Toluene → HCID 69669040, compound

HRID 535300Notes

Reaction equation

HRID 535300 reaction equation
P([O-])([O-])([O-])=O.[K+].[K+].[K+].C1(C)C=CC=CC=1P([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[CH3:29])C1C=CC=CC=1C.Br[C:32]1[C:44]2[C:43]3[C:38](=[CH:39][CH:40]=[CH:41][CH:42]=3)[C:37]3([C:56]4[C:55]([O:57][CH3:58])=[CH:54][CH:53]=[C:52](Br)[C:51]=4[C:50]4[C:45]3=[CH:46][CH:47]=[CH:48][CH:49]=4)[C:36]=2[C:35]([O:60][CH3:61])=[CH:34][CH:33]=1.[C:62]1(B(O)O)[C:71]2[C:66](=[CH:67][CH:68]=[CH:69][CH:70]=2)[CH:65]=[CH:64][CH:63]=1.[C:75]1(C)[CH:80]=CC=C[CH:76]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.O1CCOCC1>[C:62]1([C:32]2[C:44]3[C:43]4[C:38](=[CH:39][CH:40]=[CH:41][CH:42]=4)[C:37]4([C:56]5[C:55]([O:57][CH3:58])=[CH:54][CH:53]=[C:52]([C:25]6[C:24]7[C:23](=[CH:76][CH:75]=[CH:80][CH:29]=7)[CH:28]=[CH:27][CH:26]=6)[C:51]=5[C:50]5[C:45]4=[CH:46][CH:47]=[CH:48][CH:49]=5)[C:36]=3[C:35]([O:60][CH3:61])=[CH:34][CH:33]=2)[C:71]2[C:66](=[CH:67][CH:68]=[CH:69][CH:70]=2)[CH:65]=[CH:64][CH:63]=1

Participants

9

Reactant 5

HCID 1140TolueneHCID 62657Potassium Phosphate, TribasicHCID 80271Tri-o-tolylphosphineHCID 2545321-Naphthaleneboronic acidHCID 11432601HCID 11432601, compound

Product 1

HCID 69669040HCID 69669040, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

25.5 g (120 mmol) of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 400 ml of water, 913 mg (3 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to a well-stirred suspension of 26.7 g (50 mmol) of 4,4′-dibromo-1,1′-dimethoxy-9,9′-spirobifluorene and 22.4 g (130 mmol) of 1-naphthylboronic acid, and the mixture is subsequently heated under reflux for 16 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 50 ml of toluene, three times with 50 ml of ethanol:water (1:1, v:v) and three times with 100 ml of ethanol and subsequently recrystallised three times from DMF (about 10 ml/g). Yield: 20 g (31 mmol), 65.0%, purity: 99.9% (HPLC).

Workup

  1. temperaturethe mixture is subsequently heated
  2. temperatureunder reflux for 16 h
  3. temperatureAfter cooling
  4. filtrationthe precipitated solid is filtered off with suction
  5. washwashed three times with 50 ml of toluene, three times with 50 ml of ethanol:water (1:1, v:v) and three times with 100 ml of ethanol
  6. customsubsequently recrystallised three times from DMF (about 10 ml/g)

Sources & evidence

ORD record
ord-07297df3ff154eb19c0e14c7cb447072
Source dataset
uspto-grants-2014_10
Patent number
US08859111B2

Reaction notes

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