Methyl acetoacetate → Methyl 2-(4-methylthiophenacyl)acetoacetate

HRID 1415760Notes

Reaction equation

HRID 1415760 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].CC(C)([O-])C.[K+].[CH3:15][C:16]1[CH:25]=[CH:24][C:19]([C:20](=[S:23])[CH2:21]Br)=[CH:18][CH:17]=1>CC(O)(C)C.C1C=CC=CC=1>[CH3:15][C:16]1[CH:25]=[CH:24][C:19]([C:20](=[S:23])[CH2:21][CH:2]([C:3]([CH3:5])=[O:4])[C:1]([O:7][CH3:8])=[O:6])=[CH:18][CH:17]=1

Participants

6

Reactant 3

HCID 7757Methyl acetoacetateHCID 183681522-Bromo-4'-methylthioacetophenoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 54143420Methyl 2-(4-methylthiophenacyl)acetoacetateYield 84.9%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6386tert-ButanolSolvent

Procedure

2.28 g (19.7 mmol) of methyl acetoacetate were dissolved in 40 ml of 2-methyl-2-propanol, and 2.21 g (19.7 mmol) of potassium t-butoxide were added to the resulting solution under a nitrogen atmosphere. The mixture was then stirred at room temperature for 1 hour, after which a solution of 4.82 g (19.7 mmol) of 4-methylthiophenacyl bromide in 30 ml of benzene was added dropwise to the resulting mixture. The mixture was then stirred at 60° C. for 3 hours, after which it was cooled. It was then poured into ice-water and extracted with ethyl acetate. The organic extract was washed with a saturated aqueous solution of sodium chloride, and then dried over anhydrous magnesium sulfate. The solvent was then removed by distillation under reduced pressure. The resulting residue was applied to a silica gel chromatography column and eluted with a 1:4 by volume mixture of ethyl acetate and hexane, to give 4.42 g (yield 80%) of the title compound as a slightly yellow powder.

Workup

  1. stirringThe mixture was then stirred at 60° C. for 3 hours
  2. temperatureafter which it was cooled
  3. extractionextracted with ethyl acetate
  4. extractionThe organic extract
  5. washwas washed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe solvent was then removed by distillation under reduced pressure
  8. washeluted with a 1:4 by volume mixture of ethyl acetate and hexane

Sources & evidence

ORD record
ord-8c6e5bc3c8044c15a75ac970763baaf7
Source dataset
uspto-grants-1999_06
Patent number
US05908858

Reaction notes

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