Triethylamine → Methyl 4-acetylamino-5-bromo-3-(3,3-dimethyl-1-butynyl)salicylate

HRID 17539

Reaction equation

HRID 17539 reaction equation
[C:1]([NH:4][C:5]1[C:6](I)=[C:7]([OH:16])[C:8](=[CH:13][C:14]=1[Br:15])[C:9]([O:11][CH3:12])=[O:10])(=[O:3])[CH3:2].[CH3:18][C:19]([CH3:23])([CH3:22])[C:20]#[CH:21].C(N(CC)CC)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.O1CCOCC1>[C:1]([NH:4][C:5]1[C:6]([C:21]#[C:20][C:19]([CH3:23])([CH3:22])[CH3:18])=[C:7]([OH:16])[C:8](=[CH:13][C:14]=1[Br:15])[C:9]([O:11][CH3:12])=[O:10])(=[O:3])[CH3:2]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 135123,3-Dimethyl-1-butyneHCID 86097515Methyl 4-acetylamino-5-bromo-3-iodosalicylate

Product 1

HCID 86630872Methyl 4-acetylamino-5-bromo-3-(3,3-dimethyl-1-butynyl)salicylate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
30 °C

Procedure

Under nitrogen atmosphere, methyl 4-acetylamino-5-bromo-3-iodosalicylate (I-250) (414 mg, 1.0 mmol), bis(triphenylphosphine)palladium(II) chloride (49 mg, 0.07 mmol), copper(I) iodide (19 mg, 0.1 mmol) and 3,3-dimethyl-1-butyne (0.13 ml, 1.1 mmol) were added to a mixed liquid of triethylamine (4 ml) and dioxane (6 ml), followed by stirring at 30° C. for 2 hours. The reaction liquid was concentrated under reduced pressure, then saturated ammonium chloride water was added to the residue, followed by extraction twice with chloroform, the organic layer was washed with saturated brine, then dried over anhydrous magnesium sulfate. After filtration and concentration under reduced pressure, the resulting residue was subjected to column, chromatography, and the eluate with n-hexane/ethyl acetate (2:1) gave the entitled compound (243 mg, 66.5) as a white solid.

Workup

  1. customThe reaction liquid
  2. concentrationwas concentrated under reduced pressure
  3. additionsaturated ammonium chloride water was added to the residue
  4. extractionfollowed by extraction twice with chloroform
  5. washthe organic layer was washed with saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationAfter filtration and concentration under reduced pressure
  8. customthe eluate with n-hexane/ethyl acetate (2:1) gave the entitled compound (243 mg, 66.5) as a white solid

Sources & evidence

ORD record
ord-edb7512fe008400fbb309091a2445737
Source dataset
uspto-grants-2010_06
Patent number
US07737166B2

Linked notes

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