Hydrochloric Acid → 3-Tert-butyl-1-methyl-6,6-di(p-tolyl)fulvene

HRID 1361565

Reaction equation

HRID 1361565 reaction equation
[CH3:1][C:2]1[CH2:6][CH:5]=[C:4]([C:7]([CH3:10])([CH3:9])[CH3:8])[CH:3]=1.C(=O)=O.CO.CCCCCC.C([Li])CCC.CN1CCN(C)C1=O.[CH3:35][C:36]1[CH:50]=[CH:49][C:39]([C:40]([C:42]2[CH:47]=[CH:46][C:45]([CH3:48])=[CH:44][CH:43]=2)=O)=[CH:38][CH:37]=1.Cl>C1COCC1>[C:7]([C:4]1[CH:3]=[C:2]([CH3:1])[C:6](=[C:40]([C:42]2[CH:47]=[CH:46][C:45]([CH3:48])=[CH:44][CH:43]=2)[C:39]2[CH:49]=[CH:50][C:36]([CH3:35])=[CH:37][CH:38]=2)[CH:5]=1)([CH3:10])([CH3:9])[CH3:8]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 66611,3-Dimethyl-2-imidazolidinoneHCID 691484,4'-DimethylbenzophenoneHCID 153463033-tert-Butyl-1-methylcyclopenta-1,3-dieneHCID 21973728Carbon dioxide methanolHCID 178418244HCID 178418244, compound

Product 1

HCID 866095443-Tert-butyl-1-methyl-6,6-di(p-tolyl)fulveneYield 57.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a 300 ml three-neck flask equipped with a magnetic stirrer chip and a three-way cock, 4.5 g (33.0 mmol) of 1-methyl-3-tert-butyl-cyclopentadiene and 150 ml of THF were charged under a nitrogen atmosphere. In the dry ice/methanol bath, 22.5 ml (34.7 mmol) of 1.54M n-butyllithium hexane solution was gradually added dropwise and then stirred at room temperature for 20 hours. To the obtained reaction solution, 4.3 ml (39.6 mmol) of 1,3-di-methyl-2-imidazolidinone was added, subsequently 8.3 g (39.6 mmol) of 4,4′-di-methylbenzophenone were changed, and the resultant solution was stirred for 120 hours under reflux. The reaction solution was poured into 100 ml of 2N hydrochloric acid. The organic layer was separated, and the aqueous layer was extracted twice with 50 ml of hexane. The separated organic layers were combined, washed with a saturated aqueous solution of sodium hydrogencarbonate, water and saturated aqueous solution of sodium chloride, and dried over magnesium sulfate and the solvent was distilled off. Thereafter, the resulting product was purified by column chromatography to obtain 6.2 g of an orange solid. The yield was 56%. Identification was done by 1H-NMR spectrum. The measurement results are shown as follows.

Workup

  1. customTo a 300 ml three-neck flask equipped with a magnetic stirrer chip
  2. additionwas added
  3. temperatureunder reflux
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted twice with 50 ml of hexane
  6. washwashed with a saturated aqueous solution of sodium hydrogencarbonate, water and saturated aqueous solution of sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. distillationthe solvent was distilled off
  9. customThereafter, the resulting product was purified by column chromatography

Sources & evidence

ORD record
ord-9fb5dd643b5140d894a0c091923dc49c
Source dataset
uspto-grants-2011_02
Patent number
US07879960B2

Linked notes

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