Réaction #1001

Équation de réaction

ethyl 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]furan-3-carboxylate

ammonium acetate

→

ethyl 4-oxo-1,4,5,6,7,8-hexahydro-cyclohepta[b]pyrrole-3-carboxylate

Rendement 50.7%

Solvants

N,N-dimethylformamide

Conditions de réaction

Traitement

1. 1
   ConcentrationThe mixture was concentrated in vacuo, ice water
2. 2
   workup.ADDITIONwas added
3. 3
   Extractionextracted 2× with dichloromethane
4. 4
   LavageThe combined organic layers were washed with saturated aqueous sodium bicarbonate
5. 5
   Séchagebrine, dried over sodium sulfate
6. 6
   Filtrationfiltered through a small pad of Silica gel (1:19 methyl alcohol/dichloromethane)
7. 7
   Concentrationthe filtrate concentrated in vacuo

Mode opératoire

A mixture of ethyl 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]furan-3-carboxylate (3.48 g, 15.7 mmol) and ammonium acetate (2.41 g, 31.3 mmol) in N,N-dimethylformamide (25 mL) was heated at 115° C. for 6 hours. The mixture was concentrated in vacuo, ice water was added, then extracted 2× with dichloromethane. The combined organic layers were washed with saturated aqueous sodium bicarbonate then brine, dried over sodium sulfate, filtered through a small pad of Silica gel (1:19 methyl alcohol/dichloromethane), and the filtrate concentrated in vacuo to give ethyl 4-oxo-1,4,5,6,7,8-hexahydro-cyclohepta[b]pyrrole-3-carboxylate (1.76 g). A solution of this ester in aqueous 5N sodium hydroxide (30 mL) and ethyl alcohol (6 mL) was heated at reflux for 1 hour, then cooled in an ice bath. The mixture was acidified with hydrochloric acid, and the precipitate collected, rinsed with water followed by diethyl ether and allowed to dry to give 4-oxo-1,4,5,6,7,8-hexahydro-cyclohepta[b]pyrrole-3-carboxylic acid (1.17 g). m.p. 225°-227° C.

Source