Diethyl Ether → 2,7-Dimethyl-3,6-ditert-butyl-fluorene

HRID 1050670Notes

Reaction equation

HRID 1050670 reaction equation
BrC1[C:14]([C:15]([CH3:18])([CH3:17])[CH3:16])=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8](Br)=[C:9]([C:19]([CH3:22])([CH3:21])[CH3:20])[CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.C(Cl)Cl.[C:27](OC)(C)(C)C.C[Mg]Br.CCO[CH2:39][CH3:40]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:27][C:8]1[C:9]([C:19]([CH3:21])([CH3:20])[CH3:22])=[CH:10][C:11]2[C:12]3[C:4](=[CH:3][C:39]([CH3:40])=[C:14]([C:15]([CH3:16])([CH3:18])[CH3:17])[CH:13]=3)[CH2:5][C:6]=2[CH:7]=1

Participants

7

Reactant 5

HCID 3283Diethyl EtherHCID 6344DichloromethaneHCID 15413tert-Butyl methyl etherHCID 135475422,7-Dibromo-3,6-DI-tert-butyl-9H-fluoreneHCID 178418573HCID 178418573, compound

Product 1

HCID 219826932,7-Dimethyl-3,6-ditert-butyl-fluorene

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Procedure

Under a nitrogen stream, a 300-ml three-necked flask was charged with 5.03 g (11.5 mmol) of 2,7-dibromo-3,6-di-t-butyl-fluorene synthesized by the procedure of Synthesis Example 2-4(i) and 0.196 g (0.24 mmol) of PdCl2(dppf).CH2Cl2, and further charged with 100 mL of dehydrated t-butylmethylether. The mixture was stirred at room temperature for 20 minutes. This solution was cooled in an ice bath, and 19.2 mL (57.6 mmol) of a 3.0 mol/L ether solution of methylmagnesium bromide was added dropwise over 15 minutes. Subsequently, a slurry solution obtained by heating to reflux for 5 days was left to be naturally cooled, and then quenched with cold 1 N hydrochloric acid in an ice bath. Subsequently, ether was added to extract the soluble fraction, and this organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water and saturated brine, and then dried over magnesium sulfate. Magnesium sulfate was separated by filtration, and the filtrate was subjected to distillation under reduced pressure using a rotary evaporator to remove the solvent. The residue was purified by column chromatography to obtain a target product (yield 2.07 g (63%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. temperatureThis solution was cooled in an ice bath
  2. customSubsequently, a slurry solution obtained
  3. temperatureby heating
  4. temperatureto reflux for 5 days
  5. waitwas left
  6. temperatureto be naturally cooled
  7. customquenched with cold 1 N hydrochloric acid in an ice bath
  8. additionSubsequently, ether was added
  9. extractionto extract the soluble fraction
  10. washthis organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water and saturated brine
  11. dry with materialdried over magnesium sulfate
  12. customMagnesium sulfate was separated by filtration
  13. distillationthe filtrate was subjected to distillation under reduced pressure
  14. customa rotary evaporator
  15. customto remove the solvent
  16. customThe residue was purified by column chromatography
  17. customto obtain a target product (yield 2.07 g (63%))

Sources & evidence

ORD record
ord-d8d8ed566a1643e083adc6f5466bc997
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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