Methylamine → 2-(diaminomethyleneamino)-4-[6-[N-(1-methylamino-2-nitrovinyl)aminomethyl]pyridin-2-yl]thiazole

HRID 1491859Notes

Reaction equation

HRID 1491859 reaction equation
Cl.Cl.Cl.[NH2:4][CH2:5][C:6]1[N:11]=[C:10]([C:12]2[N:13]=[C:14]([N:17]=[C:18]([NH2:20])[NH2:19])[S:15][CH:16]=2)[CH:9]=[CH:8][CH:7]=1.[CH2:21]([N:23]([CH2:26]C)CC)[CH3:22].CSC(SC)=C[N+:32]([O-:34])=[O:33].CN>O>[NH2:19][C:18](=[N:17][C:14]1[S:15][CH:16]=[C:12]([C:10]2[CH:9]=[CH:8][CH:7]=[C:6]([CH2:5][NH:4][C:21]([NH:23][CH3:26])=[CH:22][N+:32]([O-:34])=[O:33])[N:11]=2)[N:13]=1)[NH2:20]

Participants

6

Reactant 4

HCID 6329MethylamineHCID 8471TriethylamineHCID 836231,1-Bis(methylthio)-2-nitroethyleneHCID 189538374-(6-Aminomethylpyridin-2-yl)-2-(diaminomethyleneamino)thiazole trihydrochloride

Product 1

HCID 678210802-(diaminomethyleneamino)-4-[6-[N-(1-methylamino-2-nitrovinyl)aminomethyl]pyridin-2-yl]thiazole

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 4-(6-aminomethylpyridin-2-yl)-2-(diaminomethyleneamino)thiazole trihydrochloride (1.7 g), triethylamine (2.0 ml) and 1,1-bis(methylthio)-2-nitroethylene (0.9 g) was stirred at 70° C. for 7 hours. After cooling to ambient temperature, to the mixture was added a 40% aqueous methylamine (2.5 ml) and the mixture was stirred at ambient temperature for 15 hours. The reaction mixture was added to water, and the isolated precipitate was collected by filtration and dried. 4N-Dioxanoic hydrogen chloride (2.2 ml) was added to a mixture of above resulting precipitate in methanol (9.0 ml) and the mixture was stirred at ambient temperature for 1 hour. To the mixture was added a diisopropyl ether (9.0 ml) and the isolated precipitate was collected by filtration. The precipitate was recrystallized from an aqueous ethanol to give 2-(diaminomethyleneamino)-4-[6-[N-(1-methylamino-2-nitrovinyl)aminomethyl]pyridin-2-yl]thiazole (0.47 g).

Workup

  1. temperatureAfter cooling to ambient temperature, to the mixture
  2. stirringthe mixture was stirred at ambient temperature for 15 hours
  3. filtrationthe isolated precipitate was collected by filtration
  4. customdried
  5. addition4N-Dioxanoic hydrogen chloride (2.2 ml) was added to a mixture of above resulting precipitate in methanol (9.0 ml)
  6. stirringthe mixture was stirred at ambient temperature for 1 hour
  7. additionTo the mixture was added a diisopropyl ether (9.0 ml)
  8. filtrationthe isolated precipitate was collected by filtration
  9. customThe precipitate was recrystallized from an aqueous ethanol

Sources & evidence

ORD record
ord-98b000c9aa8a4c3791c676dd82e1985f
Source dataset
uspto-grants-1994_12
Patent number
US05371097

Reaction notes

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