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

HRID 1850078ノート

反応式

HRID 1850078 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 m-CPBA (77 wt %, 23.3 g, 104 mmol). After 15 h, 10% Na2S2O5 was added and the solution allowed to stir until the aqueous was Kl paper negative and 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 and acidified with 1M KHSO4 (220 mL) then extracted with CH2Cl2 (2×). The combined organic layers were washed with brine and dried to give a brown solid that was triturated with EtOAc/hexanes giving 17.6 g (74% yield) of the title compound as a white solid. 1H NMR (500 MHz, 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. extractionthen extracted with CH2Cl2 (2×)
  9. washThe combined organic layers were washed with brine
  10. customdried
  11. customto give a brown solid that

出典と根拠

ORDレコード
ord-ad9c4209efa140f399964a0dad4b8442
出典データセット
uspto-grants-2015_02
特許番号
US08957059B2

反応ノート

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