Dimethylformamide → 3-Chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylnitrobenzene

HRID 1638750Notes

Reaction equation

HRID 1638750 reaction equation
[Cl:1][C:2]1[C:3]([CH3:13])=[C:4]([N+:10]([O-:12])=[O:11])[CH:5]=[C:6]([CH3:9])[C:7]=1Cl.[Cl:14][C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[CH:17][C:16]=1[OH:22].C(=O)([O-])[O-].[K+].[K+].CN(C)C=O>C(OCC)(=O)C.CCCCCC>[Cl:1][C:2]1[C:3]([CH3:13])=[C:4]([N+:10]([O-:12])=[O:11])[CH:5]=[C:6]([CH3:9])[C:7]=1[O:22][C:16]1[CH:17]=[CH:18][C:19]([Cl:21])=[CH:20][C:15]=1[Cl:14]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 84492,4-DichlorophenolHCID 11430Potassium CarbonateHCID 137729272,3-Dichloro-1,4-dimethyl-5-nitrobenzene

Product 1

HCID 198414543-Chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylnitrobenzeneYield 45.6%

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

Into a 250 milliter three-necked round bottom reaction flask equipped with a magnetic stirrer and nitrogen inlet was charged 10.0 grams (45.44 mmol) of 3,4-dichloro-2,5-dimethylnitrobenzene, 7.95 grams (48.81 mmol) of 2,4-dichlorophenol, 9.41 grams (68.11 mmol) of potassium carbonate and 60 milliliters dimethylformamide. The reaction mixture was stirred and heated at a temperature of 100° C. for a period of 20 hours and then cooled to room temperature, filtered and concentrated under reduced pressure. The residue was diluted with methylene chloride and the organic layer was washed with 4% NaOH solution (2x) and brine, dried through Na2SO4 and concentrated under reduced pressure to afford the crude product as a dark brown, viscous liquid. The addition of hexane and ethyl acetate afforded a light brown solid which was subjected to Kugelrohr distillation (about 180° C. and about 0.1 mm mercury) to give pure 3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylnitrobenzene (7.17 grams, 20.7 mmol, 45%) as a yellow solid having a melting point of 118° C.-121° C. NMR spectroscopic analysis indicated the following: H'-NMR (CDCl3) 7.76 (br S, 1H), 7.53 (d, J=2 Hz, 1H), 7.12 (d,d; 2.9 Hz; 1H), 6.34 (d, J=9 Hz, 1H), 2.45 (S, 3H), 2.24 (S, 3H).

Workup

  1. customInto a 250 milliter three-necked round bottom reaction flask equipped with a magnetic stirrer and nitrogen inlet
  2. temperaturecooled to room temperature
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. additionThe residue was diluted with methylene chloride
  6. washthe organic layer was washed with 4% NaOH solution (2x) and brine
  7. dry with materialdried through Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customto afford the crude product as a dark brown, viscous liquid
  10. customafforded a light brown solid which
  11. distillationwas subjected to Kugelrohr distillation (about 180° C. and about 0.1 mm mercury)

Sources & evidence

ORD record
ord-a498489f423e489586cc4b43cec77527
Source dataset
uspto-grants-1989_11
Patent number
US04880838

Reaction notes

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