Hydrochloric Acid → HCID 54285910, compound

HRID 1660137Notes

Reaction equation

HRID 1660137 reaction equation
Cl[CH2:2][CH2:3][N:4]1[C:21](=[O:22])[N:7]2[C@H:8]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:9]=[CH:10][C@H:11]([C:12]([OH:14])=[O:13])[N:6]2[C:5]1=[O:23].[OH-].[K+].[C:26]([O-:29])(=[S:28])[CH3:27].[K+].Cl.[N+](=[CH2:34])=[N-]>CO.O>[C:26]([S:28][CH2:2][CH2:3][N:4]1[C:21](=[O:22])[N:7]2[C@@H:8]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:9]=[CH:10][C@H:11]([C:12]([O:14][CH3:34])=[O:13])[N:6]2[C:5]1=[O:23])(=[O:29])[CH3:27].[C:26]([S:28][CH2:2][CH2:3][N:4]1[C:21](=[O:22])[N:7]2[C@H:8]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:9]=[CH:10][C@H:11]([C:12]([O:14][CH3:34])=[O:13])[N:6]2[C:5]1=[O:23])(=[O:29])[CH3:27]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 9550DiazomethaneHCID 14797Potassium HydroxideHCID 23670855Potassium ethanethioateHCID 70060754HCID 70060754, compound

Product 2

HCID 54285910HCID 54285910, compoundYield 27%HCID 86738167HCID 86738167, compoundYield 1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

A cooled solution of 12.08 g (0.036 mol) of cis-2-(2-chloroethyl)-2,3,5,8-tetrahydro-1,3-dioxo-8-phenyl-1H-1,2,4-triazolo[1,2-a]pyridazine-5-carboxylic acid in 180 ml of methanol was treated with a solution of 2.37 g (0.036 ml) of potassium hydroxide in 15 ml of methanol. The methanol was removed by evaporation and the residue was dissolved in 150 ml of dimethyl sulphoxide. The solution was treated with 4.90 g (0.043 mol) of potassium thioacetate and the mixture was stirred at 80° C. for 20 hours. The cooled mixture was diluted with 150 ml of water, acidified with 2-M hydrochloric acid and extracted with ether. The combined extracts were dried over magnesium sulphate and evaporated to give a yellow oil which was treated with diazomethane in the usual manner. The resulting yellow oil was chromatographed on silica gel using chloroform/ethyl acetate (4:1) for the elution to give 3.8 g (27%) of methyl trans-2-(2-acetylthioethyl)-2,3,5,8-tetrahydro-1,3-dioxo-8-phenyl-1H-1,2,4-triazolo[1,2-a]pyridazine-5-carboxylate of melting point 101°-102° C. (from ethyl acetate) and 0.1 g (1%) of methyl cis-2-(2-acetylthioethyl)-2,3,5,8-tetrahydro-1,3-dioxo-8-phenyl-1H-1,2,4-triazolo[1,2-a]pridazine-5-carboxylate in the form of a colourless oil.

Workup

  1. customThe methanol was removed by evaporation
  2. dissolutionthe residue was dissolved in 150 ml of dimethyl sulphoxide
  3. extractionextracted with ether
  4. dry with materialThe combined extracts were dried over magnesium sulphate
  5. customevaporated
  6. customto give a yellow oil which
  7. customThe resulting yellow oil was chromatographed on silica gel
  8. washfor the elution

Sources & evidence

ORD record
ord-4225ac06d0004a8d83d28a1d8e1c61f1
Source dataset
uspto-grants-1981_12
Patent number
US04307094

Reaction notes

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