Methyl acetoacetate → Methyl 2-acetyl-3-phenylbut-3-enoate

HRID 45229Notes

Reaction equation

HRID 45229 reaction equation
[O:1]=[C:2]([CH3:8])[CH2:3][C:4]([O:6][CH3:7])=[O:5].[C:9]1([C:15]#[CH:16])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>C1(C)C=CC=CC=1.C(Cl)Cl>[C:2]([CH:3]([C:15]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[CH2:16])[C:4]([O:6][CH3:7])=[O:5])(=[O:1])[CH3:8]

Participants

5

Reactant 2

HCID 7757Methyl acetoacetateHCID 10821Phenylacetylene

Product 1

HCID 86659738Methyl 2-acetyl-3-phenylbut-3-enoateYield 84%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
50 °C

Procedure

A suspension of 3.2 g (27.5 mmol) of methyl 3-oxobutanoate, 5.6 g (55.0 mmol) of phenylacetylene and 700 mg (0.8 mmol) of *[ReBr(CO)3(THF)]2 in 55 mL of anhydrous toluene is stirred for 18 hours at 50° C. After cooling to room temperature, the medium is concentrated under reduced pressure. The residue obtained is taken up in 100 mL of DCM, washed successively with water (100 mL) and brine (100 mL), dried over Na2SO4 and then concentrated under reduced pressure and purified by chromatography on a column of silica gel, eluting with a 99/1 DCM/MeOH mixture. 5 g of methyl 2-acetyl-3-phenylbut-3-enoate are obtained in the form of a yellow oil.

Workup

  1. temperatureAfter cooling to room temperature
  2. concentrationthe medium is concentrated under reduced pressure
  3. customThe residue obtained
  4. washwashed successively with water (100 mL) and brine (100 mL)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. custompurified by chromatography on a column of silica gel
  8. washeluting with a 99/1 DCM/MeOH mixture

Sources & evidence

ORD record
ord-89fce57a9a55414fadfb10a92675a2b7
Source dataset
uspto-grants-2013_09
Patent number
US08541455B2

Reaction notes

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