Hydrochloric Acid → 2-Chloro-4-nitrobenzene-1-thiol

HRID 1577952Notes

Reaction equation

HRID 1577952 reaction equation
O.[SH-:2].[Na+].[Cl:4][C:5]1[CH:6]=[C:7]([N+:12]([O-:14])=[O:13])[CH:8]=[CH:9][C:10]=1Cl.Cl>CO>[Cl:4][C:5]1[CH:6]=[C:7]([N+:12]([O-:14])=[O:13])[CH:8]=[CH:9][C:10]=1[SH:2]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 74431,2-Dichloro-4-nitrobenzeneHCID 16211346Sodium hydrosulfide hydrate

Product 1

HCID 3057302-Chloro-4-nitrobenzene-1-thiolYield 55%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

A solution of sodium hydrosulfide hydrate (60 g technical; ~0.75 mol) in methanol (200 ml) is added to a solution of 3,4-dichloronitrobenzene (100.0 g; 0.52 mol) in methanol (750 ml) with cooling and at a rate to maintain the temperature of the reaction mixture below 40° C. After the addition is completed, the reaction mixture is stirred an additional 16 hours, and then poured on a mixture of ice and hydrochloric acid. The mixture remains strongly acidic. The precipitated yellow solid is filtered, washed and dried. This solid is purified by dissolving same in 25% aqueous sodium hydroxide, extracting the resultant solution several times with methylene chloride until the methylene chloride solution remains colorless. Next, concentrated hydrochloric acid is added to the aqueous solution dropwise to precipitate a light yellow solid and adjust the pH to 1-2. The thus formed slurry is filtered, the isolated solid is washed with water and dried to afford 52.6 g (55%) of title compound. A sample is recrystallized from cyclohexane, m.p. 77°- 78° C. Lit. 73.5°-74° C. (ref. Nippon Kagaku Kaishi 1972, 756).

Workup

  1. temperaturewith cooling and at a rate
  2. temperatureto maintain the temperature of the reaction mixture below 40° C
  3. additionAfter the addition
  4. filtrationThe precipitated yellow solid is filtered
  5. washwashed
  6. customdried
  7. customThis solid is purified
  8. dissolutionby dissolving same in 25% aqueous sodium hydroxide
  9. extractionextracting the resultant solution several times with methylene chloride until the methylene chloride solution
  10. additionNext, concentrated hydrochloric acid is added to the aqueous solution dropwise
  11. customto precipitate a light yellow solid
  12. filtrationThe thus formed slurry is filtered
  13. washthe isolated solid is washed with water
  14. customdried

Sources & evidence

ORD record
ord-4b2d9138412c40b1b04776de7f749e45
Source dataset
uspto-grants-1981_09
Patent number
US04289903

Reaction notes

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