Tris(1,1-dimethylethyl)phosphine → 3-(Dibenzofuran-4-yl)-9-[3-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole

HRID 64555Notes

Reaction equation

HRID 64555 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2[CH:21]=[CH:20][C:19]3[C:10](=[C:11]([C:28]4[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=4)[C:12]4[C:17]([C:18]=3[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[CH:16][CH:15]=[CH:14][CH:13]=4)[CH:9]=2)[CH:5]=[CH:6][CH:7]=1.[CH:34]1[C:42]2[C:41]3[CH:43]=[CH:44][CH:45]=[CH:46][C:40]=3[O:39][C:38]=2[C:37]([C:47]2[CH:48]=[CH:49][C:50]3[NH:51][C:52]4[C:57]([C:58]=3[CH:59]=2)=[CH:56][CH:55]=[CH:54][CH:53]=4)=[CH:36][CH:35]=1.CC(C)([O-])C.[Na+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)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.[Pd].CCCCCC.C1(C)C=CC=CC=1>[CH:34]1[C:42]2[C:41]3[CH:43]=[CH:44][CH:45]=[CH:46][C:40]=3[O:39][C:38]=2[C:37]([C:47]2[CH:48]=[CH:49][C:50]3[N:51]([C:6]4[CH:7]=[CH:2][CH:3]=[C:4]([C:8]5[CH:21]=[CH:20][C:19]6[C:10](=[C:11]([C:28]7[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=7)[C:12]7[C:17]([C:18]=6[C:22]6[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=6)=[CH:16][CH:15]=[CH:14][CH:13]=7)[CH:9]=5)[CH:5]=4)[C:52]4[C:57]([C:58]=3[CH:59]=2)=[CH:56][CH:55]=[CH:54][CH:53]=4)=[CH:36][CH:35]=1

Participants

8

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 575364512-(3-Bromophenyl)-9,10-diphenylanthraceneHCID 666918774-(9H-Carbazol-3-yl)dibenzofuran

Product 1

HCID 866634113-(Dibenzofuran-4-yl)-9-[3-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazoleYield 60%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolventHCID 8058HexaneSolvent

Procedure

In a 100-mL three-neck flask were put 1.0 g (2.1 mmol) of 2-(3-bromophenyl)-9,10-diphenylanthracene, 0.69 g (2.1 mmol) of 3-(dibenzofuran-4-yl)-9H-carbazole, and 0.59 g (6.2 mmol) of sodium tert-butoxide. After the air in the flask was replaced with nitrogen, to this mixture were added 20 mL of toluene and 0.2 mL of tri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture was degassed by being stirred while the pressure was reduced. After the degassing, 59 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0) was added to this mixture. This mixture was stirred at 110° C. for 5 hours under a nitrogen stream. After the stirring, the obtained mixture was suction-filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), alumina, and Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135). The filtrate was concentrated to give a yellow solid. The obtained solid was recrystallized from toluene, and the obtained crystal was purified by high performance liquid column chromatography (abbreviation: HPLC) (developing solvent: chloroform). The obtained fraction was concentrated to give 0.91 g of a pale yellow solid in 60% yield. The synthesis scheme of Step 2 is illustrated in (b-15).

Workup

  1. customIn a 100-mL three-neck flask were put
  2. customThis mixture was degassed
  3. stirringThis mixture was stirred at 110° C. for 5 hours under a nitrogen stream
  4. filtrationAfter the stirring, the obtained mixture was suction-filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), alumina, and Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135)
  5. concentrationThe filtrate was concentrated
  6. customto give a yellow solid
  7. customThe obtained solid was recrystallized from toluene
  8. customthe obtained crystal was purified by high performance liquid column chromatography (abbreviation: HPLC) (developing solvent: chloroform)
  9. concentrationThe obtained fraction was concentrated

Sources & evidence

ORD record
ord-e3cc12f0cd8042bbb886b5ff71320aa6
Source dataset
uspto-grants-2016_09
Patent number
US09450188B2

Reaction notes

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