Hydrochloric Acid → HCID 86654675, compound

HRID 880475Notes

Reaction equation

HRID 880475 reaction equation
[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[N:5]=[C:4]([N:9]2[CH2:14][CH2:13][N:12]([C:15]3[CH:16]=[CH:17][C:18]([N+:22]([O-:24])=[O:23])=[C:19]([CH:21]=3)N)[CH2:11][CH2:10]2)[CH:3]=1.N([O-])=O.[Na+].C(=O)([O-])[O-].[Na+].[Na+].[ClH:35]>O.[Cu]Cl>[Cl:35][C:19]1[CH:21]=[C:15]([N:12]2[CH2:13][CH2:14][N:9]([C:4]3[CH:3]=[C:2]([CH3:1])[CH:7]=[C:6]([CH3:8])[N:5]=3)[CH2:10][CH2:11]2)[CH:16]=[CH:17][C:18]=1[N+:22]([O-:24])=[O:23].[Cl:35][C:19]1[CH:21]=[C:15]([N:12]2[CH2:13][CH2:14][N:9]([C:4]3[CH:3]=[C:2]([CH3:1])[CH:7]=[C:6]([CH3:8])[N:5]=3)[CH2:10][CH2:11]2)[CH:16]=[CH:17][C:18]=1[N+:22]([O-:24])=[O:23]

Participants

7

Reactant 4

HCID 313Hydrochloric Acid2×HCID 10340Sodium CarbonateHCID 23668193Sodium NitriteHCID 66851029HCID 66851029, compound

Product 1

HCID 86654675HCID 86654675, compoundYield 54%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent

Procedure

50% Aqueous hydrochloric acid (30 mL) was cooled to −20° C., 5-[4-(4,6-dimethyl-2-pyridyl)piperazin-1-yl]-2-nitro-aniline (1.4 g, 4.28 mmol) was added and the reaction mixture stirred for 15 min. A solution of sodium nitrite (350 mg, 5.14 mmol) in water (8 mL) was added and the reaction mixture stirred for 15 min. This solution was added dropwise to a cooled solution of copper (I) chloride (635 mg, 6.42 mmol) in 50% hydrochloric acid (20 mL) over a period of 20 min and stirred for a further 10 min before basifying with saturated sodium carbonate solution. The mixture was extracted with ethyl acetate and the organic phase was washed with water, brine, dried over anhydrous sodium sulfate and concentrated under vacuum to give a crude residue. Purification by column chromatography over silica gel (100-200 mesh) using 8% ethyl acetate in petroleum ether as eluent afforded 1-(3-chloro-4-nitro-phenyl)-4-(4,6-dimethyl-pyridin-2-yl)-piperazine 1-(3-chloro-4-nitro-phenyl)-4-(4,6-dimethyl-2-pyridyl)piperazine (800 mg, 54%) as a yellow solid.

Workup

  1. stirringthe reaction mixture stirred for 15 min
  2. stirringstirred for a further 10 min
  3. extractionThe mixture was extracted with ethyl acetate
  4. washthe organic phase was washed with water, brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated under vacuum
  7. customto give a crude residue
  8. customPurification by column chromatography over silica gel (100-200 mesh)

Sources & evidence

ORD record
ord-23fc1f5269fc44eea2c4e9800e5aea4f
Source dataset
uspto-grants-2015_03
Patent number
US08993574B2

Reaction notes

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