1,2-Dimethoxyethane → 2,7-Di(2-naphthyl)-3,6-ditert-butyl-fluorene

HRID 1050657Notes

Reaction equation

HRID 1050657 reaction equation
CO[CH2:3][CH2:4]OC.Br[C:8]1[C:20]([C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:19][C:18]2[C:17]3[C:12](=[CH:13][C:14](Br)=[C:15]([C:25]([CH3:28])([CH3:27])[CH3:26])[CH:16]=3)[CH2:11][C:10]=2[CH:9]=1.[CH:30]1[C:39]2[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=2)[CH:33]=[CH:32][C:31]=1OB(O)O.C(=O)([O-])[O-].[Na+].[Na+]>C(O)C.ClCCl.CCCCCC>[CH:30]1[C:39]2[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=2)[CH:33]=[CH:32][C:31]=1[C:14]1[C:15]([C:25]([CH3:27])([CH3:26])[CH3:28])=[CH:16][C:17]2[C:18]3[C:10](=[CH:9][C:8]([C:4]4[CH:3]=[CH:17][C:18]5[C:10](=[CH:9][CH:8]=[CH:20][CH:19]=5)[CH:11]=4)=[C:20]([C:21]([CH3:24])([CH3:23])[CH3:22])[CH:19]=3)[CH2:11][C:12]=2[CH:13]=1

Participants

8

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 135475422,7-Dibromo-3,6-DI-tert-butyl-9H-fluoreneHCID 219179972-Naphthylboric acid

Product 1

HCID 866231922,7-Di(2-naphthyl)-3,6-ditert-butyl-fluoreneYield 74%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 6344DichloromethaneSolventHCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, 45 mL of dehydrated 1,2-dimethoxyethane was added to 3.02 g (6.92 mmol) of 2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis Example 1-1(i) and 0.40 g (0.35 mmol) of Pd(PPh3), and the mixture was stirred at room temperature for 20 minutes. To this solution, a solution prepared by dissolving 2.62 g (15.2 mmol) of 2-naphthylboric acid in 15 mL of ethanol was added, and the mixture was stirred at room temperature for 20 minutes. Then, 13.8 mL (27.7 mmol) of a 2.0 mol/L aqueous solution of sodium carbonate was added. The mixture was heated to reflux for 21 hours, and then left to be naturally cooled. Subsequently, the reaction was terminated with 1N hydrochloric acid in an ice bath. Thereafter, dichloromethane was added to perform liquid-liquid phase separation. The aqueous layer was subjected to extraction with diethyl ether twice, and the resultant was combined with the organic layer obtained previously. The resulting liquid 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. Subsequently, the solvent was distilled off, and the resulting solids were subjected to separation by silica gel chromatography. To the yellow powder obtained, a mixed solution of n-hexane and a small amount of dichloromethane was added. The mixture was heated to 65° C. to dissolve the powder completely, and was then left to stand overnight at room temperature. Crystals precipitated were washed three times with 10 mL of n-hexane to obtain a target product as a white powder (yield 2.71 g (74%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. customTo this solution, a solution prepared
  2. additionwas added
  3. stirringthe mixture was stirred at room temperature for 20 minutes
  4. temperatureThe mixture was heated
  5. temperatureto reflux for 21 hours
  6. waitleft
  7. temperatureto be naturally cooled
  8. customSubsequently, the reaction was terminated with 1N hydrochloric acid in an ice bath
  9. additionThereafter, dichloromethane was added
  10. customliquid-liquid phase separation
  11. extractionThe aqueous layer was subjected to extraction with diethyl ether twice
  12. customobtained previously
  13. washThe resulting liquid was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  14. dry with materialonce with saturated brine, and then dried over magnesium sulfate
  15. distillationSubsequently, the solvent was distilled off
  16. customthe resulting solids were subjected to separation by silica gel chromatography
  17. customTo the yellow powder obtained
  18. temperatureThe mixture was heated to 65° C.
  19. dissolutionto dissolve the powder completely
  20. waitwas then left
  21. waitto stand overnight at room temperature
  22. customCrystals precipitated
  23. washwere washed three times with 10 mL of n-hexane

Sources & evidence

ORD record
ord-f17dd51ee109412390323462b6b183e4
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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