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

HRID 1526487Notes

Reaction equation

HRID 1526487 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 placed a solution of cyclohex-2-en-1-one (15.00 g, 156.04 mmol, 1.00 equiv) in anhydrous THF (300 mL) was added 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) 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 purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:5) to give 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate (28.50 g, 71%) as yellow oil.

Workup

  1. customInto a 1 L round-bottom flask 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
  7. customThe residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:5)

Sources & evidence

ORD record
ord-465f489a6d3a49839bbbfb8a10e55180
Source dataset
uspto-grants-2015_07
Patent number
US09085586B2

Reaction notes

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