Hydrochloric Acid → (3-Tert-butyl-5-methy-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)diphenylmethane

HRID 2404926Notes

Reaction equation

HRID 2404926 reaction equation
[C:1]([C:5]1[CH:17]=[CH:16][C:15]2[C:14]3[C:9](=[CH:10][C:11]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:12][CH:13]=3)[CH2:8][C:7]=2[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].C([Li])CCC.[C:27]([C:31]1[CH:32]=[C:33]([CH3:49])[C:34](=[C:36]([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH:35]=1)([CH3:30])([CH3:29])[CH3:28].Cl>C(OCC)C.CCCCCC>[C:27]([C:31]1[CH:32]=[C:33]([CH3:49])[CH:34]([C:36]([C:10]2[C:9]3[CH2:8][C:7]4[C:15](=[CH:16][CH:17]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:6]=4)[C:14]=3[CH:13]=[CH:12][C:11]=2[C:18]([CH3:21])([CH3:20])[CH3:19])([C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C:43]2[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=2)[CH:35]=1)([CH3:28])([CH3:29])[CH3:30]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 40900822,7-Di-tert-butylfluoreneHCID 231070913-Tert-butyl-1-methyl-6,6-diphenylfulveneHCID 178418339Butyllithium

Product 1

HCID 131727280(3-Tert-butyl-5-methy-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)diphenylmethaneYield 31.3%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent3×HCID 8058HexaneSolvent

Procedure

A 200-ml three-necked flask equipped with a magnetic stirring bar and a three-way cock was sufficiently purged with nitrogen, and then 2.53 g (9.10 mmol) of 2,7-di-tert-butylfluorene was dissolved in 70 ml of dehydrated diethyl ether under a nitrogen atmosphere. To this solution was added 6.4 ml of a hexane solution of n-butyllithium (1.56 M: 9.98 mmol) gradually dropwise in an ice bath, and the resultant solution was stirred overnight at room temperature. To the reaction solution was added a solution prepared by dissolving 3.01 g (10.0 mmol) of 3-tert-butyl-1-methyl-6,6-diphenylfulvene in 40 ml of dehydrated diethyl ether, and the solution was stirred under reflux for 7 days. The reaction mixture was poured into 100 ml of hydrochloric acid (1 N), diethyl ether was added to separate an organic layer, and the organic layer was washed with saturated sodium hydrogen carbonate aqueous solution and saturated brine and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was distilled off from the filtrate under reduced pressure to obtain a reddish-brown liquid, which was purified with column chromatography using 180 g of silica gel (developing solvent: n-hexane). The developing solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol and dried under reduced pressure to yield 1.65 g (2.85 mmol) of the target compound as pale yellow solid (Yield: 31%).

Workup

  1. customA 200-ml three-necked flask equipped with a magnetic stirring bar
  2. customa three-way cock was sufficiently purged with nitrogen
  3. additionTo the reaction solution was added a solution
  4. customprepared
  5. temperatureunder reflux for 7 days
  6. additionwas added
  7. customto separate an organic layer
  8. washthe organic layer was washed with saturated sodium hydrogen carbonate aqueous solution and saturated brine
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationThe drying agent was filtered off
  11. distillationthe solvent was distilled off from the filtrate under reduced pressure
  12. customto obtain a reddish-brown liquid, which
  13. customwas purified with column chromatography
  14. distillationThe developing solvent was distilled off under reduced pressure
  15. customthe residue was recrystallized from methanol
  16. customdried under reduced pressure

Sources & evidence

ORD record
ord-4b6cbb4b1db140189efabba41c647472
Source dataset
uspto-grants-2014_08
Patent number
US08802779B2

Reaction notes

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