Triethylamine → 4,4,5-Trimethyl-2-(2-nitro-4-methylsulfonylbenzoyl)cyclohexane-1,3-dione

HRID 2108243Notes

Reaction equation

HRID 2108243 reaction equation
[CH3:1][C:2]1([CH3:11])[CH:7]([CH3:8])[CH2:6][C:5](=[O:9])[CH2:4][C:3]1=[O:10].C(N(CC)CC)C.[N+:19]([C:22]1[CH:30]=[C:29]([S:31]([CH3:34])(=[O:33])=[O:32])[CH:28]=[CH:27][C:23]=1[C:24](Cl)=[O:25])([O-:21])=[O:20].[C-]#N.[K+]>C(Cl)Cl.C(#N)C>[CH3:11][C:2]1([CH3:1])[CH:7]([CH3:8])[CH2:6][C:5](=[O:9])[CH:4]([C:24](=[O:25])[C:23]2[CH:27]=[CH:28][C:29]([S:31]([CH3:34])(=[O:33])=[O:32])=[CH:30][C:22]=2[N+:19]([O-:21])=[O:20])[C:3]1=[O:10]

Participants

7

Reactant 4

HCID 8471Triethylamine2×HCID 9032Potassium CyanideHCID 148001864-(Methanesulfonyl)-2-nitrobenzoyl chlorideHCID 148237354,4,5-Trimethyl-cyclohexane-1,3-dione

Product 1

HCID 148237364,4,5-Trimethyl-2-(2-nitro-4-methylsulfonylbenzoyl)cyclohexane-1,3-dioneYield 23.5%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent2×

Procedure

4,4,5-trimethyl-cyclohexane-1,3-dione (0.98 g, 6.36 mmole) and triethylamine (0.77 g, 7.26 mmole) were dissolved in methylene chloride (30 ml). Into the resulting solution cooled with ice, a methylene chloride solution (5 ml) of 2-nitro-4-methylsulfonylbenzoyl chloride (1.68 g, 6.38 mmole) was dropped, and then this solution was stirred at room temperature for an hour. The resulting solution was washed with water, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was dissolved in acetonitrile (40 ml), into which triethylamine (0.77 g, 7.62 mmole) and potassium cyanide (0.1 g, 1.54 mmole) were added to stir at room temperature for 16 hours. The reaction solution was concentrated under reduced pressure. The residue was dissolved by adding ethyl acetate and water. To the resulting solution, diluted hydrochloric acid was added until the aqueous layer became acidic (pH 2 or below). The organic layer was washed with water, dried with anhydrous magnesium sulfate and concentrated under reduced pressure. Methanol was added to the residue to crystallize to give crystal (0.57 g, mp: 166°-7° C.).

Workup

  1. temperatureInto the resulting solution cooled with ice
  2. washThe resulting solution was washed with water
  3. dry with materialdried with anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. additionwere added
  6. stirringto stir at room temperature for 16 hours
  7. concentrationThe reaction solution was concentrated under reduced pressure
  8. dissolutionThe residue was dissolved
  9. additionby adding ethyl acetate and water
  10. additionTo the resulting solution, diluted hydrochloric acid was added until the aqueous layer
  11. washThe organic layer was washed with water
  12. dry with materialdried with anhydrous magnesium sulfate
  13. concentrationconcentrated under reduced pressure
  14. additionMethanol was added to the residue
  15. customto crystallize

Sources & evidence

ORD record
ord-8d7e25df7f72472fb41efbf28afd6f54
Source dataset
uspto-grants-1990_06
Patent number
US04937386

Reaction notes

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