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

HRID 1918971Notes

Reaction equation

HRID 1918971 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 99%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

According to US 2009/0318448, into a solution of 5-bromo-2-nitropyridine (2.0 g, 9.85 mmol) in DMSO (10 mL) was added K2CO3 (2.72 g, 19.7 mmol) and 1-methylpiperazine (1.64 mL, 14.8 mmol), and tetrabutylammonium iodide (36 mg). The mixture was stirred at 120 degree C. for overnight. It was allowed to cool down and acidified with 1N HCl. The mixture was extracted with DCM. The aqueous layer was basified with saturated Na2CO3, and further extracted with DCM. The combined organic layers were dried over Na2SO4 and concentrated to give a brown solid, which was washed with small amount of water. The solid was dried under vacuum to give 2.16 g of 1-methyl-4-(6-nitropyridin-3-yl)piperazine (99% yield) as a yellow powder. LCMS: (M+H)+ 223

Workup

  1. temperatureto cool down
  2. extractionThe mixture was extracted with DCM
  3. extractionfurther extracted with DCM
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. concentrationconcentrated
  6. customto give a brown solid, which
  7. washwas washed with small amount of water
  8. customThe solid was dried under vacuum

Sources & evidence

ORD record
ord-7f5858db848749d0bdf537723b085cac
Source dataset
uspto-grants-2013_12
Patent number
US08618107B2

Reaction notes

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