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

HRID 1244354ノート

反応式

HRID 1244354 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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+).

後処理

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

出典と根拠

ORDレコード
ord-b105e948edd94d0fb8d490a87d047d02
出典データセット
uspto-grants-2006_10
特許番号
US07122545B2

反応ノート

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