Tris(1,1-dimethylethyl)phosphine → 3-(dibenzothiophen-4-yl)-9-(9,10-diphenyl-2-anthryl)-9H-carbazole

HRID 239998Notes

Reaction equation

HRID 239998 reaction equation
I[C:2]1[CH:15]=[CH:14][C:13]2[C:4](=[C:5]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C:6]3[C:11]([C:12]=2[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:10][CH:9]=[CH:8][CH:7]=3)[CH:3]=1.[CH:28]1[C:36]2[C:35]3[CH:37]=[CH:38][CH:39]=[CH:40][C:34]=3[S:33][C:32]=2[C:31]([C:41]2[CH:42]=[CH:43][C:44]3[NH:45][C:46]4[C:51]([C:52]=3[CH:53]=2)=[CH:50][CH:49]=[CH:48][CH:47]=4)=[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>[CH:28]1[C:36]2[C:35]3[CH:37]=[CH:38][CH:39]=[CH:40][C:34]=3[S:33][C:32]=2[C:31]([C:41]2[CH:42]=[CH:43][C:44]3[N:45]([C:15]4[CH:2]=[CH:3][C:4]5[C:13](=[C:12]([C:16]6[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=6)[C:11]6[C:6]([C:5]=5[C:22]5[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=5)=[CH:7][CH:8]=[CH:9][CH:10]=6)[CH:14]=4)[C:46]4[C:51]([C:52]=3[CH:53]=2)=[CH:50][CH:49]=[CH:48][CH:47]=4)=[CH:30][CH:29]=1

Participants

8

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 575365142-Iodo-9,10-diphenylanthraceneHCID 666918723-(Dibenzothiophen-4-yl)-9H-carbazole

Product 1

HCID 866634043-(dibenzothiophen-4-yl)-9-(9,10-diphenyl-2-anthryl)-9H-carbazoleYield 76%

Reagents, catalysts & solvents 3

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

Procedure

To a 100-mL three-neck flask were added 1.4 g (3.0 mmol) of 2-iodo-9,10-diphenylanthracene, 1.1 g (3.0 mmol) of 3-(dibenzothiophen-4-yl)-9H-carbazole, and 0.86 g (9.0 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, 86 mg (0.15 mmol) of bis(dibenzylideneacetone)palladium(0) was added to the mixture. This mixture was stirred at 110° C. for 4 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 purified by silica gel column chromatography (developing solvent, hexane:toluene=5:1). The obtained fraction was concentrated to give a yellow solid. The obtained yellow solid was recrystallized from toluene/hexane, so that 1.5 g of a yellow solid was obtained in 76% yield. The synthesis scheme of Step 2 is illustrated in (b-7).

Workup

  1. customThis mixture was degassed
  2. stirringThis mixture was stirred at 110° C. for 4 hours under a nitrogen stream
  3. 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)
  4. concentrationThe filtrate was concentrated
  5. customto give a yellow solid
  6. customThe obtained solid was purified by silica gel column chromatography (developing solvent, hexane:toluene=5:1)
  7. concentrationThe obtained fraction was concentrated
  8. customto give a yellow solid
  9. customThe obtained yellow solid was recrystallized from toluene/hexane, so that 1.5 g of a yellow solid
  10. customwas obtained in 76% yield
  11. customThe synthesis scheme of Step 2

Sources & evidence

ORD record
ord-3e2f9515065541cbb0045245a57f69e4
Source dataset
uspto-grants-2014_02
Patent number
US08642782B2

Reaction notes

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