1,2-Dichloro-4-nitrobenzene → 2-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexandione

HRID 542675Notes

Reaction equation

HRID 542675 reaction equation
[CH3:1][C:2]1([CH3:10])[CH2:7][C:6](=[O:8])[CH2:5][C:4](=[O:9])[CH2:3]1.C(=O)([O-])[O-].[K+].[K+].[Cl:17][C:18]1[CH:19]=[C:20]([N+:25]([O-:27])=[O:26])[CH:21]=[CH:22][C:23]=1Cl>CN(C)C=O>[Cl:17][C:18]1[CH:19]=[C:20]([N+:25]([O-:27])=[O:26])[CH:21]=[CH:22][C:23]=1[CH:5]1[C:6](=[O:8])[CH2:7][C:2]([CH3:10])([CH3:1])[CH2:3][C:4]1=[O:9]

Participants

5

Reactant 3

HCID 74431,2-Dichloro-4-nitrobenzeneHCID 11430Potassium CarbonateHCID 31358Dimedone

Product 1

HCID 128766182-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexandioneYield 36%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
75 °C

Procedure

A solution containing 42.05 g (0.300 mol) of 5,5-dimethyl-1,3-cyclohexanedione and 100 g (0.718 g-atom) of anhydrous potassium carbonate in 300 ml of dry dimethylformamide was heated to 75° C. under nitrogen and stirred for one hour. The 3,4-dichloronitrobenzene, 57.60 g (0.300 mol) was dissolved in 100 ml of dimethylformamide and added dropwise to the reaction mixture while stirring and maintaining the temperature of the reaction mixture at 75° C. A deep red-colored solution formed, and when the addition was complete the reaction temperature was raised to 100° C. and held at this temperature for 3 hours. Most of the dimethylformamide was removed by vacuum distillation. The residue was poured into 2 L of ice water and extracted three times with 500 ml of benzene. Nitrogen was then passed through the aqueous solution while warming to remove dissolved benzene. The aqueous solution was cooled in an ice bath and acidified to give a tacky precipitate, which, upon warming solidified and was collected by suction filtration. The reaction product was recrystallized from acetone to give 31.7 g (36%) of 2-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione as a white power, m.p. 250°-253° C.

Workup

  1. additionadded dropwise to the reaction mixture
  2. stirringwhile stirring
  3. temperaturemaintaining the temperature of the reaction mixture at 75° C
  4. customA deep red-colored solution formed
  5. additionwhen the addition
  6. temperaturewas raised to 100° C.
  7. waitheld at this temperature for 3 hours
  8. customMost of the dimethylformamide was removed by vacuum distillation
  9. additionThe residue was poured into 2 L of ice water
  10. extractionextracted three times with 500 ml of benzene
  11. temperaturewhile warming
  12. customto remove
  13. dissolutiondissolved benzene
  14. temperatureThe aqueous solution was cooled in an ice bath
  15. customto give a tacky precipitate, which
  16. temperatureupon warming solidified
  17. filtrationwas collected by suction filtration
  18. customThe reaction product was recrystallized from acetone

Sources & evidence

ORD record
ord-f737fe831acd4d78b6e6c471efe862a7
Source dataset
uspto-grants-1987_04
Patent number
US04659372

Reaction notes

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