Ethyl Acetoacetate → HCID 68724534, compound

HRID 1471383Notes

Reaction equation

HRID 1471383 reaction equation
[C:1]1(=[CH:6][C:7](=[O:9])[CH3:8])[CH2:5][CH2:4][CH2:3][CH2:2]1.C1(CC(=O)C)CCCC=1.[C:19]([O:25][CH2:26][CH3:27])(=[O:24])[CH2:20][C:21]([CH3:23])=O>CCCCCCC.C1C=CC=CC=1.[Cl-].[Zn+2].[Cl-]>[CH3:23][C:21]1[CH:20]([C:19]([O:25][CH2:26][CH3:27])=[O:24])[C:1]2([CH2:6][C:7](=[O:9])[CH:8]=1)[CH2:5][CH2:4][CH2:3][CH2:2]2

Participants

6

Reactant 2

HCID 8868Ethyl AcetoacetateHCID 86647584HCID 86647584, compound

Product 1

HCID 68724534HCID 68724534, compoundYield 12.1%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolventHCID 8900HeptaneSolvent

Procedure

A mixture of 1-cyclopentylidenepropan-2-one/1-cyclopentenylpropan-2-one (25:75, 100 g, 0.805 mol), ethyl acetoacetate (105 g, 0.805 mol), and zinc chloride (16.5 g, 0.12 mol) in heptane (100 ml) and benzene (100 ml) was refluxed for 6 days using a Dean-Stark apparatus. The resulting mixture was cooled, washed with water (250 ml), with a 5% aqueous solution of NaHCO3 (250 ml), with water, dried (MgSO4) and concentrated. Vigreux-Distillation (0.1 mbar, bath temperature 150° C., head temp. 106-130° C.) of the crude product (174 g) followed by FC (SiO2, hexane/MTBE 10:1 to 5:1) gave ethyl 7-methyl-9-oxospiro[4.5]dec-7-ene-6-carboxylate (23 g, 12%).

Workup

  1. temperaturewas refluxed for 6 days
  2. temperatureThe resulting mixture was cooled
  3. washwashed with water (250 ml), with a 5% aqueous solution of NaHCO3 (250 ml), with water
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. distillationVigreux-Distillation (0.1 mbar, bath temperature 150° C., head temp. 106-130° C.) of the crude product (174 g)

Sources & evidence

ORD record
ord-9c3118d5fa3b42e1b11403339ead1ac7
Source dataset
uspto-grants-2015_04
Patent number
US09012391B2

Reaction notes

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