Hydrochloric Acid → 1-(6-Chloro-3-pyridylmethyl)-3-methyl2-nitroguanidine

HRID 1012227Notes

Reaction equation

HRID 1012227 reaction equation
[Cl-].[Na+].[CH3:3][NH:4][C:5](=[N:8][N+:9]([O-:11])=[O:10])OC.[OH-].[Na+].[Cl:14][C:15]1[CH:20]=[CH:19][C:18]([CH2:21][NH2:22])=[CH:17][N:16]=1.Cl>O>[Cl:14][C:15]1[CH:20]=[CH:19][C:18]([CH2:21][NH:22][C:5]([NH:4][CH3:3])=[N:8][N+:9]([O-:11])=[O:10])=[CH:17][N:16]=1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 5234Sodium Chloride2×HCID 14798Sodium HydroxideHCID 70209275-(Aminomethyl)-2-chloropyridineHCID 136414659(E)-N-methyl-N'-nitromethoxymethanimidamide

Product 1

HCID 1362181961-(6-Chloro-3-pyridylmethyl)-3-methyl2-nitroguanidineYield 88.9%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Procedure

1.3 g of sodium chloride and 4.65 g of water were mixed, and the resulting mixture was cooled to −10 degree centigrade. N,O-dimethyl-N′-nitroisourea (4.5 g, 0.03 mole) was introduced into the above solution, and 0.58 g (4.64 mmole) of 32% NaOH was further added to the suspension and stirred. Thereafter, [(2-chloro-5-pyridyl)methyl]amine (4.93 g, 0.03 mole) was introduced dropwise to the suspension. Sodium chloride was dissolved in water with 78% of the saturated solubility at a water temperature of −10 degree centigrade. The solution was stirred at −10 degree centigrade for 4 hours and then heated to 20 degree centigrade, and further stirred for 6 hours. Then, 35% hydrochloric acid (0.7 g, 6.71 mmole) was added to the suspension so that the pH became not more than 4. The resulting solution was extracted with ethyl acetate and concentrated under a reduced pressure, and then recrystallized. Thus, 6.5 g of a 1-[(2-chloro-5-pyridyl)methyl]-3-methyl-2-nitroguanidine was obtained. The isolated yield at this time was 81%.

Workup

  1. temperaturethe resulting mixture was cooled to −10 degree centigrade
  2. additionwas further added to the suspension
  3. stirringThe solution was stirred at −10 degree centigrade for 4 hours
  4. temperatureheated to 20 degree centigrade
  5. stirringfurther stirred for 6 hours
  6. extractionThe resulting solution was extracted with ethyl acetate
  7. concentrationconcentrated under a reduced pressure
  8. customrecrystallized

Sources & evidence

ORD record
ord-92a3d774019c4b4781bba48825b47577
Source dataset
uspto-grants-2011_07
Patent number
US07977496B2

Reaction notes

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