Pentane → 3-(2-Chloro-5-methoxyphenyl)pyridine-2,6-diamine

HRID 1094789Notes

Reaction equation

HRID 1094789 reaction equation
I[C:2]1[C:3]([NH2:9])=[N:4][C:5]([NH2:8])=[CH:6][CH:7]=1.[Cl:10][C:11]1[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][C:12]=1B(O)O.C(=O)([O-])[O-].[Cs+].[Cs+].CCCCC>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[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][C:12]=1[C:2]1[C:3]([NH2:9])=[N:4][C:5]([NH2:8])=[CH:6][CH:7]=1

Participants

8

Reactant 4

HCID 8003PentaneHCID 10796Cesium carbonateHCID 4762183-Iodopyridine-2,6-diamineHCID 17750233(2-Chloro-5-methoxyphenyl)boronic acid2×

Product 1

HCID 575823413-(2-Chloro-5-methoxyphenyl)pyridine-2,6-diamineYield 109%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
80 °C

Procedure

To a suspension of 3-iodopyridine-2,6-diamine (Preparation 44, 2 g, 8.51 mmol) in 1,4-dioxane (10 ml) and water (5 ml) was added 2-chloro-5-methoxyphenyl boronic acid (0.793 g, 4.25 mmol), cesium carbonate (2.77 g, 8.51 mmol) and palladium tetrakis(triphenylphosphine) (0.123 g, 0.0125 mmol). The reaction was purged with nitrogen and heated at 80° C. for 20 minutes. Three further portions of palladium tetrakis(triphenylphosphine) (0.123 g, 0.0125 mmol) and 2-chloro-5-methoxyphenyl boronic acid (0.793 g, 4.25 mmol) were added at 20 minute intervals. The reaction was heated at 80° C. for 18 hours before concentrating in vacuo. The residue was taken up in ethyl acetate (20 ml) and washed with a saturated aqueous solution of brine (20 ml) before drying over Na2SO4 and concentrating in vacuo. The residue was purified by silica gel column chromatography, eluting with 50:50 to 100:0 ethyl acetate:pentane to afford the title compound as a brown foam (1.157 g, 55% yield).

Workup

  1. customThe reaction was purged with nitrogen
  2. temperatureThe reaction was heated at 80° C. for 18 hours
  3. concentrationbefore concentrating in vacuo
  4. washwashed with a saturated aqueous solution of brine (20 ml)
  5. dry with materialbefore drying over Na2SO4
  6. concentrationconcentrating in vacuo
  7. customThe residue was purified by silica gel column chromatography
  8. washeluting with 50:50 to 100:0 ethyl acetate

Sources & evidence

ORD record
ord-d20b20bb5df8404abc3c510ea048878b
Source dataset
uspto-grants-2012_03
Patent number
US08134007B2

Reaction notes

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