Dichloromethane → tert-Butyl 6-Oxa-3-azabicyclo(3.1.0)hexane-3-carboxylate

HRID 252089

反応式

HRID 252089 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]=[CH:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].ClC1C=C(C=CC=1)C(OO)=[O:18].ClCCl>ClCCCl>[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]2[CH:10]([O:18]2)[CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

参加物

5

反応物 3

HCID 6344DichloromethaneHCID 70297m-Chloroperbenzoic acid2 回HCID 5148195tert-Butyl 2,5-dihydro-1H-pyrrole-1-carboxylate

生成物 1

HCID 10103880tert-Butyl 6-Oxa-3-azabicyclo(3.1.0)hexane-3-carboxylate収率 71%

試薬・触媒・溶媒 1

HCID 111,2-Dichloroethane溶媒

実験手順

Stir a mixture of 2,5-dihydropyrrole-1-carboxylic acid tert-butyl ester (2 g, 11.8 mmol), 3-chloroperoxybenzoic acid (77%, 3.1 g, 14.2 mmol) and 3-tert-butyl-4-hydroxy-5-methylsulfide (254 mg, 0.7 mmol) in 1,2-dichloroethane (50 mL) at 85° C. for 4 h under nitrogen. Add extra 3-chloroperoxybenzoic acid (77%, 1.16 g, 4.7 mmol) and stir at 85° C. for 5 h. Allow to cool to room temperature and add dichloromethane (120 mL), wash with 5% aqueous sodium bisulfate, then with saturated aqueous sodium hydrogen carbonate and finally with saturated aqueous sodium chloride, dry (magnesium sulfate), concentrate and chromatograph on silica gel, eluting with 0:100 to 40:60 ethyl acetate:cyclohexane to give 6-oxa-3-azabicyclo[3.1.0]hexane-3-carboxylic acid tert-butyl ester (1.55 g, 71%). 1H NMR (400 MHz, CDCl3) δ 3.82 (1H, d, J=13.20 Hz), 3.74 (1H, d, J=12.72 Hz), 3.67 (2H, d, J=3.42 Hz), 3.31 (2H, dd, J=13.45, 5.14 Hz), 1.44 (9H, s).

後処理

  1. stirringstir at 85° C. for 5 h
  2. washwash with 5% aqueous sodium bisulfate
  3. dry with materialwith saturated aqueous sodium hydrogen carbonate and finally with saturated aqueous sodium chloride, dry (magnesium sulfate)
  4. concentrationconcentrate
  5. washchromatograph on silica gel, eluting with 0:100 to 40:60 ethyl acetate

出典と根拠

ORDレコード
ord-81f91683b3604389a8c6adac3c43ded9
出典データセット
uspto-grants-2011_01
特許番号
US07868014B2

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