4-Aminothiophenol → 4-{[(3,6-Dichloropyridin-2-yl)methyl]sulfanyl}aniline

HRID 1730017Notes

Reaction equation

HRID 1730017 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([SH:8])=[CH:4][CH:3]=1.[OH-].[Na+].[Cl:11][C:12]1[C:13]([CH2:19]Cl)=[N:14][C:15]([Cl:18])=[CH:16][CH:17]=1>CS(C)=O>[Cl:11][C:12]1[C:13]([CH2:19][S:8][C:5]2[CH:6]=[CH:7][C:2]([NH2:1])=[CH:3][CH:4]=2)=[N:14][C:15]([Cl:18])=[CH:16][CH:17]=1

Participants

5

Reactant 3

HCID 145104-AminothiophenolHCID 14798Sodium HydroxideHCID 203661743,6-Dichloro-2-(chloromethyl)pyridine

Product 1

HCID 203661654-{[(3,6-Dichloropyridin-2-yl)methyl]sulfanyl}aniline

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent3×

Procedure

p-Aminothiophenol (6.25 grams; 0.05 mole) was dissolved in 40 ml. of dimethylsulfoxide and powdered dry sodium hydroxide (2.0 grams; 0.05 mole) added thereto. The resulting mixture was warmed slightly, stirred and an additional 20 ml. of dimethylsulfoxide added thereto to clear the solution. A solution of 3,6-dichloro-2-chloromethylpyridine (8.6 grams; 0.05 mole) in 20 ml. of dimethylsulfoxide was added thereto slowly, with stirring, over a period of about one hour. The temperature of the reaction mixture increased to about 30°-45° C. during the addition. Following the completion of the addition, the reaction mixture was cooled and poured over ice and allowed to stand for about 15 hours. The aqueous layer was then decanted and the residue extracted with 5-500 ml. portions of hexane and the product precipitate recovered therefrom. Recrystallization of the precipitate from benzene gave the desired N-(4-((3,6-dichloro-2-pyridinyl)methylio)benzenamine compound as a crystalline solid having a melting point of 110°-111° C.

Workup

  1. additionadded
  2. temperatureThe resulting mixture was warmed slightly
  3. stirringslowly, with stirring, over a period of about one hour
  4. temperatureThe temperature of the reaction mixture increased to about 30°-45° C. during the addition
  5. additionthe completion of the addition
  6. temperaturethe reaction mixture was cooled
  7. additionpoured over ice
  8. customThe aqueous layer was then decanted
  9. extractionthe residue extracted with 5-500 ml
  10. customportions of hexane and the product precipitate recovered
  11. customRecrystallization of the precipitate from benzene
  12. customgave the

Sources & evidence

ORD record
ord-ebd2889e31f8497ca7db2b1c6ba399ec
Source dataset
uspto-grants-1976_11
Patent number
US03991068

Reaction notes

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