Toluene → 4-(9,9-Dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-YL)-9H-fluoren-2-YL)-N,N-diphenylaniline

HRID 11189

反応式

HRID 11189 の反応式
Br[C:2]1[CH:20]=[CH:19][C:5]([N:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)=[CH:4][CH:3]=1.[CH2:21]([C:29]1([CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH3:67])[C:41]2[CH:40]=[C:39]([B:42]3[O:46][C:45]([CH3:48])([CH3:47])[C:44]([CH3:50])([CH3:49])[O:43]3)[CH:38]=[CH:37][C:36]=2[C:35]2[C:30]1=[CH:31][C:32](B1OC(C)(C)C(C)(C)O1)=[CH:33][CH:34]=2)[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28].C(=O)([O-])[O-].[Na+].[Na+].C1(C)C=CC=CC=1>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].CC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C)C=CC=CC=1.CCCCCC.O>[CH2:60]([C:29]1([CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[C:30]2[CH:31]=[C:32]([C:2]3[CH:20]=[CH:19][C:5]([N:6]([C:13]4[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=4)[C:7]4[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=4)=[CH:4][CH:3]=3)[CH:33]=[CH:34][C:35]=2[C:36]2[C:41]1=[CH:40][C:39]([B:42]1[O:43][C:44]([CH3:49])([CH3:50])[C:45]([CH3:47])([CH3:48])[O:46]1)=[CH:38][CH:37]=2)[CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH3:67]

参加物

11

反応物 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 6428384-BromotriphenylamineHCID 219820749,9-Dioctylfluorene-2,7-diboronic acid bis(pinacol) ester

生成物 1

HCID 219820994-(9,9-Dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-YL)-9H-fluoren-2-YL)-N,N-diphenylaniline

試薬・触媒・溶媒 6

HCID 21218Trioctylmethylammonium chloride触媒HCID 15220664Palladium--triphenylphosphane (1/1)触媒HCID 178418397HCID 178418397、化合物触媒HCID 180Acetone溶媒HCID 962Water溶媒HCID 21889329Toluene hexane溶媒

実験手順

4-Bromo-N,N-diphenylaniline (19.44 g, 60 mmole, 1 equiv), 2-[9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (76.9 g, 120 mmole, 2 equiv), Aliquat™ 336 (tricaprylylmethylammonium chloride) (6 g, 15 mmole, 0.25 equiv) and 2M sodium carbonate solution (75 mL, 150 mmole, 2.5 equiv) were added to 600 mL of toluene. This was purged with a stream of nitrogen for about 30 min. Under a nitrogen purge, tetrakis(triphenylphosphine palladium (0) (348 mg, 0.30 mmole, 0.005 equiv) was added. The reaction mixture was then refluxed for 16 hrs. The reaction was cooled to room temperature and water added. The organic layer was separated and washed with water followed by brine. Drying of the organic layer over Na2SO4 and evaporation of the solvent gave a light yellow solid. This was suspended in acetone and the mixture brought to reflux and then allowed to stand at room temperature overnight. Filtration of the solid and concentration of the filtrate gave a solid that was subjected to column chromatography (toluene:hexane 3:7) to give 4-[9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl]-N,N-diphenylaniline.

後処理

  1. customThis was purged with a stream of nitrogen for about 30 min
  2. customUnder a nitrogen purge
  3. temperatureThe reaction mixture was then refluxed for 16 hrs
  4. customThe organic layer was separated
  5. washwashed with water
  6. dry with materialDrying of the organic layer over Na2SO4 and evaporation of the solvent
  7. customgave a light yellow solid
  8. temperatureto reflux
  9. filtrationFiltration of the solid and concentration of the filtrate
  10. customgave a solid

出典と根拠

ORDレコード
ord-b2dbec03729041cdb275660146cddfe5
出典データセット
uspto-grants-2006_08
特許番号
US07094902B2

関連ノート

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