Methanol → 1-N-methyl-4-nitrobenzene-1,2-diamine

HRID 1390361Notes

Reaction equation

HRID 1390361 reaction equation
[N+:1]([C:4]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:5]=1[NH:6][CH3:7])([O-])=O.C(=O)([O-])O.[Na+].CO.[S-2].[Na+].[Na+]>O.[OH-].[Na+]>[NH2:1][C:4]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:5]=1[NH:6][CH3:7]

Participants

7

Reactant 4

HCID 887MethanolHCID 14804Sodium SulfideHCID 74891N-methyl-2,4-dinitroanilineHCID 516892Sodium Bicarbonate

Product 1

HCID 34200251-N-methyl-4-nitrobenzene-1,2-diamineYield 94.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
25 °C

Procedure

71 Parts of 2,4-dinitro-N-methylaniline and 53 parts of sodium hydrogen carbonate are stirred in 144 parts of methanol. The yellow suspension is heated in the course of 20 minutes to 40° C. Simultaneously, 81.9 parts of 60% sodium sulphide are dissolved in 144 parts of water of approx. 40° C and 1.2 parts of 30% sodium hydroxide solution are added to the resultant solution. The turbid yellow solution is filtered. The clear yellow filtrate is added dropwise in the course of 2 hours to the suspension of 2,4-dinitro-N-methylaniline. An exothermic reaction occurs during the dropwise addition. The contents of the flask turn dark in colour. The new suspension is heated in the course of 1 hour to 70° C and stirred for 15 minutes at this temperature (reflux). Then 144 parts of methanol are distilled off. The residue is cooled to 25° C and 50 parts of ice are added. After suction filtration at 8° C, the filter cake is washed three times with 160 parts of water and dried in vacuo at 60° C, affording 56.8 parts of 2-amino-4-nitro-N-methylaniline (94.4% of theory). The melting point of the product is 177°-178° C.

Workup

  1. temperatureThe yellow suspension is heated in the course of 20 minutes to 40° C
  2. filtrationThe turbid yellow solution is filtered
  3. additionThe clear yellow filtrate is added dropwise in the course of 2 hours to the suspension of 2,4-dinitro-N-methylaniline
  4. customAn exothermic reaction
  5. additionoccurs during the dropwise addition
  6. temperatureThe new suspension is heated in the course of 1 hour to 70° C
  7. distillationThen 144 parts of methanol are distilled off
  8. addition50 parts of ice are added
  9. filtrationAfter suction filtration at 8° C
  10. washthe filter cake is washed three times with 160 parts of water
  11. customdried in vacuo at 60° C

Sources & evidence

ORD record
ord-d7f27637653a41e0a1945b969a420bb7
Source dataset
uspto-grants-1979_02
Patent number
US04138568

Reaction notes

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