Ethylenediamine → {2-[(6-Amino-5-nitro(2-pyridyl))amino]ethyl}[6-(2,4-dichlorophenyl)-5-imidazolyl(2-pyridyl)]amine

HRID 1823484Notes

Reaction equation

HRID 1823484 reaction equation
[NH2:1][CH2:2][CH2:3][NH:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[NH:12][CH:13]=[CH:14][N:15]=2)=[C:7]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=2[Cl:23])[N:6]=1.Cl[C:25]1[N:30]=[C:29]([NH2:31])[C:28]([N+:32]([O-:34])=[O:33])=[CH:27][CH:26]=1.CCN(C(C)C)C(C)C.C(N)CN>CN(C)C(=O)C>[NH2:31][C:29]1[N:30]=[C:25]([NH:1][CH2:2][CH2:3][NH:4][C:5]2[CH:10]=[CH:9][C:8]([C:11]3[NH:15][CH:14]=[CH:13][N:12]=3)=[C:7]([C:16]3[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=3[Cl:23])[N:6]=2)[CH:26]=[CH:27][C:28]=1[N+:32]([O-:34])=[O:33]

Participants

6

Reactant 4

HCID 3301EthylenediamineHCID 81531DiisopropylethylamineHCID 27240356-Chloro-3-nitropyridin-2-ylamineHCID 57126782HCID 57126782, compound

Product 1

HCID 22142808{2-[(6-Amino-5-nitro(2-pyridyl))amino]ethyl}[6-(2,4-dichlorophenyl)-5-imidazolyl(2-pyridyl)]amineYield 61%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Conditions

Temperature
87.5 °C

Procedure

A mixture of (2-aminoethyl)[6-(2,4-dichlorophenyl)-5-imidazolyl(2-pyridyl)]amine (0.14 M), 6-chloro-3-nitro-2-pyridylamine (0.14 M), N,N-dimethylacetamide (40 ml), and Hünig's base (2.5 ml) was stirred for 12 hours at 85-90° C. under argon. Ethylene diamine (3.8 ml) was added to remove the unreacted chloropyridine, and the mixture was stirred for an additional 0.75-1 hour at 85-90° C. under argon. After cooling, the reaction was diluted with ethyl acetate (500-600 ml), extracted with saturated sodium bicarbonate (4×200 ml), distilled water (3×150 ml), saturated sodium chloride (150 ml). The organic layer was dried with sodium sulfate briefly (2-3 minutes) so as not to initiate precipitation of the product. The organic layer was filtered, concentrated, and dried in vacuo. To cause precipitation of the product, a minimal amount of methanol (3-5 ml) was added followed with the addition of an equal volume of ethyl acetate. The mixture was allowed to age for 2-3 hours. The solid was collected by filtration, washed with minimal 1:1 methanol/ethyl acetate (5 ml), and a finally 100% ethyl acetate (2×10 ml). The yellow solid was dried in vacuo to give {2-[(6-amino-5-nitro(2-pyridyl))amino]ethyl}[6-(2,4-dichlorophenyl)-5-imidazolyl(2-pyridyl)]amine in 61% yield.

Workup

  1. customto remove the unreacted chloropyridine
  2. stirringthe mixture was stirred for an additional 0.75-1 hour at 85-90° C. under argon
  3. temperatureAfter cooling
  4. additionthe reaction was diluted with ethyl acetate (500-600 ml)
  5. extractionextracted with saturated sodium bicarbonate (4×200 ml)
  6. distillationdistilled water (3×150 ml), saturated sodium chloride (150 ml)
  7. dry with materialThe organic layer was dried with sodium sulfate briefly (2-3 minutes) so as not
  8. customprecipitation of the product
  9. filtrationThe organic layer was filtered
  10. concentrationconcentrated
  11. customdried in vacuo
  12. customprecipitation of the product
  13. additiona minimal amount of methanol (3-5 ml) was added
  14. additionfollowed with the addition of an equal volume of ethyl acetate
  15. waitThe mixture was allowed to age for 2-3 hours
  16. filtrationThe solid was collected by filtration
  17. washwashed with minimal 1:1 methanol/ethyl acetate (5 ml)
  18. customThe yellow solid was dried in vacuo

Sources & evidence

ORD record
ord-f8156c07d5d143f2abae5bb3ebbaa60c
Source dataset
uspto-grants-2006_05
Patent number
US07037918B2

Reaction notes

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