Acetone Cyanohydrin → 2-(2-Chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione

HRID 1368810Notes

Reaction equation

HRID 1368810 reaction equation
[CH3:1][C:2]1([CH3:10])[CH2:9][C:7](=[O:8])[CH2:6][C:4](=[O:5])[CH2:3]1.C1(N=C=NC2CCCCC2)CCCCC1.[Cl:26][C:27]1[C:35]([CH:36]=[N:37][O:38][CH2:39][CH3:40])=[C:34]([S:41]([CH3:44])(=[O:43])=[O:42])[CH:33]=[CH:32][C:28]=1[C:29](O)=[O:30].CC(C)(O)C#N.C(N(CC)CC)C>C(#N)C.O>[Cl:26][C:27]1[C:35]([CH:36]=[N:37][O:38][CH2:39][CH3:40])=[C:34]([S:41]([CH3:44])(=[O:43])=[O:42])[CH:33]=[CH:32][C:28]=1[C:29]([CH:6]1[C:4](=[O:5])[CH2:3][C:2]([CH3:10])([CH3:1])[CH2:9][C:7]1=[O:8])=[O:30]

Participants

8

Reactant 5

HCID 6406Acetone CyanohydrinHCID 8471TriethylamineHCID 10868DicyclohexylcarbodiimideHCID 31358DimedoneHCID 541651472-Chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoic acid

Product 1

HCID 731946162-(2-Chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent2×

Procedure

1.26 g (0.009 mol) of dimedone and 1.90 g (0.009 mol) of dicyclohexylcarbodiimide were added to a solution of 2.95 g (0.009 mol) of 2-chloro-3-ethoxyiminomethyl-4-methylsulfonyl-benzoic acid in 130 ml of anhydrous acetonitrile. After stirring for 12 hours at room temperature, 0.42 g (0.005 mol) of acetone cyanohydrin and 3.27 g (0.032 mol) of triethylamine in 10 ml of absolute acetonitrile were added dropwise. The reaction mixture was then stirred for a further 2 hours at room temperature. With stirring, the reaction mixture was poured into 200 ml of water, the precipitate was filtered off with suction and the filtrate was added to 100 ml of 5% strength potassium carbonate solution. The aqueous phase was washed with ethyl acetate, the pH was adjusted to 2 using 10% strength hydrochloric acid and the mixture was extracted with ethyl acetate. The combined organic phases were washed with water until neutral, dried and concentrated under reduced pressure. This gave 2.52 g of crude product which was recrystallized from toluene. (mp.: 156-157° C.)

Workup

  1. stirringThe reaction mixture was then stirred for a further 2 hours at room temperature
  2. stirringWith stirring
  3. filtrationthe precipitate was filtered off with suction
  4. additionthe filtrate was added to 100 ml of 5% strength potassium carbonate solution
  5. washThe aqueous phase was washed with ethyl acetate
  6. extractionthe mixture was extracted with ethyl acetate
  7. washThe combined organic phases were washed with water until neutral,
  8. customdried
  9. concentrationconcentrated under reduced pressure
  10. customThis gave 2.52 g of crude product which was recrystallized from toluene

Sources & evidence

ORD record
ord-2a5408bdf53646b7b5387b6cf1f52d05
Source dataset
uspto-grants-2003_06
Patent number
US06576596B1

Reaction notes

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