Acetic Acid → Methyl 4-(4-Acetoxy-1-oxobutyl)benzoate

HRID 2050532Notes

Reaction equation

HRID 2050532 reaction equation
[OH:1][CH2:2][CH2:3][C:4]#[C:5][C:6]1[CH:15]=[CH:14][C:9]([C:10]([O:12][CH3:13])=[O:11])=[CH:8][CH:7]=1.S(=O)(=O)(O)[OH:17].[C:21](O)(=[O:23])[CH3:22]>>[C:21]([O:1][CH2:2][CH2:3][CH2:4][C:5]([C:6]1[CH:7]=[CH:8][C:9]([C:10]([O:12][CH3:13])=[O:11])=[CH:14][CH:15]=1)=[O:17])(=[O:23])[CH3:22]

Participants

4

Reactant 3

HCID 176Acetic AcidHCID 1118Sulfuric AcidHCID 146031084-(4-Hydroxy-1-Butynyl)benzoic Acid Methyl Ester

Product 1

HCID 15734961Methyl 4-(4-Acetoxy-1-oxobutyl)benzoate

Conditions

Temperature
140 °C

Procedure

To 10.0 g (1 eq) of methyl 4-(4-hydroxy-1-butynyl)benzoate in 200 ml of 90% aqueous acetic acid and 2.4 g (0.15 eq) of mercuric acetate were added 1.0 ml of concentrated sulfuric acid. The mixture was refluxed for 2 hours at approximately 140° C., and cooled to room temperature to facilitate precipitation of mercury salts. The precipitated mercury salts were removed by filtration and the filtrate extracted three times with dichloromethane. The acidic extract was neutralized to pH 7 with solid sodium bicarbonate and the aqueous layer then extracted with dichloromethane. The extracts were dried over magnesium sulfate and evaporated under reduced pressure to yield the product which was further purified by flash chromatography eluting with 1:2 ethylacetate:hexanes. m.p. 61-62° C. M.S.: m/z=264 (M+, CI), 233.0812 (M+ --CH3O, calc. for C13H13O5 : 233.0814), 204 (M+ -AcOH), 176, 163 (100%), 143. 1H-N.M.R. (CDCl3, 300 MHz): δ=2.08 (s, 3H, CH3 --CO); 2.10 (quin, 2H, CH2 --CH2 --CH2, J=7.5 Hz); 3.12 (t, 2H, CH2 --CO, J=7.5 Hz); 3.96 (s, 3H, CH3O); 4.20 (t, 2H, CH2O, J=7.5 Hz); 8.02 (d, 2Harom., J=9 Hz); 8.18 (d, 2Harom., J=9 Hz).

Workup

  1. temperaturecooled to room temperature
  2. customprecipitation of mercury salts
  3. customThe precipitated mercury salts were removed by filtration
  4. extractionthe filtrate extracted three times with dichloromethane
  5. extractionThe acidic extract
  6. extractionthe aqueous layer then extracted with dichloromethane
  7. dry with materialThe extracts were dried over magnesium sulfate
  8. customevaporated under reduced pressure
  9. customto yield the product which
  10. customwas further purified by flash chromatography
  11. washeluting with 1:2 ethylacetate

Sources & evidence

ORD record
ord-713a1483757b4dabb663a95ea4afd0cd
Source dataset
uspto-grants-1991_05
Patent number
US05013738

Reaction notes

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