Methyl iodide → HCID 22031524, compound

HRID 1792468Notes

Reaction equation

HRID 1792468 reaction equation
[OH-].[K+].[Br:3][C:4]1[CH:5]=[CH:6][C:7]2[N:8]([C:10]([C:13]([NH:15][NH2:16])=O)=[CH:11][N:12]=2)[CH:9]=1.CI.O.C1(C)C=C[C:23]([S:26](O)(=O)=O)=CC=1.C(=O)(O)[O-].[Na+].[C:36](=S)=[S:37]>O.O1CCCC1.C(OCC)(=O)C.C1(C)C=CC=CC=1.CO>[Br:3][C:4]1[CH:5]=[CH:6][C:7]2[N:8]([C:10]([C:13]3[S:37][C:36]([S:26][CH3:23])=[N:16][N:15]=3)=[CH:11][N:12]=2)[CH:9]=1

Participants

12

Reactant 6

HCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 14797Potassium HydroxideHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 23537414HCID 23537414, compound

Product 1

HCID 22031524HCID 22031524, compoundYield 5.1%

Reagents, catalysts & solvents 5

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

66 mg potassium hydroxide (powder) was added to a mixture of 306 mg of 6-bromoimidazo[1,2-a]pyridine-3-carboxylic acid hydrazide (compound in Production Example 276), 195 mg carbon disulfide and 12 mL methanol under cooling with ice-water, and the mixture was stirred for 2.5 hours. Then, the reaction mixture was returned to room temperature, and 4 hours later, 75 μL methyl iodide was added thereto and stirred overnight. Ethyl acetate and water were added to the reaction solution, and the organic layer was separated, then washed with an aqueous saturated sodium bicarbonate solution and brine and dried over anhydrous sodium sulfate. The drying agent was filtered off, and the filtrate was evaporated. 243 mg crude product of methyl N′-(6-bromoimidazo[1,2-a]pyridine-3-carbonyl)hydrazine carbodithioate was obtained as pale yellow crystals. A mixture of this compound, 255 mg p-toluenesulfonic acid monohydrate and 15 mL toluene was heated for 1.5 hours under reflux. Ethyl acetate, tetrahydrofuran and water were added to the reaction solution which was then basified with sodium bicarbonate. The organic layer was separated, washed with brine and dried over anhydrous sodium sulfate. The drying agent was filtered off, and the filtrate was evaporated. The resulting residue was purified by NH silica gel column chromatography (ethyl acetate/hexane) to give 20 mg of the title compound as a white solid.

Workup

  1. customwas returned to room temperature
  2. stirringstirred overnight
  3. customthe organic layer was separated
  4. washwashed with an aqueous saturated sodium bicarbonate solution and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationThe drying agent was filtered off
  7. customthe filtrate was evaporated
  8. custom243 mg crude product of methyl N′-(6-bromoimidazo[1,2-a]pyridine-3-carbonyl)hydrazine carbodithioate was obtained as pale yellow crystals
  9. temperaturewas heated for 1.5 hours
  10. temperatureunder reflux
  11. customThe organic layer was separated
  12. washwashed with brine
  13. dry with materialdried over anhydrous sodium sulfate
  14. filtrationThe drying agent was filtered off
  15. customthe filtrate was evaporated
  16. customThe resulting residue was purified by NH silica gel column chromatography (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-116314e1f49e4302b21416115f54041d
Source dataset
uspto-grants-2006_07
Patent number
US07074801B1

Reaction notes

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