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

HRID 237247노트

반응식

HRID 237247 반응식
[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]

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-7ac7d892a6ff48a298a2733aeaeeedcb
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08642583B2

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