Tris(1,1-dimethylethyl)phosphine → 3-(6-Phenyldibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole

HRID 240003Notes

Reaction equation

HRID 240003 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]3[C:14]([C:15]([C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)=[C:16]4[C:21]=2[CH:20]=[CH:19][CH:18]=[CH:17]4)=[CH:13][CH:12]=[CH:11][CH:10]=3)=[CH:4][CH:3]=1.[C:28]1([C:34]2[C:42]3[S:41][C:40]4[C:43]([C:47]5[CH:48]=[CH:49][C:50]6[NH:51][C:52]7[C:57]([C:58]=6[CH:59]=5)=[CH:56][CH:55]=[CH:54][CH:53]=7)=[CH:44][CH:45]=[CH:46][C:39]=4[C:38]=3[CH:37]=[CH:36][CH:35]=2)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=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>[C:28]1([C:34]2[C:42]3[S:41][C:40]4[C:43]([C:47]5[CH:48]=[CH:49][C:50]6[N:51]([C:2]7[CH:3]=[CH:4][C:5]([C:8]8[C:21]9[C:16]([C:15]([C:22]%10[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=%10)=[C:14]%10[C:9]=8[CH:10]=[CH:11][CH:12]=[CH:13]%10)=[CH:17][CH:18]=[CH:19][CH:20]=9)=[CH:6][CH:7]=7)[C:52]7[C:57]([C:58]=6[CH:59]=5)=[CH:56][CH:55]=[CH:54][CH:53]=7)=[CH:44][CH:45]=[CH:46][C:39]=4[C:38]=3[CH:37]=[CH:36][CH:35]=2)[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1

Participants

8

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 221382759-(4-Bromophenyl)-10-phenylanthraceneHCID 23676156Sodium t-butoxideHCID 666916643-(6-phenyldibenzothiophen-4-yl)-9H-carbazole

Product 1

HCID 866634073-(6-Phenyldibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazoleYield 80%

Reagents, catalysts & solvents 3

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

Procedure

In a 50-mL three-neck flask were put 1.3 g (3.3 mmol) of 9-(4-bromophenyl)-10-phenylanthracene, 1.0 g (2.4 mmol) of 3-(6-phenyldibenzothiophen-4-yl)-9H-carbazole, and 0.95 g (9.9 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, 11 mg (0.18 mmol) of bis(dibenzylideneacetone)palladium(0) was added to this mixture. This mixture was stirred at 110° C. for 6 hours under a nitrogen stream. After the stirring, the aqueous layer of this mixture was subjected to extraction with toluene, and the solution of the extract and the organic layer were combined and washed with saturated brine. The organic layer was dried over magnesium sulfate. This mixture was gravity-filtered, and the filtrate was concentrated to give a solid. The obtained solid was purified by silica gel column chromatography (developing solvent, toluene:hexane=1:9 and then toluene:hexane=3:7). The obtained solid was recrystallized from toluene/hexane to give 1.4 g of a pale yellow solid which was the object of the synthesis in a yield of 80%. The synthesis scheme of Step 2 is illustrated in (b-11).

Workup

  1. customIn a 50-mL three-neck flask were put
  2. customThis mixture was degassed
  3. stirringThis mixture was stirred at 110° C. for 6 hours under a nitrogen stream
  4. extractionAfter the stirring, the aqueous layer of this mixture was subjected to extraction with toluene
  5. extractionthe solution of the extract
  6. washwashed with saturated brine
  7. dry with materialThe organic layer was dried over magnesium sulfate
  8. filtrationThis mixture was gravity-filtered
  9. concentrationthe filtrate was concentrated
  10. customto give a solid
  11. customThe obtained solid was purified by silica gel column chromatography (
  12. customThe obtained solid was recrystallized from toluene/hexane

Sources & evidence

ORD record
ord-5031887383c344aabbba864e99594a51
Source dataset
uspto-grants-2014_02
Patent number
US08642782B2

Reaction notes

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