Ethyl Acetate → Tert-butyl 8-oxa-4-azabicyclo[5.1.0]octane-4-carboxylate

HRID 1244354노트

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HRID 1244354 반응식
[C:1]([O:5][C:6]([N:8]1[CH2:14][CH2:13][CH:12]=[CH:11][CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].ClC1C=CC=C(C(OO)=[O:23])C=1.C(OC(=O)C)C>ClCCl>[C:1]([O:5][C:6]([N:8]1[CH2:14][CH2:13][CH:12]2[CH:11]([O:23]2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

참가 물질

5

반응물 3

HCID 8857Ethyl AcetateHCID 70297m-Chloroperbenzoic acidHCID 12969195tert-Butyl 2,3,6,7-tetrahydro-1H-azepine-1-carboxylate

생성물 1

HCID 58717040Tert-butyl 8-oxa-4-azabicyclo[5.1.0]octane-4-carboxylate수율 82%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a stirred solution of 16.4 g 2,3,6,7-tetrahydro-azepine-1-carboxylic acid tert-butyl ester in 420 ml dichloromethane was added at −60° C. 35.8 g m-chloroperbenzoic acid (70% purity). The mixture was allowed to slowly warm to room temperature overnight, 1 l ethylacetate was added and the solution was extracted with aqueous sodium bicarbonate, 1N aqueous sodium hydroxide and brine. Evaporation of the solvent and chromatography yielded 14.5 g (82%) 8-oxa-4-aza-bicyclo[5.1.0]octane-4-carboxylic acid tert-butyl ester as colorless liquid; MS (EI): m/e=213 (M+,5%), 158 (22%), 140 (12%), 57 (100%). To a solution of 14.3 g 8-oxa-4-aza-bicyclo[5.1.0]octane-4-carboxylic acid tert-butyl ester in 750 ethanol was added 150 ml water, 35.8 g ammonium chloride and 43.6 g sodium azide. The mixture was stirred at 75° C. over night, the solvents were greatly removed by distillation under vacuum and the residue was suspended in ethanol and filtered. The ethanol was distilled off and the residue was suspended in ethylacetate and filtered. Removal of the solvent and chromatography on silicagel with ethylacetate/hexane 1:1, yielded 13.5 g (79%) 4-azido-5-hydroxy-azepane-1-carboxylic acid tert-butyl ester as a viscous oil; MS (ISP): m/e=257 (M+H+).

후처리

  1. extractionthe solution was extracted with aqueous sodium bicarbonate, 1N aqueous sodium hydroxide and brine
  2. customEvaporation of the solvent and chromatography

출처 및 근거

ORD 기록
ord-b105e948edd94d0fb8d490a87d047d02
출처 데이터셋
uspto-grants-2006_10
특허 번호
US07122545B2

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