Hydrogen Peroxide → 1,3-Dichloro-2-nitrobenzene

HRID 1470693Notes

Reaction equation

HRID 1470693 reaction equation
S(=O)(=O)(O)[OH:2].[Cl:6][C:7]1[CH:13]=[CH:12][CH:11]=[C:10]([Cl:14])[C:8]=1[NH2:9].OO.[OH-:17].[K+]>CO.O.O.[O-][W]([O-])(=O)=O.[Na+].[Na+].O.C1(C)C=CC=CC=1>[Cl:6][C:7]1[CH:13]=[CH:12][CH:11]=[C:10]([Cl:14])[C:8]=1[N+:9]([O-:2])=[O:17]

Participants

9

Reactant 4

HCID 784Hydrogen PeroxideHCID 1118Sulfuric AcidHCID 118462,6-Dichloroaniline2×HCID 14797Potassium Hydroxide

Product 1

HCID 117591,3-Dichloro-2-nitrobenzeneYield 92%

Reagents, catalysts & solvents 4

HCID 150191Sodium Tungstate DihydrateCatalystHCID 887MethanolSolvent2×HCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
40 °C

Procedure

1.32 g (4.0 mmol) of sodium tungstate dihydrate and 4.0 g (40 mmol) of concentrated sulfuric acid were added to a solution of 16.2 g (100 mmol) of 2,6-dichloroaniline in 120 ml of methanol, and the mixture was heated to 40° C. 30 ml (291 mmol) of a 30% hydrogen peroxide solution was added dropwise over 10 hours. The pH value at this time was 0.5. After the completion of the dropwise addition, the mixture was stirred at 40° C. for 9 hours. After the disappearance of the 2,6-dichloroaniline was confirmed by gas chromatography (area percentage method), a solution of 9.8 g (150 mmol) of 86% potassium hydroxide in 24.3 ml of methanol was added dropwise while the temperature of the reaction liquid was adjusted to 40° C. or less. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the reaction was completed. After the completion of the reaction, 95 ml of toluene and 32 ml of water were added, and the mixture was stirred for a while, and filtered. The filtrate was separated. The obtained organic phase was washed with 8 ml of water, and then heated to reflux, and dehydrated. Thus, 2,6-dichloronitrobenzene was obtained as a toluene solution. This solution was analyzed by gas chromatography by the absolute calibration method, and as a result, the yield was 92%. The amount of the potassium hydroxide added is sufficient to make the pH condition alkaline.

Workup

  1. additionAfter the completion of the dropwise addition
  2. customwas adjusted to 40° C. or less
  3. additionAfter the completion of the dropwise addition
  4. stirringthe mixture was stirred at room temperature for 2 hours
  5. additionwere added
  6. stirringthe mixture was stirred for a while
  7. filtrationfiltered
  8. customThe filtrate was separated
  9. washThe obtained organic phase was washed with 8 ml of water
  10. temperatureheated
  11. temperatureto reflux

Sources & evidence

ORD record
ord-1ed4e7f0fbc442b2a3f0751ba80a4eb2
Source dataset
uspto-grants-2015_04
Patent number
US09006477B2

Reaction notes

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