Iodobenzene → HCID 59276430, compound

HRID 2070883Notes

Reaction equation

HRID 2070883 reaction equation
Br[C:2]1[N:7]2[N:8]=[C:9]([NH:11][C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[N:10]=[C:6]2[CH:5]=[CH:4][CH:3]=1.BrC1N2N=C(N)N=C2C=CC=1.IC1C=CC=CC=1.CC(C)([O-])C.[Na+].C1(P(C2C=CC=CC=2)C2C3[O:61][C:60]4[C:55](=[CH:56][CH:57]=[CH:58][C:59]=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.O.[Cl-].[Na+].O>O1CCOCC1>[C:12]1([NH:11][C:9]2[N:10]=[C:6]3[CH:5]=[CH:4][CH:3]=[C:2]([C:58]4[CH:59]=[C:60]([OH:61])[CH:55]=[CH:56][CH:57]=4)[N:7]3[N:8]=2)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

8

Reactant 6

HCID 11575IodobenzeneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23676156Sodium t-butoxideHCID 23713072Sodium chloride dihydrateHCID 252159395-Bromo-[1,2,4]triazolo[1,5-a]pyridin-2-amineHCID 86640815HCID 86640815, compound

Product 1

HCID 59276430HCID 59276430, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

5-Bromo-N-phenyl-[1,2,4]triazolo[1,5-a]pyridin-2-amine. To a solution of 5-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-amine (2 g, 9.39 mmol) in 100 mL of dioxane was added iodobenzene (3.83 g, 18.78 mmol), sodium tert-butoxide (1.804 g, 18.78 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (1.086 g, 1.878 mmol) and tris(dibezylideneacetone)palladium (0.903 g, 0.986 mmol) at room temperature under nitrogen. The reaction mixture was heated at 100° C. for 2 h. Upon completion of the reaction, as indicated by LCMS, the reaction mixture was poured into water/brine, and extracted with ethyl acetate several times. The combined organic layers were dried over anhydrous magnesium sulfate and concentrated. The crude mixture was purified by silica gel column chromatography (eluting with 0-80% ethyl acetate in hexanes) to give the title compound as a brown solid (1.3 g, 48% yield). 1H NMR (400 MHz DMSO-d6) δ (ppm) 9.84 (s, 1H), 7.74-7.71 (m, 2H), 7.62-7.60 (m, 1H), 7.52-7.48 (m, 1H), 7.40-7.38 (m, 1H), 7.32-7.28 (m, 2H), 6.92-6.88 (m, 1H); MS (ESI) m/z 290.13 [M+1]+

Workup

  1. customUpon completion of the reaction
  2. extractionextracted with ethyl acetate several times
  3. dry with materialThe combined organic layers were dried over anhydrous magnesium sulfate
  4. concentrationconcentrated
  5. customThe crude mixture was purified by silica gel column chromatography (eluting with 0-80% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-710381a8c94741c9a78553d67dfd2288
Source dataset
uspto-grants-2012_10
Patent number
US08299056B2

Reaction notes

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