Acetone Cyanohydrin → 2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione

HRID 868470

Reaction equation

HRID 868470 reaction equation
[N+:1]([C:4]1[CH:12]=[C:11]([Cl:13])[CH:10]=[CH:9][C:5]=1[C:6](Cl)=[O:7])([O-:3])=[O:2].[CH3:14][C:15]1([CH3:26])[C:20](=[O:21])[C:19]([CH3:23])([CH3:22])[C:18](=[O:24])[CH2:17][C:16]1=[O:25].C(N(CC)CC)C.CC(C)(O)C#N>C(Cl)Cl>[N+:1]([C:4]1[CH:12]=[C:11]([Cl:13])[CH:10]=[CH:9][C:5]=1[C:6]([CH:17]1[C:16](=[O:25])[C:15]([CH3:26])([CH3:14])[C:20](=[O:21])[C:19]([CH3:23])([CH3:22])[C:18]1=[O:24])=[O:7])([O-:3])=[O:2]

Participants

6

Reactant 4

HCID 6406Acetone CyanohydrinHCID 8471Triethylamine2×HCID 108677844-Chloro-2-nitrobenzoyl chlorideHCID 117691662,2,4,4-Tetramethylcyclohexane-1,3,5-trione

Product 1

HCID 143017242-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrioneYield 46.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and 4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were dissolved in methylene chloride. Triethylamine was added and the resulting solution stirred at room temperature for 30 minutes. The solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine), dried over anhydrous magnesium sulfate (MgSO4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K2CO3. The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO4 and concentrated under vacuum, yielding 2.2 g of crude product. This was recrystallized from benzene to remove syncarpic acid still present. Concentration of the mother liquor under vacuum gave 1.7 g of the desired product as an oil, which solidified on standing (m.p. 76°-82° C.). It was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.

Workup

  1. washThe solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine)
  2. dry with materialdried over anhydrous magnesium sulfate (MgSO4)
  3. concentrationconcentrated under vacuum
  4. dissolutionThe residue was dissolved in 20 ml acetonitrile
  5. stirringthe mixture stirred at room temperature for 4 hours
  6. washAfter dilution with ether, the solution was washed with 1N HCl
  7. extractionextracted with 5% K2CO3
  8. extractionThe basic extract
  9. extractionextracted with ether
  10. extractionThe ether extract
  11. washwas washed with brine
  12. dry with materialdried over MgSO4
  13. concentrationconcentrated under vacuum
  14. customyielding 2.2 g of crude product
  15. customThis was recrystallized from benzene
  16. customto remove syncarpic acid still present

Sources & evidence

ORD record
ord-b3ef2eb1f7df4e2dadb911d6a9dceea6
Source dataset
uspto-grants-1988_10
Patent number
US04780127

Linked notes

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