Ammonium Acetate → Ethyl 4-oxo-1,4,5,6,7,8-hexahydrocyclohepta[B]pyrrole-3-carboxylate

HRID 1290087

Reaction equation

HRID 1290087 reaction equation
[O:1]=[C:2]1[C:11]2[C:10]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:9]O[C:7]=2[CH2:6][CH2:5][CH2:4][CH2:3]1.C([O-])(=O)C.[NH4+:21]>CN(C)C=O>[O:1]=[C:2]1[C:11]2[C:10]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:9][NH:21][C:7]=2[CH2:6][CH2:5][CH2:4][CH2:3]1

Participants

4

Reactant 2

HCID 517165Ammonium AcetateHCID 18696560ethyl 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]furan-3-carboxylate

Product 1

HCID 18696565Ethyl 4-oxo-1,4,5,6,7,8-hexahydrocyclohepta[B]pyrrole-3-carboxylateYield 50.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
115 °C

Procedure

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, and extracted 2X 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 (5% 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; the resulting precipitate was 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.

Workup

  1. concentrationThe mixture was concentrated in vacuo, ice water
  2. additionwas added
  3. extractionextracted 2X with dichloromethane
  4. washThe combined organic layers were washed with saturated aqueous sodium bicarbonate
  5. dry with materialbrine, dried over sodium sulfate
  6. filtrationfiltered through a small pad of Silica gel (5% methyl alcohol/dichloromethane)
  7. concentrationthe filtrate concentrated in vacuo

Sources & evidence

ORD record
ord-eb7882379a2d48b3ba19c20e616e58b7
Source dataset
uspto-grants-1998_05
Patent number
US05750702

Linked notes

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