p-Toluenesulfonic acid monohydrate → HCID 10198961, compound

HRID 1250887Notes

Reaction equation

HRID 1250887 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:14])=[C:6](NCCCNC)[CH:7]=1.[C:15]([N:22]1[CH:26]=NC=N1)([N:17]1[CH:21]=NC=N1)=[S:16].O.[C:28]1(C)C=CC(S(O)(=O)=O)=C[CH:29]=1>O1CCOCC1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:14])=[C:4]([N:22]2[CH2:26][CH2:29][CH2:28][N:17]([CH3:21])[C:15]2=[S:16])[CH:3]=1

Participants

5

Reactant 3

HCID 521998p-Toluenesulfonic acid monohydrate3×HCID 11137714Bis(1H-1,2,4-triazol-1-yl)methanethioneHCID 18324841HCID 18324841, compound

Product 1

HCID 10198961HCID 10198961, compoundYield 63.9%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of the diamine of Step A (3.8 g) in dioxane (100 mL) under nitrogen was added 1,1′-thiocarbonyl-di-1,2,4-triazole (3.38 g). After 45 minutes additional thiocarbonyl reagent (0.5 g) was added, followed after 30 minutes by para-toluenesulfonic acid monohydrate (6.88 g). The reaction mixture was heated at reflux for 4 hours at which point additional para-toluenesulfonic acid monohydrate (2.0 g) was added. After refluxing for 18 hours, another portion of para-toluenesulfonic acid monohydrate (1.5 g) was added. The reaction mixture was refluxed for an additional 24 hours, cooled and concentrated in vacuo to give a brown oil which crystallized on standing. The crude material was dissolved in dichloromethane and absorbed onto a column of Merck-60 flash silica gel. Elution with 20% ethyl acetate in hexane provided a light pink solid which was triturated with diethyl ether to give the title compound (2.9 g, 63.9%) as a white solid, m.p. 143-145° C.

Workup

  1. additionAfter 45 minutes additional thiocarbonyl reagent (0.5 g) was added
  2. temperatureThe reaction mixture was heated
  3. additionwas added
  4. temperatureAfter refluxing for 18 hours
  5. temperatureThe reaction mixture was refluxed for an additional 24 hours
  6. temperaturecooled
  7. concentrationconcentrated in vacuo
  8. customto give a brown oil which
  9. customcrystallized
  10. dissolutionThe crude material was dissolved in dichloromethane
  11. customabsorbed onto a column of Merck-60 flash silica gel
  12. washElution with 20% ethyl acetate in hexane
  13. customprovided a light pink solid which
  14. customwas triturated with diethyl ether

Sources & evidence

ORD record
ord-5104511a583f4aac8980555e727293b0
Source dataset
uspto-grants-2002_01
Patent number
US06340687B1

Reaction notes

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