Potassium Phosphate, Tribasic → HCID 68243356, compound

HRID 525988Notes

Reaction equation

HRID 525988 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([N:8]([C:51]2[CH:56]=[CH:55][CH:54]=[C:53]([CH3:57])[CH:52]=2)[C:9]2[CH:21]=[CH:20][C:19]3[C:18]4[C:13](=[CH:14][C:15]([N:22]([C:30]5[CH:35]=[CH:34][CH:33]=[C:32]([CH3:36])[CH:31]=5)[C:23]5[CH:28]=[CH:27][CH:26]=[C:25]([CH3:29])[CH:24]=5)=[CH:16][CH:17]=4)[C:12]4([C:48]5[CH:47]=[C:46](Br)[CH:45]=[CH:44][C:43]=5[C:42]5[C:37]4=[CH:38][C:39](Br)=[CH:40][CH:41]=5)[C:11]=3[CH:10]=2)[CH:5]=[CH:6][CH:7]=1.[C:58]1(B(O)O)[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:75]1(C)[CH:80]=[CH:79][CH:78]=[CH:77][C:76]=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)(=O)C.C(O)C.O1CCOCC1.O.C1(C)C=CC=CC=1>[CH3:1][C:2]1[CH:3]=[C:4]([N:8]([C:51]2[CH:56]=[CH:55][CH:54]=[C:53]([CH3:57])[CH:52]=2)[C:9]2[CH:21]=[CH:20][C:19]3[C:18]4[C:13](=[CH:14][C:15]([N:22]([C:30]5[CH:35]=[CH:34][CH:33]=[C:32]([CH3:36])[CH:31]=5)[C:23]5[CH:28]=[CH:27][CH:26]=[C:25]([CH3:29])[CH:24]=5)=[CH:16][CH:17]=4)[C:12]4([C:48]5[CH:47]=[C:46]([C:58]6[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=6)[CH:45]=[CH:44][C:43]=5[C:42]5[C:37]4=[CH:38][C:39]([C:75]4[CH:80]=[CH:79][CH:78]=[CH:77][CH:76]=4)=[CH:40][CH:41]=5)[C:11]=3[CH:10]=2)[CH:5]=[CH:6][CH:7]=1

Participants

10

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 66827Phenylboronic AcidHCID 80271Tri-o-tolylphosphineHCID 71208816HCID 71208816, compound

Product 1

HCID 68243356HCID 68243356, compound

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 312751,4-DioxaneSolventHCID 18476134Acetic acid ethanolSolvent

Procedure

134.5 g (190 mmol) of N,N,N′,N′-tetrakis(3-methylphenyl)-2′,7′-dibromo-9,9′-spirobifluorene-2,7-diamine, 50.4 g (420 mmol) of benzene-boronic acid and potassium phosphate (195.5 g, 0.92 mol) are initially introduced into a 4 l flask, and 1200 ml of toluene, 1200 ml of water and 475 ml of dioxane are then added. The mixture is degassed for 30 minutes by passing-through of argon with stirring. The tris-o-tolylphosphine (4.0 g, 13.2 mmol) is then added, and the mixture is stirred briefly. Palladium(II) acetate (480 mg, 2.1 mmol) is subsequently added. Finally, the mixture is heated under reflux for 12 hours. A further 10 g of boronic acid ester are added, and the mixture is heated under reflux for a further 10 h. The mixture is then allowed to cool. Glacial acetic acid/ethanol 1:1 (1500 ml) is subsequently added. The precipitated solid is filtered off with suction, rinsed 2× with about 250 ml of toluene, 2× with about 450 ml of water/ethanol mixture (ratio 1:1) and finally 2× with 550 ml of ethanol. The solid is extracted with 2 l of toluene in a hot extractor for 5 days and subsequently recrystallised 4× from degassed dioxane. The product is sublimed at 5× 10−6 mbar and about 330° C.

Workup

  1. customThe mixture is degassed for 30 minutes
  2. stirringthe mixture is stirred briefly
  3. temperatureFinally, the mixture is heated
  4. temperatureunder reflux for 12 hours
  5. temperaturethe mixture is heated
  6. temperatureunder reflux for a further 10 h
  7. temperatureto cool
  8. filtrationThe precipitated solid is filtered off with suction
  9. washrinsed 2× with about 250 ml of toluene, 2× with about 450 ml of water/ethanol mixture (ratio 1:1) and finally 2× with 550 ml of ethanol
  10. extractionThe solid is extracted with 2 l of toluene in a hot extractor for 5 days
  11. customsubsequently recrystallised 4×
  12. customfrom degassed dioxane
  13. customis sublimed at 5× 10−6 mbar and about 330° C.

Sources & evidence

ORD record
ord-5f5987496ed54f8db28344ca89415822
Source dataset
uspto-grants-2016_05
Patent number
US09343683B2

Reaction notes

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