反応物 3

HCID 6854CarbazoleHCID 71104,4'-DibromobiphenylHCID 23676156Sodium t-butoxide

生成物 1

HCID 112487164,4'-Bis(9H-carbazol-9-yl)biphenyl収率 75,527.898%

試薬・触媒・溶媒 3

HCID 83681Tris(1,1-dimethylethyl)phosphine触媒HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒3 回

実験手順

Tri-tert-butylphosphine (304 mg, 1.50 mmol) in toluene (38 ml) was added under nitrogen to a deoxygenated mixture of carbazole (16.9 g, 0.100 mmol), 4,4′-dibromobiphenyl (15.7 g, 50.4 mmol), sodium tert-butoxide (30.9 g, 321 mmol) and palladium acetate (115 mg, 0.512 mmol) in toluene (50 ml) and the resulting mixture was heated at reflux under nitrogen for 10 days. The reaction mixture was cooled to room temperature and then diluted with more toluene (200 ml). The reaction mixture was filtered to remove the sodium salts. The filtrate was concentrated to dryness to give the crude product as a pale brown solid. The crude product was purified first by chromatography on silica using dichloromethane as the eluent followed by recrystallisation from toluene. The material was then sublimed at 280-281° C. at 10−6 mm Hg to give the product 4,4′-bis(carbazol-9-yl)biphenyl (1) (18.3 g, 75%), as an off-white solid with melting point 280-281° C. (lit. m.p. 281° C.).

後処理

  1. temperaturethe resulting mixture was heated
  2. temperatureat reflux under nitrogen for 10 days
  3. filtrationThe reaction mixture was filtered
  4. customto remove the sodium salts
  5. concentrationThe filtrate was concentrated to dryness
  6. customto give the crude product as a pale brown solid
  7. customThe crude product was purified first by chromatography on silica
  8. customfollowed by recrystallisation from toluene
  9. customwas then sublimed at 280-281° C. at 10−6 mm Hg

出典と根拠

ORDレコード
ord-cde1b627deb84233936c4eac8d7f92d5
出典データセット
uspto-grants-2010_06
特許番号
US07736534B2

関連ノート

読み込み中…