Citric Acid → N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-methyl-p-toluenesulfonamide

HRID 1648794Notes

Reaction equation

HRID 1648794 reaction equation
[CH3:1][NH:2][S:3]([C:6]1[CH:11]=[CH:10][C:9]([CH3:12])=[CH:8][CH:7]=1)(=[O:5])=[O:4].C([N:15]([CH2:18]C)CC)C.[S:20](Cl)Cl.CN[CH:25]=[N:26][C:27]1[CH:32]=[C:31]([Cl:33])[CH:30]=[CH:29][C:28]=1[CH3:34].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O.C(Cl)Cl>[Cl:33][C:31]1[CH:30]=[CH:29][C:28]([CH3:34])=[C:27]([N:26]=[CH:25][CH2:18][NH:15][S:20][N:2]([CH3:1])[S:3]([C:6]2[CH:11]=[CH:10][C:9]([CH3:12])=[CH:8][CH:7]=2)(=[O:4])=[O:5])[CH:32]=1

Participants

8

Reactant 5

HCID 311Citric AcidHCID 8471Triethylamine2×HCID 12543Benzenesulfonamide, N,4-dimethyl-HCID 25353Sulfur dichlorideHCID 178484923HCID 178484923, compound

Product 1

HCID 86739104N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-methyl-p-toluenesulfonamideYield 8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution cooled to -10° of 18.5 g. (0.1 mole) of N-methyl-p-toluenesulfonamide and 10.1 g. (0.1 mole) of triethylamine in 300 ml. of methylene chloride is added dropwise 10.3 g. (0.1 mole) sulfur dichloride. The reaction mixture is stirred at ambient temperature for 0.5 hour and cooled to 10°. A solution of 18.3 g (0.1 mole) of N-methyl-N'-(4-chloro-o-tolyl)formamidine and 10.1 g. (0.1 mole) triethylamine in 100 ml. of methylene chloride is added rapidly with stirring. The reaction mixture is stirred at ambient temperature for 0.5 hour and extracted successively with 300 ml. of water, 300 ml. aqueous citric acid solution containing 10.5 g. (0.05 mole) of citric acid, and 300 ml. of water. The organic layer is dried and the solvent removed under reduced pressure. The residue is chromatographed over 100 g. silica gel using Hexane:Et2O:Et3N (18:2:3 by volume) to obtain 3.2 g. (8% yield) of N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-methyl-p-toluenesulfonamide as a viscous oil.

Workup

  1. temperatureTo a stirred solution cooled to -10° of 18.5 g
  2. temperaturecooled to 10°
  3. stirringwith stirring
  4. stirringThe reaction mixture is stirred at ambient temperature for 0.5 hour
  5. extractionextracted successively with 300 ml
  6. additionaqueous citric acid solution containing 10.5 g
  7. customThe organic layer is dried
  8. customthe solvent removed under reduced pressure
  9. customThe residue is chromatographed over 100 g
  10. customto obtain 3.2 g

Sources & evidence

ORD record
ord-32b959f5850741daa9940681b2d38dea
Source dataset
uspto-grants-1983_11
Patent number
US04413013

Reaction notes

Loading…