2-Bromothiazole → HCID 22618309, compound

HRID 1421228Notes

Reaction equation

HRID 1421228 reaction equation
Cl[C:2]1[CH:3]=[C:4](C#C)[C:5]2[O:9][C:8]([CH2:10][C:11]3[CH:16]=C(C(C)(C)C)C(O)=C(C(C)(C)C)C=3)=[N:7][C:6]=2[CH:26]=1.BrC1[S:31][CH:32]=[CH:33][N:34]=1>C(N(CC)CC)C.[Pd](Cl)Cl.[Cu]I>[S:31]1[CH:32]=[CH:33][N:34]=[C:16]1[C:11]#[C:10][C:8]1[O:9][C:5]2[CH:4]=[CH:3][CH:2]=[CH:26][C:6]=2[N:7]=1

Participants

6

Reactant 2

HCID 764302-BromothiazoleHCID 15521191HCID 15521191, compound

Product 1

HCID 22618309HCID 22618309, compoundYield 210.7%

Reagents, catalysts & solvents 3

HCID 24290Palladium ChlorideCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8471TriethylamineSolvent

Procedure

A suspension of 5-chloro-2-(3,5-di-t-butyl-4-hydroxy-benzyl)-7-ethynyl-benzoxazole (2.38 g, 6.0 mmol), 2-bromothiazole (1.13 ml, 95%, 12 mmol), bistriphenylphosphine)palladium(II) dichloride (21.1 mg, 30 μmol), and copper (I) iodide (1.2 mg, 6 μmol) in triethylamine (12 ml) was heated at 90 EC, under argon, for 3 hours. The triethylamine was removed in-vacuo and the residue dissolved in ether (70 ml) and water (30 ml). The organics were washed with 1 N HCl (30 ml) and saturated sodium hydrogen carbonate (30 ml), dried (Na2SO4) and evaporated--to give 2.86 g (100%) of crude thiazolylethynylbenzoxazole, which was purified by flash chromatography (SiO2 ; dichloromethane). The product was crystallized and recrystallized from methanol to give 1.43 g (50.4%) of the title compound (mp 137-41 EC).

Workup

  1. temperaturewas heated at 90 EC, under argon, for 3 hours
  2. customThe triethylamine was removed in-vacuo
  3. dissolutionthe residue dissolved in ether (70 ml)
  4. washThe organics were washed with 1 N HCl (30 ml) and saturated sodium hydrogen carbonate (30 ml)
  5. dry with materialdried (Na2SO4)
  6. customevaporated

Sources & evidence

ORD record
ord-fb7f6245e61e470f8b51037547a59fae
Source dataset
uspto-grants-2000_06
Patent number
US06075016

Reaction notes

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