Hydrochloric Acid → 3-tert-Butyl-1-ethylcyclopenta-1,3-diene

HRID 1361560Notes

Reaction equation

HRID 1361560 reaction equation
[CH2:1](OCC)[CH3:2].C([Mg]Br)C.[C:10]([C:14]1[CH2:18][CH2:17][C:16](=O)[CH:15]=1)([CH3:13])([CH3:12])[CH3:11].Cl>O>[CH2:1]([C:17]1[CH2:16][CH:15]=[C:14]([C:10]([CH3:13])([CH3:12])[CH3:11])[CH:18]=1)[CH3:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 3283Diethyl Ether2×HCID 119769972-Cyclopenten-1-one, 3-(1,1-dimethylethyl)-HCID 178418443HCID 178418443, compound

Product 1

HCID 206271323-tert-Butyl-1-ethylcyclopenta-1,3-dieneYield 78%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a 300 ml three-neck flask equipped with a magnetic stirrer chip and a three-way cock, 200 ml of dehydrated diethyl ether and 52 ml (154 mmol) of diethyl ether solution of 3.0 M ethyl magnesium bromide were charged under a nitrogen atmosphere. In the ice and water bath, 17.8 g (129 mmol) of 3-tert-butylcyclopentenone was added dropwise over 1 hour. The resultant solution was stirred at room temperature for 20 hours, and then 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 ether. The obtained organic layers were combined, washed twice with a saturated aqueous solution of sodium hydrogencarbonate, twice with water, and twice with saturated brine, and dried over magnesium sulfate and distilled off the solvent under reduced pressure. Thereafter, the resulting product was purified by column chromatography to obtain 20.2 g (GC purity 75%) of a pale yellowy transparent solution. The yield was 78%. 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. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted twice with 50 ml of ether
  4. washwashed twice with a saturated aqueous solution of sodium hydrogencarbonate, twice with water
  5. dry with materialtwice with saturated brine, and dried over magnesium sulfate
  6. distillationdistilled off the solvent under reduced pressure
  7. customThereafter, the resulting product was purified by column chromatography
  8. customto obtain 20.2 g (GC purity 75%) of a pale yellowy transparent solution
  9. customThe measurement results

Sources & evidence

ORD record
ord-780aeca7bee84e53b012e769f5976d64
Source dataset
uspto-grants-2011_02
Patent number
US07879960B2

Reaction notes

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