Ethyl Acetate → HCID 90403371, compound

HRID 1049263Notes

Reaction equation

HRID 1049263 reaction equation
Cl[C:2]1[CH:7]=[C:6]([O:8][C:9]2[CH:10]=[N:11][C:12]([N+:15]([O-:17])=[O:16])=[CH:13][CH:14]=2)[CH:5]=[CH:4][N:3]=1.[CH3:18][C:19]1[O:20][C:21](B2OC(C)(C)C(C)(C)O2)=[CH:22][N:23]=1.C([O-])([O-])=O.[K+].[K+].CCOC(C)=O>O1CCOCC1.O.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>[CH3:18][C:19]1[O:20][C:21]([C:2]2[CH:7]=[C:6]([O:8][C:9]3[CH:10]=[N:11][C:12]([N+:15]([O-:17])=[O:16])=[CH:13][CH:14]=3)[CH:5]=[CH:4][N:3]=2)=[CH:22][N:23]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 569730962-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)Oxazole2×HCID 593227792-Chloro-4-((6-nitropyridin-3-yl)oxy)pyridine

Product 1

HCID 90403371HCID 90403371, compoundYield 45.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of Example A1 (600 mg, 2.38 mmol), 2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)oxazole (648 mg, 3.10 mmol), K2CO3 (989 mg, 7.15 mmol) and Pd(PPh3)4 (138 mg, 0.119 mmol) in dioxane (8 mL) and water (2 mL) was sparged with Ar and heated at 80° C. overnight. Additional 2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)oxazole (100 mg) and Pd(PPh3)4 (50 mg) were added, the mixture heated at 80° C. for 5 h, then cooled to RT and treated with water and EtOAc. The solids were removed via filtration through diatomaceous earth, the layers of the filtrate separated and the organic layer was washed with brine, dried over Na2SO4, concentrated to dryness and purified via silica gel chromatography (MeOH/EtOAc) to afford 2-methyl-5-(4-((6-nitropyridin-3-yl)oxy)pyridin-2-yl)oxazole (323 mg, 45%). MS (ESI) m/z: 299.1 (M+H+).

Workup

  1. temperaturethe mixture heated at 80° C. for 5 h
  2. temperaturecooled to RT
  3. customThe solids were removed via filtration through diatomaceous earth
  4. customthe layers of the filtrate separated
  5. washthe organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to dryness
  8. custompurified via silica gel chromatography (MeOH/EtOAc)

Sources & evidence

ORD record
ord-9065ef05ceee4652a29deb206f3ebc45
Source dataset
uspto-grants-2016_07
Patent number
US09382228B2

Reaction notes

Loading…