Tris(1,1-dimethylethyl)phosphine → 2-[4-{3-(Dibenzofuran-4-yl)-9H-carbazol-9-yl}phenyl]-1-phenylbenzimidazole

HRID 2176384Notes

Reaction equation

HRID 2176384 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[N:12]=2)=[CH:4][CH:3]=1.[CH:23]1[C:35]2[NH:34][C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[C:27]=2[CH:26]=[C:25]([C:36]2[C:41]3[O:42][C:43]4[CH:48]=[CH:47][CH:46]=[CH:45][C:44]=4[C:40]=3[CH:39]=[CH:38][CH:37]=2)[CH:24]=1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.CC(C)([O-])C.[Na+]>CCCCCC.C1(C)C=CC=CC=1>[CH:39]1[C:40]2[C:44]3[CH:45]=[CH:46][CH:47]=[CH:48][C:43]=3[O:42][C:41]=2[C:36]([C:25]2[CH:24]=[CH:23][C:35]3[N:34]([C:2]4[CH:7]=[CH:6][C:5]([C:8]5[N:9]([C:17]6[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=6)[C:10]6[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=6[N:12]=5)=[CH:4][CH:3]=4)[C:33]4[C:28]([C:27]=3[CH:26]=2)=[CH:29][CH:30]=[CH:31][CH:32]=4)=[CH:37][CH:38]=1

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 230940702-(4-Bromophenyl)-1-phenyl-1H-benzo(d)imidazoleHCID 23676156Sodium t-butoxideHCID 666918774-(9H-Carbazol-3-yl)dibenzofuran

Product 1

HCID 666924982-[4-{3-(Dibenzofuran-4-yl)-9H-carbazol-9-yl}phenyl]-1-phenylbenzimidazoleYield 71%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8058HexaneSolvent

Procedure

To a 100-mL three-neck flask were added 0.70 g (1.0 mmol) of 2-(4-bromophenyl)-3-phenylbenzimidazole and 0.67 g (1.0 mmol) of 4-(9H-carbazol-3-yl)dibenzofuran, and the air in the flask was replaced with nitrogen. To this mixture were added 15 mL of toluene, 0.10 mL of tri(tert-butyl)phosphine (a 10 wt % hexane solution), 0.48 g (4.3 mmol) of sodium tert-butoxide. This mixture was degassed while being stirred under reduced pressure. This mixture was stirred at 110° C. for 20 hours. After the stirring, the mixture was washed twice with about 30 mL of water, and the mixture was separated into an organic layer and an aqueous layer. Then, the aqueous layer was subjected to extraction twice with about 30 mL of toluene. The organic layer and the solution of the extract were combined and washed once with about 100 mL of saturated brine. The obtained organic layer was dried over magnesium sulfate, and this mixture was subjected to filtration through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina. The obtained filtrate was concentrated to give a brown solid. The obtained brown solid was purified by silica gel column chromatography (a developing solvent in which the ethyl acetate/toluene ratio was 5:95), and further recrystallized from hexane/toluene, so that 0.86 g of a pale brown solid was obtained in 71% yield. The synthesis scheme of Step 2 is illustrated in (b-2).

Workup

  1. customThis mixture was degassed
  2. stirringThis mixture was stirred at 110° C. for 20 hours
  3. washAfter the stirring, the mixture was washed twice with about 30 mL of water
  4. customthe mixture was separated into an organic layer
  5. extractionThen, the aqueous layer was subjected to extraction twice with about 30 mL of toluene
  6. washwashed once with about 100 mL of saturated brine
  7. dry with materialThe obtained organic layer was dried over magnesium sulfate
  8. filtrationthis mixture was subjected to filtration through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina
  9. concentrationThe obtained filtrate was concentrated
  10. customto give a brown solid
  11. customThe obtained brown solid was purified by silica gel column chromatography (a developing solvent in which the ethyl acetate/toluene ratio
  12. customfurther recrystallized from hexane/toluene, so that 0.86 g of a pale brown solid
  13. customwas obtained in 71% yield
  14. customThe synthesis scheme of Step 2

Sources & evidence

ORD record
ord-096405d2a3ba4f0eaa588cbc5619d6b9
Source dataset
uspto-grants-2015_06
Patent number
US09065058B2

Reaction notes

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