Acetic Acid → HCID 12677755, compound

HRID 2419470Notes

Reaction equation

HRID 2419470 reaction equation
[C:1]([CH:4]1[C:13](=[O:14])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[O:6][CH2:5]1)(=[O:3])[CH3:2].[H-].[Na+].[C:17](OCC)(=[O:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19].C(O)(=O)C>O1CCCC1>[CH2:21]([O:20][C:18](=[O:19])[C:17](=[O:23])[CH2:2][C:1]([CH:4]1[C:13](=[O:14])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[O:6][CH2:5]1)=[O:3])[CH3:22]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 12677753HCID 12677753, compound

Product 1

HCID 12677755HCID 12677755, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-40 °C

Procedure

A solution of 3-acetyl-4-chromanone (1.8 g, 9.5 mmoles, described in Example 5) in dry tetrahydrofuran (20 ml) is added dropwise to a suspension of 57% sodium hydride (1.17 g, 28.5 mmoles) in tetrahydrofuran (30 ml) and the mixture is heated at reflux temperature for 15 min. A solution of diethyl oxalate (1.39 g, 9.5 mmoles) is added dropwise under an atmosphere of nitrogen. The reaction mixture is heated at reflux temperature overnight and cooled to -40° C. A solution of 50% aqueous acetic acid (4 ml) is added and the reaction mixture evaporated. The residue is partitioned between chloroform and water, the organic phase is separated and the aqueous phase is re-extracted with chloroform. The combined chloroform extracts are dried and evaporated. The residue is subjected to chromatography on silica gel. Elution with chloroform affords 4-(4-chromanon-3-yl)-2,4-dioxobutyric acid ethyl ester (VII; R1, R2, R3R4 and R17 = H, R19 = C2H5 and X = O), which is crystallized from ether, m.p. 117°-119° C.

Workup

  1. temperaturethe mixture is heated
  2. temperatureat reflux temperature for 15 min
  3. temperatureThe reaction mixture is heated
  4. temperatureat reflux temperature overnight
  5. customthe reaction mixture evaporated
  6. customThe residue is partitioned between chloroform and water
  7. customthe organic phase is separated
  8. extractionthe aqueous phase is re-extracted with chloroform
  9. dry with materialThe combined chloroform extracts are dried
  10. customevaporated
  11. washElution with chloroform

Sources & evidence

ORD record
ord-93f4c1684ab94eeeabbc297faa657f81
Source dataset
uspto-grants-1978_08
Patent number
US04105778

Reaction notes

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