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

HRID 1450305Notes

Reaction equation

HRID 1450305 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 temperature, and heated at 70° C. for 15 hours. The white suspension is cooled to room temperature, 200 ml of ice water is added and the 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 dissolved 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.

Workup

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

Sources & evidence

ORD record
ord-f140f8bf505e48b88ccc5d8e0ffceec5
Source dataset
uspto-grants-1997_02
Patent number
US05602118

Reaction notes

Loading…