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

HRID 2081561Notes

Reaction equation

HRID 2081561 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 portionwise 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-91c7e1f71e6c4f4ab013ffbd53f1cf37
Source dataset
uspto-grants-1993_02
Patent number
US05185335

Reaction notes

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