Chlorotrimethylsilane → 1,3-Diethyl 2-(3-oxocyclohexyl)propanedioate

HRID 1504008Notes

Reaction equation

HRID 1504008 reaction equation
[C:1]1(=[O:7])[CH2:6][CH2:5][CH2:4][CH:3]=[CH:2]1.Br[CH:9]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:10]([O:12][CH2:13][CH3:14])=[O:11].C[Si](Cl)(C)C>C1COCC1>[O:7]=[C:1]1[CH2:6][CH2:5][CH2:4][CH:3]([CH:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:2]1

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 135942-Cyclohexen-1-oneHCID 69637Diethyl bromomalonate

Product 1

HCID 3170491,3-Diethyl 2-(3-oxocyclohexyl)propanedioateYield 71.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Into a 1 L round-bottom flask was placed a solution of cyclohex-2-en-1-one (15.00 g, 156.04 mmol, 1.00 equiv) in anhydrous THF (300 mL). 1,3-diethyl 2-bromopropanedioate (56.00 g, 234.25 mmol, 1.50 equiv), In powder (18.00 g, 1.00 equiv) and TMSCl (87.00 g, 800.81 mmol, 5.00 equiv) were added under nitrogen. The resulting solution was stirred for 30 min at room temperature and quenched by the addition of 200 mL of saturated aqueous sodium carbonate, extracted with 3×300 mL of ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (1:5) to give 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate (28.50 g, 71%) as a yellow oil.

Workup

  1. customInto a 1 L round-bottom flask was placed
  2. customquenched by the addition of 200 mL of saturated aqueous sodium carbonate
  3. extractionextracted with 3×300 mL of ethyl acetate
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-38de6a07b78640c8b5275369539c8688
Source dataset
uspto-grants-2015_12
Patent number
US09212190B2

Reaction notes

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