1,4-Dioxane → HCID 86731661, compound

HRID 1504764Notes

Reaction equation

HRID 1504764 reaction equation
O1CCOCC1.[CH3:7][N:8]1[CH:12]=[C:11](B2OC(C)(C)C(C)(C)O2)[N:10]=[CH:9]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Br[C:31]1[CH:32]=[CH:33][C:34]([NH2:38])=[N:35][C:36]=1[CH3:37]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.O>[CH3:37][C:36]1[N:35]=[C:34]([NH2:38])[CH:33]=[CH:32][C:31]=1[C:11]1[N:10]=[CH:9][N:8]([CH3:7])[CH:12]=1

Participants

7

Reactant 4

HCID 312751,4-DioxaneHCID 62657Potassium Phosphate, TribasicHCID 1706782-Pyridinamine, 5-bromo-6-methyl-HCID 71128159HCID 71128159, compound

Product 1

HCID 86731661HCID 86731661, compound

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

Dioxane (3.61 mL), 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-imidazole (200 mg, 0.962 mmol), water (0.40 mL) and tribasic potassium phosphate, (511 mg, 2.41 mmol) were added to 5-bromo-6-methylpyridin-2-amine (150 mg, 0.802 mmol) in a scintillation vial. The vial was purged and flushed with argon 3 times before adding PdCl2(dppf)-CH2Cl2 adduct (66 mg, 0.080 mmol). The vial was then purged with argon, sealed, and heated to 100° C. After 16 hours, the reaction mixture was cooled to room temperature, filtered through CELITE (washed with chloroform), and diluted with water. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (10-100% (10% methanol in chloroform)/hexanes, linear gradient) to afford 6-methyl-5-(1-methyl-1H-imidazol-4-yl)pyridin-2-amine. MS ESI calc'd. for C10H13N4 [M+H]+ 189. found 189. 1H NMR (500 MHz, CDCl3) δ 7.52 (s, 1H), 7.37 (s, 1H), 7.35 (d, J=8.3 Hz, 1H), 6.38 (d, J=8.3 Hz, 1H), 3.94 (s, 3H), 2.44 (s, 3H).

Workup

  1. customThe vial was purged
  2. customflushed with argon 3 times
  3. customThe vial was then purged with argon
  4. customsealed
  5. temperaturethe reaction mixture was cooled to room temperature
  6. filtrationfiltered through CELITE (washed with chloroform)
  7. additiondiluted with water
  8. dry with materialThe organic layer was dried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by silica gel chromatography (10-100% (10% methanol in chloroform)/hexanes, linear gradient)

Sources & evidence

ORD record
ord-d190e4e398d94e7c910463b9e25693fb
Source dataset
uspto-grants-2015_12
Patent number
US09216173B2

Reaction notes

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