Triethylamine → 2-chloro-5,6-dimethyl-3-nitro-N-prop-2-ynylpyridin-4-amine

HRID 606087Notes

Reaction equation

HRID 606087 reaction equation
[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[C:6](Cl)[C:5]([CH3:12])=[C:4]([CH3:13])[N:3]=1.C(N(CC)CC)C.Cl.[CH2:22]([NH2:25])[C:23]#[CH:24].C(N)C#C>CN(C=O)C>[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[C:6]([NH:25][CH2:22][C:23]#[CH:24])[C:5]([CH3:12])=[C:4]([CH3:13])[N:3]=1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 239041PropargylamineHCID 11205720Prop-2-ynylamine hydrochlorideHCID 121091232,4-Dichloro-5,6-dimethyl-3-nitropyridine

Product 1

HCID 862476282-chloro-5,6-dimethyl-3-nitro-N-prop-2-ynylpyridin-4-amineYield 416.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Under a nitrogen atmosphere, a solution of 2,4-dichloro-5,6-dimethyl-3-nitropyridine (137.9 g, 0.624 mol) in anhydrous DMF (1.4 L) was cooled to 0° C., and anhydrous triethylamine (109 mL, 0.780 mol) was added. Propargyl amine hydrochloride (4.72 g, 51.6 mmol) and propargyl amine (38.4 g, 0.697 mol) were sequentially added dropwise, and the reaction was allowed to warm to room temperature and then heated at 40° C. for 22 hours. The volatiles were removed under reduced pressure, and water (1.5 L) and solid sodium carbonate (75 g) were added to the resulting oil. The mixture was then extracted with dichloromethane, and the combined extracts were washed sequentially with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (eluting sequentially with 60:40 dichloromethane/hexane and dichloromethane) to provide 51.54 g of 2-chloro-5,6-dimethyl-3-nitro-N-prop-2-ynylpyridin-4-amine as a brown solid.

Workup

  1. temperatureheated at 40° C. for 22 hours
  2. customThe volatiles were removed under reduced pressure, and water (1.5 L) and solid sodium carbonate (75 g)
  3. additionwere added to the resulting oil
  4. extractionThe mixture was then extracted with dichloromethane
  5. washthe combined extracts were washed sequentially with water and brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude product was purified by column chromatography on silica gel (
  10. washeluting sequentially with 60:40 dichloromethane/hexane and dichloromethane)

Sources & evidence

ORD record
ord-c4d5823b69534e7ebcd7ae45b3a502e1
Source dataset
uspto-grants-2011_03
Patent number
US07915281B2

Reaction notes

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