Hydrochloric Acid → 1-Methyl-4-(6-nitropyridin-3-yl)piperazine

HRID 1916054Notes

Reaction equation

HRID 1916054 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([N+:8]([O-:10])=[O:9])=[N:6][CH:7]=1.C(=O)([O-])[O-].[K+].[K+].[CH3:17][N:18]1[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]1.Cl>CS(C)=O.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH3:17][N:18]1[CH2:23][CH2:22][N:21]([C:2]2[CH:7]=[N:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=2)[CH2:20][CH2:19]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 531671-MethylpiperazineHCID 8176205-Bromo-2-nitropyridine

Product 1

HCID 517114841-Methyl-4-(6-nitropyridin-3-yl)piperazineYield 83.1%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
120 °C

Procedure

To 5-Bromo-2-nitro-pyridine (2.00 g, 9.85 mmol) in 10 mL dimethylsulfoxide was added potassium carbonate (2.72 g, 19.7 mmol), 1-methylpiperazine (1.64 mL, 14.8 mmol), and tetrabutylammonium iodide (36 mg, 0.097 mmol) and was heated at 120° C. for 18 hours. The mixture was made acidic with 1M aq. HCl and was partitioned between dichloromethane and water. The aqueous layer was made basic with 2M aq. sodium carbonate and was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated in vacuo, and was triturated with water to yield 1-Methyl-4-(6-nitro-pyridin-3-yl)-piperazine (1.82 g, 8.19 mmol). MS (ESI) 223.1 (M+H)+.

Workup

  1. customwas partitioned between dichloromethane and water
  2. extractionwas extracted with dichloromethane
  3. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customwas triturated with water

Sources & evidence

ORD record
ord-1d5890c33b0d4321886c7aaf846a08ab
Source dataset
uspto-grants-2013_12
Patent number
US08618098B2

Reaction notes

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