Hydrochloric Acid → 2-(2,4-Dichlorobenzoyl)cyclohexane-1,3-dione

HRID 620937Notes

Reaction equation

HRID 620937 reaction equation
[C:1]1(=[O:8])[CH2:6][CH2:5][CH2:4][C:3](=[O:7])[CH2:2]1.[Cl:9][C:10]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:11]=1[C:12](C#N)=[O:13].C(N(CC)CC)C.Cl>C(Cl)Cl.CCOCC.[Cl-].[Zn+2].[Cl-].C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[Cl:9][C:10]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:11]=1[C:12]([CH:2]1[C:3](=[O:7])[CH2:4][CH2:5][CH2:6][C:1]1=[O:8])=[O:13]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 104341,3-CyclohexanedioneHCID 98342322,4-Dichlorobenzoyl Cyanide

Product 1

HCID 143016212-(2,4-Dichlorobenzoyl)cyclohexane-1,3-dioneYield 77.7%

Reagents, catalysts & solvents 4

HCID 8895Cupric acetateCatalystHCID 3007855ZincchlorideCatalystHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na2CO3 four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was dissolved in ether and stirred with 250 ml of 5% copper (II) acetate. The resulting copper salt was filtered, washed with ether and stirred with 6N hydrochloric acid to destroy the salt. The extract was washed with ether to yield 22.15 grams of the desired product m.p. 138°-140° C. (77.7% yield). The structure was confirmed by instrumental analysis.

Workup

  1. temperaturewith cooling
  2. washthe organic phase was washed with 150 ml 5% Na2CO3 four times
  3. extractionextracted with methylene chloride
  4. customdried
  5. concentrationconcentrated
  6. customto yield 25.3 g of crude product
  7. filtrationThe resulting copper salt was filtered
  8. washwashed with ether
  9. stirringstirred with 6N hydrochloric acid
  10. customto destroy the salt
  11. washThe extract was washed with ether

Sources & evidence

ORD record
ord-8d14374b1bf841f4a373783e072158a9
Source dataset
uspto-grants-1989_04
Patent number
US04822906

Reaction notes

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