m-Chloroperbenzoic acid → 3-(5-Bromo-2-hydroxy-phenoxy)-azetidine-1-carboxylic acid tert-butyl ester

HRID 237247ノート

反応式

HRID 237247 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([O:12][C:13]2[CH:18]=[C:17]([Br:19])[CH:16]=[CH:15][C:14]=2C=O)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1C=C(Cl)C=C(C(OO)=[O:30])C=1>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([O:12][C:13]2[CH:18]=[C:17]([Br:19])[CH:16]=[CH:15][C:14]=2[OH:30])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

4

反応物 2

HCID 70297m-Chloroperbenzoic acidHCID 866570483-(5-Bromo-2-formyl-phenoxy)-azetidine-1-carboxylic acid tert-butyl ester

生成物 1

HCID 673444423-(5-Bromo-2-hydroxy-phenoxy)-azetidine-1-carboxylic acid tert-butyl ester

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a CH2Cl2 (280 mL) solution of the title compound of Step B (24.7 g, 69.4 mmol) was added 77% m-CPBA (23.3 g, 104 mmol). After 15 h, 10% Na2S2O5 (aq.) was added and the solution allowed to stir until the aqueous was KI paper negative then extracted with CH2Cl2 (2×). The combined organic layers were washed with saturated NaHCO3 (aq.), concentrated and treated with MeOH (220 mL) and 1N NaOH (220 mL). After 15 h, the reaction was partially concentrated to remove the MeOH, acidified with 1M KHSO4 (220 mL) and extracted with CH2Cl2 (2×). The combined organic layers were washed with brine and dried providing a brown solid that was triturated with EtOAc/hexanes giving 17.6 g (74%) of the title compound as a white solid. 1H NMR (CDCl3): 7.03 (dd, J=8.5, 2.1 Hz, 1H), 6.84 (d, J=8.5 Hz, 1H), 6.64 (d, J=2.2 Hz, 1H), 4.93-4.89 (m, 1H), 4.34 (dd, J=10.1, 6.8 Hz, 1H), 4.03 (dd, J=9.9, 3.7 Hz, 1H), 1.46 (s, 9H).

後処理

  1. extractionextracted with CH2Cl2 (2×)
  2. washThe combined organic layers were washed with saturated NaHCO3 (aq.)
  3. concentrationconcentrated
  4. additiontreated with MeOH (220 mL) and 1N NaOH (220 mL)
  5. waitAfter 15 h
  6. concentrationthe reaction was partially concentrated
  7. customto remove the MeOH
  8. extractionextracted with CH2Cl2 (2×)
  9. washThe combined organic layers were washed with brine
  10. customdried
  11. customproviding a brown solid that
  12. customwas triturated with EtOAc/hexanes giving 17.6 g (74%) of the title compound as a white solid

出典と根拠

ORDレコード
ord-7ac7d892a6ff48a298a2733aeaeeedcb
出典データセット
uspto-grants-2014_02
特許番号
US08642583B2

反応ノート

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