4-Bromobiphenyl → 10-(Biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole

HRID 719051Notes

Reaction equation

HRID 719051 reaction equation
[CH3:1][C:2]1([CH3:22])[C:14]2[C:6]([N:7]=[C:8]3[C:13]=2[CH:12]=[CH:11][CH:10]=[CH:9]3)=[CH:5][C:4]2[CH:15]=[C:16]3[C:21]([C:3]1=2)=[CH:20][CH2:19][CH:18]=[CH:17]3.Br[C:24]1[CH:29]=[CH:28][C:27]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[CH:26][CH:25]=1.S(=O)(O)[O-].[Na+].C(C1C=C(C(C)(C)C)C=C(C(O)=O)C=1O)(C)(C)C.C(=O)([O-])[O-].[K+].[K+].C(C1C=CC=CC=1)CCCCCCCCCCC>[Cu].C1(C)C=CC=CC=1>[C:27]1([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[CH:28]=[CH:29][C:24]([CH:19]2[CH:20]=[C:21]3[C:16](=[CH:15][C:4]4[CH:5]=[C:6]5[C:14]([C:2]([CH3:22])([CH3:1])[C:3]=43)=[C:13]3[C:8]([CH:9]=[CH:10][CH:11]=[CH:12]3)=[N:7]5)[CH:17]=[CH:18]2)=[CH:25][CH:26]=1

Participants

9

Reactant 6

HCID 71014-BromobiphenylHCID 11430Potassium CarbonateHCID 31237DodecylbenzeneHCID 882083,5-Bis(1,1-dimethylethyl)-2-hydroxybenzoic acidHCID 23665763Sodium BisulfiteHCID 8668501212,12-Dimethyl-10,12-dihydroindeno[2,1-b]carbazole

Product 1

HCID 8668501610-(Biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazoleYield 88.9%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 1140TolueneSolvent

Conditions

Temperature
190 °C

Procedure

12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (35.5 g), 4-bromobiphenyl (35.0 g), sodium bisulfite (6.0 g), a copper powder (2.4 g), 3,5-di(tert-butyl)salicylic acid (9.4 g), potassium carbonate (31.2 g), and dodecylbenzene (52 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 190° C. for 26 hours. After cooled to 120° C., the mixture was stirred after adding toluene (35 ml), and a crude product was collected by filtration. After adding toluene (1.6 L) to the crude product, the crude product was heated and extracted at 110° C. After cooled to a room temperature, the crude product was concentrated under reduced pressure. The product was crystallized with methanol (120 ml) to obtain a white powder of 10-(biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole (48.5 g; yield 88.1%).

Workup

  1. temperatureheated
  2. temperatureAfter cooled to 120° C.
  3. stirringthe mixture was stirred
  4. filtrationa crude product was collected by filtration
  5. additionAfter adding toluene (1.6 L) to the crude product
  6. temperaturethe crude product was heated
  7. extractionextracted at 110° C
  8. temperatureAfter cooled to a room temperature
  9. concentrationthe crude product was concentrated under reduced pressure
  10. customThe product was crystallized with methanol (120 ml)

Sources & evidence

ORD record
ord-d185369012ed447b9fbc9c576297007e
Source dataset
uspto-grants-2015_11
Patent number
US09196837B2

Reaction notes

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