Potassium Carbonate → 4-Chloro-6-methylpyridin-2-amine

HRID 1028051Notes

Reaction equation

HRID 1028051 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6](Cl)[N:5]=[C:4]([NH2:9])[CH:3]=1.[CH3:10]B1OB(C)OB(C)O1.C([O-])([O-])=O.[K+].[K+]>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.O1CCOCC1>[Cl:1][C:2]1[CH:7]=[C:6]([CH3:10])[N:5]=[C:4]([NH2:9])[CH:3]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 574072TrimethylboroxineHCID 53166492-Amino-4,6-dichloropyridine

Product 1

HCID 190505094-Chloro-6-methylpyridin-2-amineYield 23%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

To a 10% aqueous solution of dioxane (0.1 M) was added 4,6-dichloropyridin-2-amine (1.0 equiv.), trimethylboroxine (1.5 equiv.), Pd(PPh3)4 (0.10 equiv.) and K2CO3 (3.0 equiv.). The solution was heated in an oil bath to 120° C. for 18 hrs, cooled to room temperature (not all of starting material was consumed), extracted with EtOAc, dried with Na2SO4, and concentrated. The crude material was purified via SiO2 column chromatography eluting with 5% MeOH/DCM to yield 4-chloro-6-methylpyridin-2-amine as an off-white solid in 23% yield. LCMS (m/z): 143 (MH+); LC Rt=1.11 min.

Workup

  1. temperaturecooled to room temperature (not all of starting material
  2. customwas consumed),
  3. extractionextracted with EtOAc
  4. dry with materialdried with Na2SO4
  5. concentrationconcentrated
  6. customThe crude material was purified via SiO2 column chromatography
  7. washeluting with 5% MeOH/DCM

Sources & evidence

ORD record
ord-86e6319e42c74e94ba3aee01172c6838
Source dataset
uspto-grants-2014_05
Patent number
US08735424B2

Reaction notes

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