2,6-Dichloro-3-pyridylamine → 6-Chloro-2-ethylpyridin-3-amine

HRID 1438389Notes

Reaction equation

HRID 1438389 reaction equation
[NH2:1][C:2]1[C:3](Cl)=[N:4][C:5]([Cl:8])=[CH:6][CH:7]=1.[CH2:10]([Al](CC)CC)[CH3:11]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:8][C:5]1[N:4]=[C:3]([CH2:10][CH3:11])[C:2]([NH2:1])=[CH:7][CH:6]=1

Participants

5

Reactant 2

HCID 1128462,6-Dichloro-3-pyridylamineHCID 16682930Triethylaluminum

Product 1

HCID 573592636-Chloro-2-ethylpyridin-3-amineYield 35%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 3-amino-2,6-dichloropyridine (8.1 g, 50 mmol, purchased from TCl) in 1,4-dioxane (248 ml) was added tetrakis(triphenylphosphine)palladium(0) (920 mg, 0.80 mmol) and triethylaluminum (52 mmol, 0.94 M in hexane) at room temperature, and the mixture was stirred for 3 hours at 100° C. Themixture was quenched with 2 M HCl aqueous solution after cooling, and then it was separated between the aqueous and organic phases. The aqueous phase was extracted with EtOAc. The combined organic phases were dried over magnesium sulfate and concentrated. The crude product was purified by silica gel column chromatography, eluting with hexane/EtOAc (2:1), to give the title compound (2.73 g, 35%).

Workup

  1. customThemixture was quenched with 2 M HCl aqueous solution
  2. temperatureafter cooling
  3. customit was separated between the aqueous and organic phases
  4. extractionThe aqueous phase was extracted with EtOAc
  5. dry with materialThe combined organic phases were dried over magnesium sulfate
  6. concentrationconcentrated
  7. customThe crude product was purified by silica gel column chromatography
  8. washeluting with hexane/EtOAc (2:1)

Sources & evidence

ORD record
ord-d490016fe75849ceb850757c1fe58087
Source dataset
uspto-grants-2009_11
Patent number
US07622589B2

Reaction notes

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