Methanol → 2-Methyl-3-sulfanyl-1,2-dihydro-1,2,4-triazine-5,6-dione

HRID 1600110Notes

Reaction equation

HRID 1600110 reaction equation
C([O:3][C:4](=O)[C:5]([O:7]CC)=O)C.[CH3:11][N:12]([C:14]([NH2:16])=[S:15])[NH2:13].C[O-].[Na+].CO>C(Cl)Cl>[CH3:11][N:12]1[C:14](=[S:15])[NH:16][C:4](=[O:3])[C:5](=[O:7])[NH:13]1

Participants

6

Reactant 4

HCID 887MethanolHCID 7268Diethyl OxalateHCID 30341902-Methyl-3-thiosemicarbazideHCID 10942334Sodium Methoxide

Product 1

HCID 30346402-Methyl-3-sulfanyl-1,2-dihydro-1,2,4-triazine-5,6-dioneYield 12.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
60 °C

Procedure

Under anhydrous condition, 35 g of diethyloxalate is added, dropwise, to a vigorously stirred solution of 21 g of 2-methyl-3-thiosemicarbazide, 32.4 g of fresh sodium methoxide, and 750 ml of methyl alcohol. The resulting suspension is heated at 60° C. for 4 hours, stirred overnight at room teperature, and heated at 70° C. for 15 hours. The white suspension is cooled to room temperature, 200 ml of ice water is added andthe reaction concentrated in vacuo. The residue is cooled to 0° C. and made acidic with 2N hydrochloric acid. The reaction mixture is concentrated, ethyl alcohol is added and the suspension is heated to boiling. The white precipitate is collected, washed with hexane and dried to give 11 g of the crude product. Eight grams of the crude product is heated in methylene chloride and filtered while hot. The collected solid is resuspended in methyl alcohol and a solution of 4N potassium-2-ethyl hexanoate is added. The mixture is cooled to 0° C. and the precipitate collected. The solid is dissolvd in water, filtered, and 2N hydrochloric acid is added to the clear 0° C. solution. The resulting precipitate is collected and dried to give 4.1 g of the pure product. 13C NMR(CDCl3):δ 44,145, 150.115, 152.559, 169.786.

Workup

  1. temperatureheated at 70° C. for 15 hours
  2. temperatureThe white suspension is cooled to room temperature
  3. concentrationconcentrated in vacuo
  4. temperatureThe residue is cooled to 0° C.
  5. concentrationThe reaction mixture is concentrated
  6. additionethyl alcohol is added
  7. temperaturethe suspension is heated to boiling
  8. customThe white precipitate is collected
  9. washwashed with hexane
  10. customdried
  11. customto give 11 g of the crude product
  12. filtrationfiltered while hot
  13. additiona solution of 4N potassium-2-ethyl hexanoate is added
  14. temperatureThe mixture is cooled to 0° C.
  15. customthe precipitate collected
  16. dissolutionThe solid is dissolvd in water
  17. filtrationfiltered
  18. addition2N hydrochloric acid is added to the clear 0° C. solution
  19. customThe resulting precipitate is collected
  20. customdried

Sources & evidence

ORD record
ord-ca5dffb2137e455098a5afa9b616485a
Source dataset
uspto-grants-1998_04
Patent number
US05744465

Reaction notes

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