Dimethyl Sulfide → 2-Carbomethoxymethyl-2-ethyl-5-phenylcyclohexanone

HRID 483133Notes

Reaction equation

HRID 483133 reaction equation
[C:1]([CH2:5][C:6]1([CH2:13][CH3:14])[C:11](=[O:12])[CH:10]=[CH:9][CH2:8][CH2:7]1)([O:3][CH3:4])=[O:2].S(C)C.[C:18]1([Mg]Br)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C1COCC1>[C:1]([CH2:5][C:6]1([CH2:13][CH3:14])[CH2:7][CH2:8][CH:9]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH2:10][C:11]1=[O:12])([O:3][CH3:4])=[O:2]

Participants

5

Reactant 3

HCID 1068Dimethyl Sulfide2×HCID 136492416-Carbomethoxymethyl-6-ethyl-2-cyclohexen-1-oneHCID 178418255HCID 178418255, compound

Product 1

HCID 142014352-Carbomethoxymethyl-2-ethyl-5-phenylcyclohexanoneYield 71%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

The enone, 6-carbomethoxymethyl-6-ethyl-2-cyclohexen-1-one (X) prepared by the process of Example 1, Step (c) (61.1 mmol, 12.0 g), CuBr.Me2S (6.11 mmol, 1.256 g) and Me2S (12.3 ml) were stirred in 85 ml of dry THF at -40° C. under nitrogen and treated with 61.1 mmol (20.4 ml of 3M in THF), of PhMgBr added dropwise over 30 minutes. The reaction was then quenched with 250 ml of 1M HCl (aq.) and extracted with 4×100 ml of petroleum ether. Drying (Na2SO4) and flash chromatography afforded 11.87 g (43.3 mmol, 71%) of product. The two diastereomers were separated by preparative HPLC on a Prep 500A using a brand of silica gel available from Waters Associates, Milford, Ma., affording 4.8 g of each isomer, designated "less polar isomer" and "more polar isomer."

Workup

  1. additionadded dropwise over 30 minutes
  2. customThe reaction was then quenched with 250 ml of 1M HCl (aq.)
  3. extractionextracted with 4×100 ml of petroleum ether
  4. dry with materialDrying (Na2SO4) and flash chromatography

Sources & evidence

ORD record
ord-666cf08ad51c4b83b31cd58ea97b9b92
Source dataset
uspto-grants-1986_03
Patent number
US04578398

Reaction notes

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