Potassium Carbonate → 2-[5-(9,9-Dimethylfluoren-2-yl)-4'-(2-pyridyl)biphenyl-3-yl]-4,6-diphenylpyrimidine

HRID 2273499Notes

Reaction equation

HRID 2273499 reaction equation
[CH3:1][C:2]1([CH3:18])[C:14]2[CH:13]=[C:12](B(O)O)[CH:11]=[CH:10][C:9]=2[C:8]2[C:3]1=[CH:4][CH:5]=[CH:6][CH:7]=2.Br[C:20]1[CH:21]=[C:22]([C:27]2[N:32]=[C:31]([C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[CH:30]=[C:29]([C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)[N:28]=2)[CH:23]=[C:24](Br)[CH:25]=1.C([O-])([O-])=O.[K+].[K+].[N:51]1[CH:56]=[CH:55][CH:54]=[CH:53][C:52]=1[C:57]1[CH:62]=[CH:61][C:60](B(O)O)=[CH:59][CH:58]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(O)C.C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:18])[C:14]2[CH:13]=[C:12]([C:20]3[CH:21]=[C:22]([C:27]4[N:32]=[C:31]([C:33]5[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=5)[CH:30]=[C:29]([C:39]5[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=5)[N:28]=4)[CH:23]=[C:24]([C:60]4[CH:59]=[CH:58][C:57]([C:52]5[CH:53]=[CH:54][CH:55]=[CH:56][N:51]=5)=[CH:62][CH:61]=4)[CH:25]=3)[CH:11]=[CH:10][C:9]=2[C:8]2[C:3]1=[CH:4][CH:5]=[CH:6][CH:7]=2

Participants

8

Reactant 4

HCID 11430Potassium Carbonate2×HCID 18980112B-(4-(2-Pyridinyl)phenyl)boronic acidHCID 22348454(9,9-Dimethyl-9H-fluoren-2-yl)boronic acidHCID 591334782-(3,5-Dibromophenyl)-4,6-diphenylpyrimidine

Product 1

HCID 679836992-[5-(9,9-Dimethylfluoren-2-yl)-4'-(2-pyridyl)biphenyl-3-yl]-4,6-diphenylpyrimidineYield 43.3%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

In a stream of argon, 0.71 g (3 mmol) of 9,9-dimethyl-2-fluoreneboronic acid, 1.4 g (3 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenylpyrimidine and 34.7 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium were suspended in a mixed solvent composed of 115 mL of toluene and 15 mL of ethanol, and the resultant suspension was heated to 50° C. To the suspension, 9 mL (9 mmol) of an aqueous 1M K2CO3 solution was gradually added dropwise, and the mixture was stirred for 18 hours. The resultant reaction mixture was cooled to room temperature, and then, 0.896 g (4.5 mmol) of 4-(2-pyridyl)phenylboronic acid and 9 mL (9 mmol) of an aqueous 1M K2CO3 solution were added to the reaction mixture. The resultant mixture was heated to 60° C., and maintained at that temperature for 3.5 hours while being stirred. The obtained reaction mixture was cooled to room temperature, and then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The obtained crude product was purified by silica gel chromatography using a hexane/chloroform (1:2) mixed solvent as an eluent to give 0.85 g of the target 2-[5-(9,9-dimethylfluoren-2-yl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenylpyrimidine as a white solid (yield: 43.3%).

Workup

  1. customThe resultant reaction mixture
  2. temperaturemaintained at that temperature for 3.5 hours
  3. stirringwhile being stirred
  4. customThe obtained reaction mixture
  5. temperaturewas cooled to room temperature
  6. distillationdistilled under a reduced pressure
  7. customto remove all volatile materials
  8. additionMethanol was added to the concentrate
  9. filtrationthe thus-deposited solid was collected by filtration
  10. customThe obtained crude product
  11. customwas purified by silica gel chromatography
  12. additionmixed solvent as an eluent

Sources & evidence

ORD record
ord-496890ca3bf14f62be00c01134a23db3
Source dataset
uspto-grants-2015_09
Patent number
US09120773B2

Reaction notes

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