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

HRID 620940

반응식

HRID 620940 반응식
[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]

참가 물질

6

반응물 4

HCID 6406Acetone CyanohydrinHCID 8471Triethylamine2회HCID 108677844-Chloro-2-nitrobenzoyl chlorideHCID 117691662,2,4,4-Tetramethylcyclohexane-1,3,5-trione

생성물 1

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

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-60577742eaec48bd87a5fc0ee1048761
출처 데이터셋
uspto-grants-1989_04
특허 번호
US04822906

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