Potassium Phosphate, Tribasic → HCID 131736878, compound

HRID 1488320Notes

Reaction equation

HRID 1488320 reaction equation
BrC1C=CC2C3C=C4C(CCCCCCCC)(CCCCCCCC)C5C(=CC=C(Br)C=5)C4=CC=3C(CCCCCCCC)(CCCCCCCC)C=2C=1.BrC1C=CC(N(C2C=CC(Br)=CC=2)C2C=C[C:66]([C:69](C)([CH3:72])[C:70]#[N:71])=CC=2)=CC=1.[CH3:81][C:82]1([CH3:122])[C:86]([CH3:88])([CH3:87])[O:85][B:84]([C:89]2[CH:94]=[CH:93][C:92]([N:95]([C:107]3[CH:112]=[CH:111][C:110]([B:113]4[O:117][C:116]([CH3:119])([CH3:118])[C:115]([CH3:121])([CH3:120])[O:114]4)=[CH:109][CH:108]=3)[C:96]3[CH:101]=[CH:100][C:99]([C:102]([CH3:106])([CH3:105])[C:103]#[N:104])=[CH:98][CH:97]=3)=[CH:91][CH:90]=2)[O:83]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].C1(C)C=CC=CC=1.O1CCOCC1.O>[CH3:120][C:115]1([CH3:121])[C:116]([CH3:118])([CH3:119])[O:117][B:113]([C:110]2[CH:111]=[CH:112][C:107]([N:95]([C:92]3[CH:91]=[CH:90][C:89]([B:84]4[O:85][C:86]([CH3:88])([CH3:87])[C:82]([CH3:122])([CH3:81])[O:83]4)=[CH:94][CH:93]=3)[C:96]3[CH:97]=[CH:98][C:99]([C:102]([CH3:105])([CH3:106])[C:103]#[N:104])=[CH:100][CH:101]=3)=[CH:108][CH:109]=2)[O:114]1.[CH:69]([C:70]#[N:71])([CH3:72])[CH3:66]

Participants

9

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 586688742,8-Dibromo-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2-b]fluoreneHCID 71061181HCID 71061181, compoundHCID 71061642HCID 71061642, compound

Product 1

HCID 131736878HCID 131736878, compound

Reagents, catalysts & solvents 4

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

2,8-dibromo-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2-b]fluorene (2.60 g), 2-(4-(bis(4-bromophenyl)amino)phenyl)-2-methylpropanenitrile (947 mg), 2-(4-(bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amino)phenyl)-2-methylpropanenitrile (2.84 g), potassium phosphate (4.27 g) and Aliquat 336 (2 drops) were dissolved in a mixture of toluene (32 mL), dioxane (16 mL) and water (16 mL). The solution was degassed for 15 minutes before adding tris(dibenzylideneacetone)dipalladium(0) (23 mg) and tri(o-tolyl)phosphine (46 mg) and heating to 90° C. for 17 hours. The reaction mixture was poured onto methanol (320 mL) and the resulting precipitate was filtered, dissolved in toluene (200 mL), washed with 1N NaOH, brine, water, dried (MgSO4) and concentrated. The residue was dissolved in toluene (150 mL) and passed through a pad of silica, washing through with toluene, toluene/THF and THF. The filtrates were concentrated and charcoal treated (3×0.53 g). The filtrates were concentrated and the solid taken up in THF (70 mL) and added dropwise to methanol (350 mL). The solid was filtered to give the target compound as a yellow solid. Yield: 3.3 g. Mn=11341 g/mol, n=11.2, Polydispersity=1.9.

Workup

  1. customThe solution was degassed for 15 minutes
  2. additionbefore adding tris(dibenzylideneacetone)dipalladium(0) (23 mg) and tri(o-tolyl)phosphine (46 mg)
  3. additionThe reaction mixture was poured onto methanol (320 mL)
  4. filtrationthe resulting precipitate was filtered
  5. dissolutiondissolved in toluene (200 mL)
  6. washwashed with 1N NaOH, brine, water
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. dissolutionThe residue was dissolved in toluene (150 mL)
  10. washwashing through with toluene, toluene/THF and THF
  11. concentrationThe filtrates were concentrated
  12. additioncharcoal treated (3×0.53 g)
  13. concentrationThe filtrates were concentrated
  14. additionadded dropwise to methanol (350 mL)
  15. filtrationThe solid was filtered

Sources & evidence

ORD record
ord-29c5a8c9f88c4952be283228081e86ef
Source dataset
uspto-grants-2016_08
Patent number
US09431145B2

Reaction notes

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