Hydrochloric Acid → Dibenzylmethylene(cyclopentadienyl)(2,7-di[2-naphthyl]-3,6-ditert-butylfluorene)

HRID 1050658Notes

Reaction equation

HRID 1050658 reaction equation
[C:1](OC)([CH3:4])([CH3:3])[CH3:2].[CH:7]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:10]=[CH:9][C:8]=1[C:17]1[C:29]([C:30]([CH3:33])([CH3:32])[CH3:31])=[CH:28][C:27]2[C:26]3[C:21](=[CH:22][C:23]([C:38]4[CH:47]=[CH:46][C:45]5[C:40](=[CH:41][CH:42]=[CH:43][CH:44]=5)[CH:39]=4)=[C:24]([C:34]([CH3:37])([CH3:36])[CH3:35])[CH:25]=3)[CH2:20][C:19]=2[CH:18]=1.[CH2:48]([Li])[CH2:49][CH2:50][CH3:51].Cl>C(OCC)C.CCCCCC>[CH2:2]([C:51](=[C:28]1[C:27]2[C:19]([CH:20]=[C:21]3[C:26]=2[CH:25]=[C:24]([C:34]([CH3:37])([CH3:36])[CH3:35])[C:23]([C:38]2[CH:47]=[CH:46][C:45]4[C:40](=[CH:41][CH:42]=[CH:43][CH:44]=4)[CH:39]=2)=[CH:22]3)=[C:18]([CH:21]2[CH:26]=[CH:27][CH:19]=[CH:20]2)[C:17]([C:8]2[CH:9]=[CH:10][C:11]3[C:16](=[CH:15][CH:14]=[CH:13][CH:12]=3)[CH:7]=2)=[C:29]1[C:30]([CH3:31])([CH3:32])[CH3:33])[CH2:50][C:49]1[CH:48]=[CH:16][CH:7]=[CH:8][CH:9]=1)[C:1]1[CH:4]=[CH:10][CH:11]=[CH:12][CH:3]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 15413tert-Butyl methyl etherHCID 866231922,7-Di(2-naphthyl)-3,6-ditert-butyl-fluoreneHCID 178418339Butyllithium

Product 1

HCID 131736077Dibenzylmethylene(cyclopentadienyl)(2,7-di[2-naphthyl]-3,6-ditert-butylfluorene)Yield 53%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, 80 mL of dehydrated tert-butylmethylether was added to 0.82 g (1.54 mmol) of 2,7-di(2-naphthyl)-3,6-ditert-butyl-fluorene, and the mixture was stirred. This solution was cooled in an ice bath, and 1.10 mL (1.76 mmol) of a 1.60 mol/L hexane solution of n-butyllithium was added. The mixture was stirred at room temperature for 22 hours. To the yellow suspension thus obtained, 0.44 g (1.70 mmol) of 6,6-dibenzofulvene synthesized in Synthesis Example 1-1 (iii) was added, and the mixture was heated to reflux for 19 hours. Subsequently, 30 mL of 1N hydrochloric acid was added to the light orange-brown solution obtained to terminate the reaction. Then, 100 mL of diethylether was added to perform a liquid-liquid phase separation, and the soluble fraction was extracted. This organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water, and once with saturated brine, and then dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain a target product as a pale yellow solid (yield 0.64 g (53%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. temperatureThis solution was cooled in an ice bath
  2. stirringThe mixture was stirred at room temperature for 22 hours
  3. customTo the yellow suspension thus obtained
  4. additionwas added
  5. temperaturethe mixture was heated
  6. temperatureto reflux for 19 hours
  7. customobtained
  8. customto terminate
  9. customthe reaction
  10. customa liquid-liquid phase separation
  11. extractionthe soluble fraction was extracted
  12. washThis organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  13. dry with materialonce with saturated brine, and then dried over magnesium sulfate
  14. distillationThe solvent was distilled off
  15. customthe residue was purified by column chromatography

Sources & evidence

ORD record
ord-7364c66e938e434c8b8f8f9ebf3ec2c7
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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