p-Toluenesulfonic acid monohydrate → HCID 9903890, compound

HRID 1250882Notes

Reaction equation

HRID 1250882 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][CH2:9][CH2:10][CH2:11][NH:12][CH:13]([CH3:15])[CH3:14])=[C:4]([CH3:16])[CH:3]=1.O.C1(C)C=C[C:21]([S:24](O)(=O)=O)=CC=1>O1CCOCC1.C(OCC)(=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:9][CH2:10][CH2:11][N:12]([CH:13]([CH3:14])[CH3:15])[C:21]2=[S:24])=[C:4]([CH3:16])[CH:3]=1

Participants

5

Reactant 2

HCID 521998p-Toluenesulfonic acid monohydrate2×HCID 18324826HCID 18324826, compound

Product 1

HCID 9903890HCID 9903890, compoundYield 74.6%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of the diamine of Step A (6 g) in dioxane (100 mL) under nitrogen was added N,N′-thiocarbonyl-di-1,2,4-triazole (4.5 g). After stirring at room temperature for 3 hours, para-toluene sulfonic acid monohydrate was added in one portion (9.5 g) and the mixture was heated at reflux for 8 hours. Additional para-toluene sulfonic acid monohydrate was added (1 g) and reflux was resumed for another 2 hours. The mixture was cooled and diluted with ethyl acetate. The precipitate was collected and washed with ethyl acetate. The combined filtrates were washed with brine, dried over magnesium sulfate, and evaporated to dryness. The residue was dissolved in dichloromethane and absorbed onto a column of Merck-60 flash silica gel. Elution with 20% ethyl acetate in hexane provided the title compound as a white crystalline solid (5.26 g, 74.6%). The material was slurried in hexane-ether, sonicated and collected to provide 4.91 g of pure product, m.p. 147-149° C.

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 8 hours
  3. temperaturereflux
  4. waitwas resumed for another 2 hours
  5. temperatureThe mixture was cooled
  6. customThe precipitate was collected
  7. washwashed with ethyl acetate
  8. washThe combined filtrates were washed with brine
  9. dry with materialdried over magnesium sulfate
  10. customevaporated to dryness
  11. dissolutionThe residue was dissolved in dichloromethane
  12. customabsorbed onto a column of Merck-60 flash silica gel
  13. washElution with 20% ethyl acetate in hexane

Sources & evidence

ORD record
ord-20aa43894fb6424084860b21961b4c5a
Source dataset
uspto-grants-2002_01
Patent number
US06340687B1

Reaction notes

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