Potassium Carbonate → 3-(2,3-Dichlorophenyl)pyridine-2,6-diamine

HRID 1094791Notes

Reaction equation

HRID 1094791 reaction equation
Br[C:2]1[C:3]([NH2:9])=[N:4][C:5]([NH2:8])=[CH:6][CH:7]=1.[Cl:10][C:11]1[C:16]([Cl:17])=[CH:15][CH:14]=[CH:13][C:12]=1B(O)O.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[Cl:10][C:11]1[C:16]([Cl:17])=[CH:15][CH:14]=[CH:13][C:12]=1[C:2]1[C:3]([NH2:9])=[N:4][C:5]([NH2:8])=[CH:6][CH:7]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 14158683-Bromopyridine-2,6-diamineHCID 27346612,3-Dichlorobenzeneboronic acid2×

Product 1

HCID 575823573-(2,3-Dichlorophenyl)pyridine-2,6-diamineYield 35.4%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst2×HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a suspension of 3-bromopyridine-2,6-diamine (0.376 g, 2.00 mmol) in 1,4-dioxane (12 ml) and water (6 ml) was added 2,3-dichlorophenyl boronic acid (0.573 g, 3.00 mmol), potassium carbonate (0.552 g, 4.00 mmol) and palladium tetrakis(triphenylphosphine) (0.115 g, 0.01 mmol). The reaction was purged with nitrogen and heated at 80° C. for 18 hours. Further palladium tetrakis(triphenylphosphine) (0.115 g, 0.01 mmol) and 2,3-dichlorophenyl boronic acid (0.573 g, 3.00 mmol) were added and the reaction heated at 80° C. for a further 18 hours before concentrating in vacuo. The residue was taken up in ethyl acetate (20 ml) and washed with a saturated aqueous solution of K2CO3 before drying over MgSO4 and concentrating in vacuo. The residue was purified by silica gel column chromatography, eluting with 99:1 dichloromethane:methanol, then recrystallised from toluene to afford the title compound (0.180 g, 35% yield).

Workup

  1. customThe reaction was purged with nitrogen
  2. temperaturethe reaction heated at 80° C. for a further 18 hours
  3. concentrationbefore concentrating in vacuo
  4. washwashed with a saturated aqueous solution of K2CO3
  5. dry with materialbefore drying over MgSO4
  6. concentrationconcentrating in vacuo
  7. customThe residue was purified by silica gel column chromatography
  8. washeluting with 99:1 dichloromethane
  9. custommethanol, then recrystallised from toluene

Sources & evidence

ORD record
ord-5942b936a5a347159b26a14ee07cd957
Source dataset
uspto-grants-2012_03
Patent number
US08134007B2

Reaction notes

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