Acetonitrile → Ethylcoumarin-3-carboxylate

HRID 618975Notes

Reaction equation

HRID 618975 reaction equation
ICCO[C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[O:8][C:7](=[O:15])[C:6]=1OCCI.[C:20](=[O:23])([O-])[O-:21].[Na+].[Na+].[C:26](#N)[CH3:27]>>[C:20]([C:6]1[C:7](=[O:15])[O:8][C:9]2[C:14]([CH:5]=1)=[CH:13][CH:12]=[CH:11][CH:10]=2)([O:21][CH2:26][CH3:27])=[O:23]

Participants

4

Reactant 3

HCID 6342AcetonitrileHCID 10340Sodium Carbonate2×HCID 86754529HCID 86754529, compound

Product 1

HCID 15800Ethylcoumarin-3-carboxylate

Procedure

A 1.0 g (1.8 mmol) sample of bis-iodoethoxy-coumarin (from Example 32 or Example 34) and 0.47 g (1.8 mmol) of 1,4,10,13-tetraoxa-7,16-diazacycloctadecane (i.e., 4,13-diaza-18-crown-6) were separately dissolved in 50 ml portions of dry acetonitrile. The combined solutions (100 ml total) were refluxed under nitrogen for six days in the presence of 5 equivalents (0.94 g) anhydrous sodium carbonate. During the reaction, the coarse sodium carbonate was converted to an extremely fine powder. The cooled reaction mixture was filtered and the solution was evaporated to dryness in vacuo. The residue was dissolved in methylene chloride, and the solution was filtered. Evaporation of the methylene chloride using the rotary evaporator at aspirator pressure, followed by oil pump pressure, gave a yellow foam (>100% of the calculated yield). The crude product was purified by chromatography on deactivated neutral alumina first using methylene chloride to elute unreacted starting materials, followed by a 1-5% ethanol/methylene chloride mixture to elute the product. About 50% of calculated amount of the product was recovered, consisting essentially of the desired product (VI). LRMS FAB (triethanolamine) calculated m/e for C28H40N2O10 was 564.27, whereas the observed m/e was 587, [VIII(Na)] +; free [VII]+ was not observed. UV (phosphate buffered saline) Imax =374 nm, 312 nm. Fluorescence (phosphate buffered saline) showed Iex =371 nm and Icm =453 nm.

Workup

  1. customDuring the reaction
  2. customThe cooled reaction mixture
  3. filtrationwas filtered
  4. customthe solution was evaporated to dryness in vacuo
  5. dissolutionThe residue was dissolved in methylene chloride
  6. filtrationthe solution was filtered
  7. customEvaporation of the methylene chloride using
  8. customthe rotary evaporator at aspirator pressure
  9. customgave a yellow foam (>100% of the
  10. customcalculated yield)
  11. customThe crude product was purified by chromatography on deactivated neutral alumina first
  12. washto elute unreacted
  13. washto elute the product
  14. customAbout 50% of calculated amount of the product was recovered

Sources & evidence

ORD record
ord-8f807aba173449018b6a44794d2485b2
Source dataset
uspto-grants-1999_09
Patent number
US05958782

Reaction notes

Loading…