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

HRID 1194634Notes

Reaction equation

HRID 1194634 reaction equation
[CH3:1][C:2]1([CH3:10])[CH2:7][CH2:6][C:5](=[O:8])[CH2:4][C:3]1=[O:9].[Cl:11][C:12]1[CH:21]=[C:20]([Cl:22])[CH:19]=[CH:18][C:13]=1[C:14](C#N)=[O:15].C(N(CC)CC)C.Cl>C(Cl)Cl.[Cl-].[Zn+2].[Cl-]>[CH3:1][C:2]1([CH3:10])[CH2:7][CH2:6][C:5](=[O:8])[CH:4]([C:14](=[O:15])[C:13]2[CH:18]=[CH:19][C:20]([Cl:22])=[CH:21][C:12]=2[Cl:11])[C:3]1=[O:9]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 1363601,3-Cyclohexanedione, 4,4-dimethyl-HCID 98342322,4-Dichlorobenzoyl Cyanide

Product 1

HCID 147495752-(2,4-Dichlorobenzoyl)-4,4-dimethylcyclohexane-1,3-dioneYield 40%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

4,4-Dimethyl-1,3-cyclohexanedione (14.0 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 chromatographed (2% AcOH/CH2Cl2) in 5 g aliquots then reduced on rotavap under reduced pressure at 50° C. for 30 minutes to remove AcOH. This yielded an oil (40% 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. customThe crude product was chromatographed (2% AcOH/CH2Cl2) in 5 g aliquots
  8. waitthen reduced on rotavap under reduced pressure at 50° C. for 30 minutes
  9. customto remove AcOH

Sources & evidence

ORD record
ord-b60a3c3d4f624d95ada527035cf5f2ea
Source dataset
uspto-grants-1989_03
Patent number
US04816066

Reaction notes

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