Acetylacetone → HCID 68723788, compound

HRID 1471403Notes

Reaction equation

HRID 1471403 reaction equation
[C:1]1(=[CH:6][C:7](=[O:9])[CH3:8])[CH2:5][CH2:4][CH2:3][CH2:2]1.[C:10]1([CH2:15][C:16](=[O:18])[CH3:17])CCC[CH:11]=1.C(CC(=O)C)(=O)C>C1C=CC=CC=1.CCCCCCC.[Cl-].[Zn+2].[Cl-]>[C:7]([CH:6]1[C:1]2([CH2:5][CH2:4][CH2:3][CH2:2]2)[CH2:17][C:16](=[O:18])[CH:15]=[C:10]1[CH3:11])(=[O:9])[CH3:8]

Participants

6

Reactant 2

HCID 31261AcetylacetoneHCID 86647584HCID 86647584, compound

Product 1

HCID 68723788HCID 68723788, compoundYield 2.1%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolventHCID 8900HeptaneSolvent

Procedure

In a Dean-Stark apparatus, a mixture of 1-cyclopentylidenepropan-2-one/1-cyclopentenylpropan-2-one (25:75, 600 g, 4.83 mol), acetylacetone (493 g, 4.83 mol), and zinc chloride (164.6 g, 1.21 mol) in benzene (500 ml) and heptane (500 ml) was heated at reflux for 2.5 d (44 ml water collected). The reaction mixture was poured into ice/water (1.5 l) and extracted with cyclohexane (0.6 l). The organic phase was washed with water (1 l), with a saturated aqueous solution of NaHCO3 (0.5 l), twice with a saturated aqueous solution of NaCl (1 l and 0.5 l), dried (100 g MgSO4), and concentrated (till 60° C./30 mbar). Vigreux-Distillation (0.08 mbar, bath temperature 180° C., head temp. 120-130° C.) of the crude product (615 g) followed by FC (2 kg SiO2, hexane/MTBE 2:1) gave 10-acetyl-9-methylspiro[4.5]dec-8-en-7-one (20.7 g, 2.1%). Boiling point: 150° C. (0.09 mbar).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 2.5 d
  3. custom(44 ml water collected)
  4. additionThe reaction mixture was poured into ice/water (1.5 l)
  5. extractionextracted with cyclohexane (0.6 l)
  6. washThe organic phase was washed with water (1 l), with a saturated aqueous solution of NaHCO3 (0.5 l), twice with a saturated aqueous solution of NaCl (1 l and 0.5 l)
  7. dry with materialdried (100 g MgSO4)
  8. concentrationconcentrated (till 60° C./30 mbar)
  9. distillationVigreux-Distillation (0.08 mbar, bath temperature 180° C., head temp. 120-130° C.) of the crude product (615 g)

Sources & evidence

ORD record
ord-3cb6834f597340c7bbba6af9b5902cd1
Source dataset
uspto-grants-2015_04
Patent number
US09012391B2

Reaction notes

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