Dimethyl Sulfide → HCID 20242797, compound

HRID 483134Notes

Reaction equation

HRID 483134 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]([Mg]Br)([CH3:20])=[CH2:19]>C1COCC1>[C:1]([CH2:5][C:6]1([CH2:13][CH3:14])[CH2:7][CH2:8][CH:9]([C:18]([CH3:20])=[CH2:19])[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 178456138HCID 178456138, compound

Product 1

HCID 20242797HCID 20242797, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The enone, 6-carbomethoxymethyl-6-ethyl-2-cyclohexene-1-one, (X), prepared in Example 1, Step (c), (33.12 mmol, 6.50 g), CuBr.Me2S (3.312 mmol, 681 mg) and Me2S (6.63 ml) were stirred in 97.5 ml of dry THF at -40° C. under nitrogen and treated with 49.68 mmol (66.24 ml of 0.75M in THF, prepared from treating isopropenyl bromide with 1.1 equivalents of Mg) of isopropenylmagnesium bromide added dropwise. The reaction was quenched with 120 ml of 1M HCl (aq.) and extracted with 4×60 ml of petroleum ether. Drying (Na2SO4) and flash chromatography afforded 5.6 g (23.53 mmol, 71%) of colorless oil as a mixture of diastereomers. The diastereomers were separted by preparative HPLC on a Prep 500A using a brand of silica gel available from Waters Associaes, Milford, Ma., to provide a "less polar isomer" and a "more polar isomer."

Workup

  1. additionadded dropwise
  2. customThe reaction was quenched with 120 ml of 1M HCl (aq.)
  3. extractionextracted with 4×60 ml of petroleum ether
  4. dry with materialDrying (Na2SO4) and flash chromatography

Sources & evidence

ORD record
ord-a12f9ca245be486a904b2a2ddffd4626
Source dataset
uspto-grants-1986_03
Patent number
US04578398

Reaction notes

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