1,3-Propanediamine → (3-Aminopropyl)(5-nitro(2-pyridyl))amine

HRID 31737Notes

Reaction equation

HRID 31737 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.[NH2:11][CH2:12][CH2:13][CH2:14][NH2:15]>C(#N)C>[NH2:11][CH2:12][CH2:13][CH2:14][NH:15][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1

Participants

4

Reactant 2

HCID 4281,3-PropanediamineHCID 783082-Chloro-5-nitropyridine

Product 1

HCID 22170116(3-Aminopropyl)(5-nitro(2-pyridyl))amine

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

A solution of 2-chloro-5-nitropyridine (3.16 g, 20 mmol) in dry acetonitrile (40 ml) was added dropwise to a solution of 1,3-diaminopropane (5.0 ml) in acetonitrile (20 ml) at room temperature. After 7.5 hour, a yellow solid precipitated in the reaction mixture. The solvent was removed in vacuo and the residue was partitioned between 2.5 M aqueous sodium hydroxide and dichloromethane. The layers were separated and the aqueous portion was extracted 3× with dichloromethane. The combined organic layers were back-extracted with a saturated sodium chloride solution, then dried and concentrated in vacuo using a Buchi rotary evaporator Model R-124 to give (3-aminopropyl)(5-nitro(2-pyridyl))amine as a yellow solid (2.55 g). The amine (1.14 g, 6 mmol) was shaken with benzotriazole carboxamidinium 4-methylbenzenesulfonate (2.0 g, 6 mmol) and diisopropylethyl amine (DIEA) (1.05 ml, 6 mmol) in acetonitrile (10 ml) at room temperature over two days. Dilution with ether gave the amino-{3-[(5-nitro(2-pyridyl))amino]propyl}carboxamidinium 4-methylbenzenesulfonate as a solid.

Workup

  1. customa yellow solid precipitated in the reaction mixture
  2. customThe solvent was removed in vacuo
  3. customthe residue was partitioned between 2.5 M aqueous sodium hydroxide and dichloromethane
  4. customThe layers were separated
  5. extractionthe aqueous portion was extracted 3× with dichloromethane
  6. extractionThe combined organic layers were back-extracted with a saturated sodium chloride solution
  7. customdried
  8. concentrationconcentrated in vacuo
  9. customa Buchi rotary evaporator Model R-124

Sources & evidence

ORD record
ord-f58c5da58c4a4a54914308db92c74578
Source dataset
uspto-grants-2008_09
Patent number
US07425557B2

Reaction notes

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