Potassium Iodide → Methyl 4-(acetylamino)-2-(1,1-dimethyl-2-propynyloxy)benzoate

HRID 257432Notes

Reaction equation

HRID 257432 reaction equation
[C:1]([NH:4][C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[C:7]([OH:15])[CH:6]=1)(=[O:3])[CH3:2].[H-].[Na+].[I-].[K+].Cl[C:21]([CH3:25])([CH3:24])[C:22]#[CH:23].[OH-].[Na+]>CN(C)C=O>[C:1]([NH:4][C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[C:7]([O:15][C:21]([CH3:25])([CH3:24])[C:22]#[CH:23])[CH:6]=1)(=[O:3])[CH3:2]

Participants

7

Reactant 5

HCID 4875Potassium IodideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 706791-Butyne, 3-chloro-3-methyl-HCID 77719Methyl 4-acetamidosalicylate

Product 1

HCID 19783273Methyl 4-(acetylamino)-2-(1,1-dimethyl-2-propynyloxy)benzoateYield 10.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 310 parts of methyl 4-(acetylamino]-2-hydroxybenzoate in 2820 parts of N,N-dimethylformamide there were added portion wise 71 parts of a dispersion of sodium hydride in mineral oil (50%) and, after stirring for 1 hour at room temperature, one crystal of potassium iodide and 172 parts of 3-chloro-3-methyl-1-butyne under a nitrogen atmosphere. The whole was stirred for 24 hours at 90° C. and was then poured into NaOH 10% (aq.). The product was extracted with dichloromethane and the extract was dried, filtered and evaporated. The residue was successively stirred in petroleumether and dissolved in dichloromethane. The latter solution was washed with water, NaOH 10% and water and was then dried, filtered and evaporated. The residue was purified by column chromatography (silica gel; CH2Cl2). The eluent of the desired fraction was evaporated, yielding in two fractions 41 parts (10.1%) of methyl 4-(acetylamino)-2-(1,1-dimethyl-2-propynyloxy)benzoate (interm. 1).

Workup

  1. stirringThe whole was stirred for 24 hours at 90° C.
  2. extractionThe product was extracted with dichloromethane
  3. customthe extract was dried
  4. filtrationfiltered
  5. customevaporated
  6. stirringThe residue was successively stirred in petroleumether
  7. dissolutiondissolved in dichloromethane
  8. washThe latter solution was washed with water, NaOH 10% and water
  9. customwas then dried
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue was purified by column chromatography (silica gel; CH2Cl2)
  13. customThe eluent of the desired fraction was evaporated

Sources & evidence

ORD record
ord-ea66e7a2c484481a85a479bfadc58f51
Source dataset
uspto-grants-1993_11
Patent number
US05262418

Reaction notes

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