2-Chloro-3-nitropyridine → 7-(3-Nitro-2-pyridinylamino)-1-(4-methyl-piperazinyl)-naphthalene

HRID 235126Notes

Reaction equation

HRID 235126 reaction equation
[NH2:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][CH:8]=[C:9]2[N:12]2[CH2:17][CH2:16][N:15]([CH3:18])[CH2:14][CH2:13]2)=[CH:4][CH:3]=1.Cl[C:20]1[C:25]([N+:26]([O-:28])=[O:27])=[CH:24][CH:23]=[CH:22][N:21]=1>CN(C)C1C=CN=CC=1.CN(C=O)C>[N+:26]([C:25]1[C:20]([NH:1][C:2]2[CH:11]=[C:10]3[C:5]([CH:6]=[CH:7][CH:8]=[C:9]3[N:12]3[CH2:17][CH2:16][N:15]([CH3:18])[CH2:14][CH2:13]3)=[CH:4][CH:3]=2)=[N:21][CH:22]=[CH:23][CH:24]=1)([O-:28])=[O:27]

Participants

5

Reactant 2

HCID 796132-Chloro-3-nitropyridine2×HCID 233534847-Amino-1-(4-methyl-1-piperazinyl)-naphthalene

Product 1

HCID 189675077-(3-Nitro-2-pyridinylamino)-1-(4-methyl-piperazinyl)-naphthalene

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalyst2×HCID 6228DimethylformamideSolvent2×

Procedure

7-Amino-1-(4-methyl-1-piperazinyl)-naphthalene (0.247 g, 1.02 mmol), 2-chloro-3-nitropyridine (0.325 g, 2.05 mmol), and 4-dimethylaminopyridine (0.062 g, 0.51 mmol) were combined in dry DMF (0.15 mL). The solution was refluxed 4 hours then 0.5 mL more DMF was added and the mixture was allowed to stir at ambient temperature overnight. 2-Chloro-3-nitropyridine (0.105 g, 0.69 mmol), and 4-dimethylaminopyridine (0.062 g, 0.51 mmol) were added and the mixture was refluxed 2 hours more. The solvent was removed in vacuo and the residue was taken up in methylene chloride. This organic phase was washed with 0.5N sodium hydroxide and brine; then it was dried over calcium sulfate and concentrated to a red oil which was flash chromatographed on silica gel (1×4 inches). Gradient elution with 50% to 75% ethyl acetate/hexane followed by elution with 100% ethyl acetate gave a dark colored oil which crystallized upon addition of ether (2 mL) to yield 0.19 g (51%) as a dark red solid: mp 127.5°-129° C. Analysis calculated for C20H21N5O2 ; C, 66.10; H, 5.82; N, 19.27. Found: C, 66.04; H, 5.81; N, 19.02.

Workup

  1. temperatureThe solution was refluxed 4 hours
  2. temperaturethe mixture was refluxed 2 hours more
  3. customThe solvent was removed in vacuo
  4. washThis organic phase was washed with 0.5N sodium hydroxide and brine
  5. dry with materialthen it was dried over calcium sulfate
  6. concentrationconcentrated to a red oil which
  7. customchromatographed on silica gel (1×4 inches)
  8. washGradient elution with 50% to 75% ethyl acetate/hexane
  9. washfollowed by elution with 100% ethyl acetate
  10. customgave a dark colored oil which
  11. customcrystallized upon addition of ether (2 mL)
  12. customto yield 0.19 g (51%) as a dark red solid

Sources & evidence

ORD record
ord-5e9c841e40774ef38bfd3430ce45146f
Source dataset
uspto-grants-1997_01
Patent number
US05597826

Reaction notes

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