Hydrochloric Acid → 2,4-Difluoro-3-methyl-5-nitrobenzenamine

HRID 330073Notes

Reaction equation

HRID 330073 reaction equation
Cl.C(O)C.[F:5][C:6]1[C:11]([N+:12]([O-])=O)=[CH:10][C:9]([N+:15]([O-:17])=[O:16])=[C:8]([F:18])[C:7]=1[CH3:19].S([O-])(O)(=O)=O.[Na+]>O.[Fe].C1C=CC=CC=1>[F:5][C:6]1[C:7]([CH3:19])=[C:8]([F:18])[C:9]([N+:15]([O-:17])=[O:16])=[CH:10][C:11]=1[NH2:12]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 702EthanolHCID 516919Sodium BisulfateHCID 14052561HCID 14052561, compound

Product 1

HCID 140525622,4-Difluoro-3-methyl-5-nitrobenzenamineYield 62.9%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 241BenzeneSolventHCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

To a suspension of iron powder (16.8 g, 100 mesh) in water (140 ml), with vigorous stirring at 50° C., was slowly added concentrated hydrochloric acid (3 ml). After hot ethanol (90 ml) was mixed, 2,6-difluoro-3,5-dinitrotoluene (21.8 g) was added portionwise to the suspension at 55° to 56° C. during 5 minutes. After stirring for 1.5 hours at 55° to 60° C., to the reacting mixture was added sodium hydrogensulfate (3.48 g) and stirred for further 30 minutes at the same temperature. To the reacting mixture was added benzene (100 ml), stirred for 10 minutes and insoluble materials were filtered off, and then the materials were washed with benzene. To the filtrate and washings were added water and active carbon, stirred sufficiently and filtered off. The organic layer was separated and the water layer was further extracted with benzene. The organic layer was combined, washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the title compound (11.82 g) as pale brown crystals.

Workup

  1. stirringAfter stirring for 1.5 hours at 55° to 60° C., to the reacting mixture
  2. stirringstirred for further 30 minutes at the same temperature
  3. stirringstirred for 10 minutes
  4. filtrationinsoluble materials were filtered off
  5. washthe materials were washed with benzene
  6. additionTo the filtrate and washings were added water and active carbon
  7. stirringstirred sufficiently
  8. filtrationfiltered off
  9. customThe organic layer was separated
  10. extractionthe water layer was further extracted with benzene
  11. washwashed with water
  12. dry with materialdried over anhydrous sodium sulfate
  13. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-4c9dd2aac3d041a2ae95c9fad7d2ea9d
Source dataset
uspto-grants-1990_01
Patent number
US04894458

Reaction notes

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