Hydrochloric Acid → 2,7-Dimethyl-3,6-ditert-butyl-fluorene

HRID 1050652Notes

Reaction equation

HRID 1050652 reaction equation
[CH3:1]OC(C)(C)C.BrC1[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.C[Mg]Br.Cl.C(O[CH2:37][CH3:38])C>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].C(Cl)Cl>[CH3:1][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:37]([CH3:38])=[C:20]([C:21]([CH3:22])([CH3:24])[CH3:23])[CH:19]=3)[CH2:11][C:12]=2[CH:13]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 3283Diethyl Ether2×HCID 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-fluoreneYield 63%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6344DichloromethaneSolvent

Procedure

Under a nitrogen atmosphere, 100 mL of dehydrated tertbutyl methyl ether was added to 5.03 g (11.5 mmol) of 2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis Example 1-1 (i) and 0.196 g (0.24 mmol) of PdCl2(dppf).CH2Cl2, and the mixture was stirred. This solution was cooled in an ice bath, and 19.2 mL (57.6 mmol) of a 3 mol/L diethyl ether solution of methyl magnesium bromide was added dropwise over 15 minutes. The mixture was heated to reflux for 5 days. The mixture was left to be naturally cooled, and 1 N hydrochloric acid was then added dropwise in an ice bath to terminate the reaction. Diethyl ether was added to perform liquid-liquid phase separation, and the 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 dried over magnesium sulfate. The solvent was distilled off, and the residue was subjected to separation by silica gel chromatography to obtain a target product as a white powder (yield 2.07 g (63%)). The target product was identified by 1H-NMR.

Workup

  1. temperatureThis solution was cooled in an ice bath
  2. temperatureThe mixture was heated
  3. temperatureto reflux for 5 days
  4. waitThe mixture was left
  5. temperatureto be naturally cooled
  6. customto terminate
  7. customthe reaction
  8. customliquid-liquid phase separation
  9. washthe organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  10. dry with materialonce with saturated brine, and dried over magnesium sulfate
  11. distillationThe solvent was distilled off
  12. customthe residue was subjected to separation by silica gel chromatography

Sources & evidence

ORD record
ord-93acf26f32b54cf4b0a1716136658707
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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