N,N-Dimethylpropargylamine → N,N-dimethyl-3-(6-methyl-5-nitropyridin-3-yl)prop-2-yn-1-amine

HRID 2388004Notes

Reaction equation

HRID 2388004 reaction equation
Br[C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]([CH3:8])=[N:6][CH:7]=1.[CH2:12]([N:15]([CH3:17])[CH3:16])[C:13]#[CH:14]>C(NCC)C.CCOC(C)=O.C([O-])([O-])=O.[Na+].[Na+].[Cu](I)I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:16][N:15]([CH3:17])[CH2:12][C:13]#[C:14][C:2]1[CH:7]=[N:6][C:5]([CH3:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1

Participants

8

Reactant 2

HCID 81643N,N-DimethylpropargylamineHCID 250672665-Bromo-2-methyl-3-nitropyridine

Product 1

HCID 58476572N,N-dimethyl-3-(6-methyl-5-nitropyridin-3-yl)prop-2-yn-1-amineYield 91%

Reagents, catalysts & solvents 5

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8021DiethylamineSolventHCID 8857Ethyl AcetateSolventHCID 10340Sodium CarbonateSolvent

Procedure

To a mixture of 5-bromo-2-methyl-3-nitropyridine (6.50 g, 30.0 mmol), copper iodide (280 mg, 1.5 mmol) and bis(triphenylphosphine)palladium(II) chloride (520 mg, 0.75 mmol) in diethylamine (17 mL) was added propargyl(dimethylamine) (4.04 mL, 37.5 mmol). The reaction mixture was allowed to stir for 15 h at rt. The resulting mixture was diluted with EtOAc (200 mL) and 1M aqueous Na2CO3 (150 mL). After stirring for 30 min, the organic solution was separated and the aqueous solution was extracted with EtOAc (2×100 mL). The organic solutions were combined, washed with water and brine, dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to give N,N-dimethyl-3-(6-methyl-5-nitropyridin-3-yl)prop-2-yn-1-amine (5.98 g, 91%) as a dark oil. LCMS (FA): Rt=0.77 min, m/z=220.1 (M+H).

Workup

  1. stirringAfter stirring for 30 min
  2. customthe organic solution was separated
  3. extractionthe aqueous solution was extracted with EtOAc (2×100 mL)
  4. washwashed with water and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-c0d2e0154db84b77b2e6f1365eeea44c
Source dataset
uspto-grants-2012_09
Patent number
US08268992B2

Reaction notes

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