Hydrochloric Acid → 2-(5-Bromo-2-ethylphenyl)-4,4-dimethylcyclohexane-1,3-dione

HRID 400381Notes

Reaction equation

HRID 400381 reaction equation
[CH3:1][C:2]1([CH3:10])[CH2:7][CH2:6][C:5](=[O:8])[CH2:4][C:3]1=[O:9].C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.[Br:23][C:24]1[CH:25]=[CH:26][C:27]([CH2:31][CH3:32])=[C:28]([Pb+3])[CH:29]=1.CN(C1C=CC=CN=1)C.Cl>ClCCl.C1(C)C=CC=CC=1.C(Cl)(Cl)Cl>[Br:23][C:24]1[CH:29]=[CH:28][C:27]([CH2:31][CH3:32])=[C:26]([CH:4]2[C:3](=[O:9])[C:2]([CH3:10])([CH3:1])[CH2:7][CH2:6][C:5]2=[O:8])[CH:25]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 218852-DimethylaminopyridineHCID 1363601,3-Cyclohexanedione, 4,4-dimethyl-HCID 178476533HCID 178476533, compound

Product 1

HCID 668701212-(5-Bromo-2-ethylphenyl)-4,4-dimethylcyclohexane-1,3-dioneYield 46.6%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 4,4-dimethylcyclohexane-1,3-dione (6.28 g, 45 mmol), 5-bromo-2-ethylphenyl lead triacetate (28 g, 49 mmol) and dimethylaminopyridine (27.4 g, 0.22 mol) under nitrogen are added anhydrous chloroform (300 ml) and toluene (75 ml). The reaction mixture is heated at 80° C. for 2 hours and then allowed to cool to room temperature overnight. 2M Aqueous hydrochloric acid (750 ml) and dichloromethane (500 ml) are added and the mixture is filtered through diatomaceous earth, washing through with more dichloromethane (250 ml). The two layers are separated and the aqueous phase is extracted with dichloromethane (500 ml). The organic layers are combined and washed with 2M aqueous hydrochloric acid (1000 ml) and then brine (1000 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by preparative normal phase chromatography to give 2-(5-bromo-2-ethylphenyl)-4,4-dimethylcyclohexane-1,3-dione (6.78 g).

Workup

  1. temperatureto cool to room temperature overnight
  2. filtrationthe mixture is filtered through diatomaceous earth
  3. washwashing through with more dichloromethane (250 ml)
  4. customThe two layers are separated
  5. extractionthe aqueous phase is extracted with dichloromethane (500 ml)
  6. washwashed with 2M aqueous hydrochloric acid (1000 ml)
  7. dry with materialbrine (1000 ml), dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customthe filtrate is evaporated under reduced pressure
  10. customThe residue is purified by preparative normal phase chromatography

Sources & evidence

ORD record
ord-43049f206f8e42ef882b884ec5b8105d
Source dataset
uspto-grants-2014_06
Patent number
US08741806B2

Reaction notes

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