m-Chloroperbenzoic acid → tert-butyl N-(1-oxaspiro(2.3)hexan-5-yl)carbamate

HRID 577722ノート

反応式

HRID 577722 の反応式
[C:1]([O:5][C:6](=[O:13])[NH:7][CH:8]1[CH2:11][C:10](=[CH2:12])[CH2:9]1)([CH3:4])([CH3:3])[CH3:2].ClC1C=CC=C(C(OO)=[O:22])C=1>ClCCl>[C:1]([O:5][C:6](=[O:13])[NH:7][CH:8]1[CH2:9][C:10]2([O:22][CH2:12]2)[CH2:11]1)([CH3:4])([CH3:3])[CH3:2]

参加物

4

反応物 2

HCID 70297m-Chloroperbenzoic acidHCID 28875369tert-butyl N-(3-methylidenecyclobutyl)carbamate

生成物 1

HCID 58520785tert-butyl N-(1-oxaspiro(2.3)hexan-5-yl)carbamate収率 61.2%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

A solution of (3-methylene-cyclobutyl)-carbamic acid tert-butyl ester (4.27 g, 23.3 mmol) in dichloromethane (95 mL) was cooled to 0° C. in an ice/water bath. 3-Chloroperbenzoic acid (77% technical grade, 5.84 g, 26 mmol) was added in small portions. After stirring at 0° C. for 1.5 hours, the mixture was transferred to a separatory funnel and washed sequentially with 10% aqueous Na2SO3 (50 mL), saturated aqueous NaHCO3 (30 mL), and saturated aqueous NaCl (30 mL). The organic layer was dried over magnesium sulfate, filtered, concentrated, and purified by silica gel chromatography (eluting with 30-100% ethyl acetate in heptane), affording the title compound (2.84 g, 61%) as a white solid. NMR showed a 1:1 mixture of N,O-cis/trans isomers. 1H NMR (400 MHz, chloroform-d) δ ppm 1.46 (d, J=1.26 Hz, 9H) 2.35-2.45 (m, 2H) 2.67-2.83 (m, 4H) 3.97-4.36 (m, 1H) 4.77 (br. s., 1H)

後処理

  1. customthe mixture was transferred to a separatory funnel
  2. washwashed sequentially with 10% aqueous Na2SO3 (50 mL), saturated aqueous NaHCO3 (30 mL), and saturated aqueous NaCl (30 mL)
  3. dry with materialThe organic layer was dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. custompurified by silica gel chromatography (eluting with 30-100% ethyl acetate in heptane)

出典と根拠

ORDレコード
ord-31a9ba636d8046198ace0f8864d2cddf
出典データセット
uspto-grants-2015_05
特許番号
US09040547B2

反応ノート

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