Hydrochloric Acid → 3,3'-((2,7-bis(naphthalen-1-yl(phenyl)amino)-9H-fluorene-9,9-diyl)bis(butane-4,1-diyl))dibenzaldehyde

HRID 2408317Notes

Reaction equation

HRID 2408317 reaction equation
[O:1]1CCO[CH:2]1[C:6]1[CH:7]=[C:8]([CH2:12][CH2:13][CH2:14][CH2:15][C:16]2([CH2:63][CH2:64][CH2:65][CH2:66][C:67]3[CH:72]=[CH:71][CH:70]=[C:69]([CH:73]4OCC[O:74]4)[CH:68]=3)[C:28]3[CH:27]=[C:26]([N:29]([C:36]4[C:45]5[C:40](=[CH:41][CH:42]=[CH:43][CH:44]=5)[CH:39]=[CH:38][CH:37]=4)[C:30]4[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=4)[CH:25]=[CH:24][C:23]=3[C:22]3[C:17]2=[CH:18][C:19]([N:46]([C:53]2[C:62]4[C:57](=[CH:58][CH:59]=[CH:60][CH:61]=4)[CH:56]=[CH:55][CH:54]=2)[C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)=[CH:20][CH:21]=3)[CH:9]=[CH:10][CH:11]=1.Cl>CC(C)=O>[C:36]1([N:29]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C:26]2[CH:25]=[CH:24][C:23]3[C:22]4[C:17](=[CH:18][C:19]([N:46]([C:53]5[C:62]6[C:57](=[CH:58][CH:59]=[CH:60][CH:61]=6)[CH:56]=[CH:55][CH:54]=5)[C:47]5[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=5)=[CH:20][CH:21]=4)[C:16]([CH2:63][CH2:64][CH2:65][CH2:66][C:67]4[CH:68]=[C:69]([CH:70]=[CH:71][CH:72]=4)[CH:73]=[O:74])([CH2:15][CH2:14][CH2:13][CH2:12][C:8]4[CH:7]=[C:6]([CH:11]=[CH:10][CH:9]=4)[CH:2]=[O:1])[C:28]=3[CH:27]=2)[C:45]2[C:40](=[CH:41][CH:42]=[CH:43][CH:44]=2)[CH:39]=[CH:38][CH:37]=1

Participants

4

Reactant 2

HCID 313Hydrochloric AcidHCID 580284899,9-bis(4-(3-(1,3-dioxolan-2-yl)phenyl)butyl)-N2,N7-di(naphthalen-1-yl)-N2,N7-diphenyl-9H-fluorene-2,7-diamine

Product 1

HCID 580284653,3'-((2,7-bis(naphthalen-1-yl(phenyl)amino)-9H-fluorene-9,9-diyl)bis(butane-4,1-diyl))dibenzaldehyde

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To 1-liter three-neck round bottom flask equipped with a magnetic stir bar and an addition funnel was transferred a solution of 9,9-bis(4-(3-(1,3-dioxolan-2-yl)phenyl)butyl)-N2,N7-di(naphthalen-1-yl)-N2,N7-diphenyl-9H-fluorene-2,7-diamine (12.3 g) in acetone (500 mL). Hydrochloric acid solution (61.0 mL, 2.0M) was transferred to the addition funnel atop the reaction flask by syringe. The acid solution was added to the reaction dropwise with vigorous stirring. The reaction was allowed to stir for an additional 30 minutes following the addition of acid. Reaction completion was confirmed by thin-layer chromatography and solvent was removed by rotary evaporation. Ethyl acetate (750 mL) was added to the resulting mixture and this solution was washed with DI water (5×200 mL). The organic fraction was collected and dried over anhydrous magnesium sulfate. Solids were removed by gravity filtration. Silica gel was added to the solution and solvent was removed by rotary evaporation leaving the crude material adsorbed to silica. Crude product was initially purified by flash column chromatography using ethyl acetate/hexane as an eluent. The resulting material was dissolved in a minimum amount of acetone and precipitated into cold methanol (3×750 mL). The solids collected by vacuum filtration were dried and determined to be pure product by NMR.

Workup

  1. customTo 1-liter three-neck round bottom flask equipped with a magnetic stir bar and an addition funnel
  2. additionThe acid solution was added to the reaction dropwise with vigorous stirring
  3. additionthe addition of acid
  4. customReaction completion
  5. customwas removed by rotary evaporation
  6. additionEthyl acetate (750 mL) was added to the resulting mixture
  7. washthis solution was washed with DI water (5×200 mL)
  8. customThe organic fraction was collected
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customSolids were removed by gravity filtration
  11. additionSilica gel was added to the solution and solvent
  12. customwas removed by rotary evaporation

Sources & evidence

ORD record
ord-0d30b538ea614f478b1fec79b1a073b2
Source dataset
uspto-grants-2014_08
Patent number
US08815639B2

Reaction notes

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