Acetic Acid → 7-Butyryloxy-3-carboxymethylaminocarbonyl-6-chlorocoumarin

HRID 2246037Notes

Reaction equation

HRID 2246037 reaction equation
[C:1]([O:6][C:7]1[CH:16]=[C:15]2[C:10]([CH:11]=[C:12]([C:18]([NH:20][CH2:21][C:22]([O:24]CC3C=CC=CC=3)=[O:23])=[O:19])[C:13](=[O:17])[O:14]2)=[CH:9][C:8]=1[Cl:32])(=[O:5])[CH2:2][CH2:3][CH3:4].C(O)(=O)C.[H][H].O1C2C(=CC=CC=2)C=CC1=O>O1CCOCC1.[Pd]>[C:1]([O:6][C:7]1[CH:16]=[C:15]2[C:10]([CH:11]=[C:12]([C:18]([NH:20][CH2:21][C:22]([OH:24])=[O:23])=[O:19])[C:13](=[O:17])[O:14]2)=[CH:9][C:8]=1[Cl:32])(=[O:5])[CH2:2][CH2:3][CH3:4]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 323Coumarin3×HCID 219248587-Butyryloxy-3-benzyloxycarbonylmethylaminocarbonyl-6-chlorocoumarinHCID 178418361HCID 178418361, compound2×

Product 1

HCID 219248487-Butyryloxy-3-carboxymethylaminocarbonyl-6-chlorocoumarin

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

7-Butyryloxy-3-carboxymethylaminocarbonyl-6-chlorocoumarin was prepared as follows. 920 mg (2 mmol) 7-butyryloxy-3-benzyloxycarbonylmethylaminocarbonyl-6-chlorocoumarin were dissolved in 50 ml dioxane. 100 mg palladium on carbon (10%) and 100 microliters acetic acid were added to the solution and the suspension stirred vigorously in a hydrogen atmosphere at ambient pressure. After the uptake of hydrogen seized the suspension was filtered. The product containing carbon was extracted five times with 25 ml boiling dioxane. The combined dioxane solutions were let to cool upon which the product precipitated as a white powder. Reduction of the solvent to 20 ml precipitates more product. The remaining dioxane solution is heated to boiling and heptane is added until the solution becomes cloudy. The weights of the dried powders were 245 mg, 389 mg and 58 mg, totaling 692 mg (1.88 mMol, 94%) of white product. 1H NMR (dDMSO): δ 1.02 ppm (t, 3H, J=7.4 Hz, butyric methyl), δ 1.73 ppm (m, 2H, J1≈J2=7.3 Hz, butyric methylene), δ 2.70 ppm (t, 2H, J=7.2 Hz, butyric methylene), δ 4.07 ppm (d, 2H, J=5.6 Hz, glycine methylene), δ 7.67 ppm (s, 1H, coumarin), δ 8.35 ppm (s, 1H, coumarin), δ 8.90 ppm (s, 1H, coumarin), δ 9.00 ppm (t, 1H, J=5.6 Hz, amide).

Workup

  1. filtrationwas filtered
  2. additionThe product containing carbon
  3. extractionwas extracted five times with 25 ml
  4. temperatureto cool upon which the product
  5. customprecipitated as a white powder
  6. customReduction of the solvent to 20 ml precipitates more product
  7. temperatureThe remaining dioxane solution is heated
  8. additionheptane is added until the solution

Sources & evidence

ORD record
ord-3fccc3776fcd4e37b1694b2cdb26de4c
Source dataset
uspto-grants-2010_03
Patent number
US07687282B2

Reaction notes

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