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2-(Di-tert-butylphosphino)biphenyl → 9-(4-tert-butylpyridin-2-yl)-2'-(4-phenylpyridin-2-yl)-9H-2,9'-bicarbazole

HRID 1509633
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HRID 1509633 반응식
[C:1]1([C:7]2[CH:12]=[CH:11][N:10]=[C:9]([C:13]3[CH:25]=[CH:24][C:23]4[C:22]5[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=5)[NH:16][C:15]=4[CH:14]=3)[CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:27]1[CH:39]=[CH:38][C:37]2[C:36]3[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=3)[N:30]([C:40]3[CH:45]=[C:44]([C:46]([CH3:49])([CH3:48])[CH3:47])[CH:43]=[CH:42][N:41]=3)[C:29]=2[CH:28]=1.CC(P(C(C)(C)C)C1C(C2C=CC=CC=2)=CC=CC=1)(C)C.CC([O-])(C)C.[Na+]>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]>[C:46]([C:44]1[CH:43]=[CH:42][N:41]=[C:40]([N:30]2[C:29]3[CH:28]=[C:27]([N:16]4[C:15]5[CH:14]=[C:13]([C:9]6[CH:8]=[C:7]([C:1]7[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=7)[CH:12]=[CH:11][N:10]=6)[CH:25]=[CH:24][C:23]=5[C:22]5[C:17]4=[CH:18][CH:19]=[CH:20][CH:21]=5)[CH:39]=[CH:38][C:37]=3[C:36]3[C:31]2=[CH:32][CH:33]=[CH:34][CH:35]=3)[CH:45]=1)([CH3:49])([CH3:47])[CH3:48]
참가 물질반응 조건실험 절차후처리출처 및 근거반응 노트

참가 물질

6

반응물 4

HCID 27342152-(Di-tert-butylphosphino)biphenylHCID 23676156Sodium t-butoxideHCID 1180072932-Bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazoleHCID 1181139652-(4-phenylpyridin-2-yl)-9H-carbazole

생성물 1

HCID 1181141049-(4-tert-butylpyridin-2-yl)-2'-(4-phenylpyridin-2-yl)-9H-2,9'-bicarbazole

시약·촉매·용매 1

HCID 9811564Bis(dibenzylideneacetone)palladium촉매

반응 조건

온도
100 °C

실험 절차

To a dry pressure Schlenk tube equipped with a magnetic stir bar was added 2-(4-phenylpyridin-2-yl)-9H-carbazole (676 mg, 2.11 mmol, 1.0 eq), 2-bromo-9-(4-tert-butylpyridin-2-yl)-9H-carbazole (958 mg, 2.53 mmol, 1.2 eq), Pd2(dba)3 (77 mg, 0.084 mmol, 0.04 eq), JohnPhos (50 mg, 0.169 mmol, 0.08 eq) and tBuONa (324 mg, 3.38 mmol, 1.6 eq). Then the tube was evacuated and back-filled with nitrogen, and the evacuation and back-fill procedure was repeated twice. Then dry solvent toluene (10 mL), dioxane (10 mL) were added under the protection of nitrogen. The tube was sealed and the mixture was stirred in an oil bath at a temperature of 95-105° C. for 43 hours. Then the mixture was cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10:1-8:1-5:1) as an eluent to obtain the desired product, 9-(4-tert-butylpyridin-2-yl)-2′-(4-phenylpyridin-2-yl)-9H-2,9′-bicarbazole Ligand N3NPh-ptb, as a brown solid (1175 mg in 90% yield). 1H NMR (DMSO-d6, 400 MHz): δ 1.15 (s, 9H), 7.25 (t, J=8.0 Hz, 1H), 7.31 (dd, J=5.2, 1.6 Hz, 1H), 7.34-7.57 (m, 9H), 7.74 (s, 1H), 7.78-7.82 (m, 3H), 7.91 (d, J=1.6 Hz, 1H), 8.11 (d, J=8.4 Hz, 1H), 8.21 (s, 1H), 8.24 (d, J=8.0 Hz, 1H), 8.29 (s, 1H), 8.31 (d, J=8.4 Hz, 2H), 8.45 (d, J=6.0 Hz, 1H), 8.51 (d, J=8.0 Hz, 1H), 8.57 (d, J=4.2 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz): δ 29.96, 34.72, 108.01, 109.82, 109.85, 111.36, 115.97, 117.92, 119.14, 119.31, 119.80, 119.92, 120.23, 120.72, 120.84, 121.29, 122.00, 122.39, 122.94, 123.02, 123.45, 126.63, 126.84, 127.05, 129.06, 129.16, 134.83, 136.92, 137.49, 139.73, 139.78, 141.13, 141.47, 148.33, 149.39, 149.97, 150.55, 157.15, 163.08.

후처리

  1. customTo a dry pressure Schlenk tube equipped with a magnetic stir bar
  2. customThen the tube was evacuated
  3. additionback-filled with nitrogen
  4. additionThen dry solvent toluene (10 mL), dioxane (10 mL) were added under the protection of nitrogen
  5. customThe tube was sealed
  6. temperatureThen the mixture was cooled to ambient temperature
  7. customThe solvent was removed under reduced pressure
  8. customthe residue was purified through column chromatography on silica gel

출처 및 근거

ORD 기록
ord-0871e05e1c104faaae3e6fe6c9340047
출처 데이터셋
uspto-grants-2015_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09224963B2

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