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

HRID 2379852Notes

Reaction equation

HRID 2379852 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-d2cbd063d703429883ae9bae8a89211a
Source dataset
uspto-grants-1994_11
Patent number
US05364871

Reaction notes

Loading…