Diethyl Oxalate → Ethyl 7-(benzyloxy)-1h-indole-2-carboxylate

HRID 1762939

Reaktionsgleichung

Reaktionsgleichung von HRID 1762939
C(O[C:4](=O)[C:5]([O:7][CH2:8][CH3:9])=[O:6])C.[CH2:11]([O:18][C:19]1[C:20]([N+:26]([O-])=O)=[C:21]([CH3:25])[CH:22]=[CH:23][CH:24]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C([O-])C.[K+]>C(OCC)C>[CH2:8]([O:7][C:5]([C:4]1[NH:26][C:20]2[C:21]([CH:25]=1)=[CH:22][CH:23]=[CH:24][C:19]=2[O:18][CH2:11][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)=[O:6])[CH3:9]

Komponenten

5

Edukt 3

HCID 7268Diethyl OxalateHCID 33441871-Benzyloxy-3-methyl-2-nitrobenzeneHCID 23670592Potassium ethoxide

Produkt 1

HCID 13242189Ethyl 7-(benzyloxy)-1h-indole-2-carboxylateAusbeute 36,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel2×

Versuchsvorschrift

Under agitation, 26.3 g of oxalic acid diethyl ester and, 15 minutes later, a solution of 21.9 g of 3-benzyloxy-2-nitrotoluene in 30 ml of diethyl ether are added dropwise to a suspension of 9 g of potassium ethanolate in 200 ml of diethyl ether. The reaction mixture is heated for 20 hours under reflux; the thus-separated potassium salt of 3-benzyloxy-2-nitrophenylpyruvic acid ethyl ester is vacuum-filtered and washed with diethyl ether. The salt is then dissolved in a mixture of 200 ml of ethanol and 200 ml of concentrated acetic acid, the solution is combined with 50 g of powdered iron and heated under reflux for 90 minutes. The reaction mixture is allowed to cool, poured into 1 liter of ice water, filtered over kieselguhr, and the kieselguhr washed with diethyl ether. The organic phase is separated and the aqueous phase is extracted three times with diethyl ether. The combined organic phases are washed with saturated sodium carbonate solution, dried, and concentrated under vacuum. The residue is recrystallized from ethanol, thus obtaining 9.6 g of 7-benzyloxyindole-2-carboxylic acid ethyl ester, mp 82°-83° C.

Aufarbeitung

  1. temperatureThe reaction mixture is heated for 20 hours
  2. temperatureunder reflux
  3. filtrationthe thus-separated potassium salt of 3-benzyloxy-2-nitrophenylpyruvic acid ethyl ester is vacuum-filtered
  4. washwashed with diethyl ether
  5. dissolutionThe salt is then dissolved in a mixture of 200 ml of ethanol and 200 ml of concentrated acetic acid
  6. temperatureheated
  7. temperatureunder reflux for 90 minutes
  8. temperatureto cool
  9. additionpoured into 1 liter of ice water
  10. filtrationfiltered over kieselguhr
  11. washthe kieselguhr washed with diethyl ether
  12. customThe organic phase is separated
  13. extractionthe aqueous phase is extracted three times with diethyl ether
  14. washThe combined organic phases are washed with saturated sodium carbonate solution
  15. customdried
  16. concentrationconcentrated under vacuum
  17. customThe residue is recrystallized from ethanol

Quellen und Nachweise

ORD-Eintrag
ord-63e4aa2a37db48b9a7df064c6a28374b
Quelldatensatz
uspto-grants-1989_05
Patentnummer
US04835175

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