m-Chloroperbenzoic acid → HCID 131734945, compound

HRID 921903Notes

Reaction equation

HRID 921903 reaction equation
C1C=C(Cl)C=C(C(OO)=[O:9])C=1.[Cl:12][C:13]1[C:18]([CH:19]=[CH2:20])=[CH:17][C:16]([C:21]#[N:22])=[CH:15][C:14]=1[NH:23][C:24](=[O:30])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27]>C(Cl)Cl>[Cl:12][C:13]1[C:18]([CH:19]2[CH2:20][O:9]2)=[CH:17][C:16]([C:21]#[N:22])=[CH:15][C:14]=1[NH:23][C:24](=[O:30])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27]

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 131734946HCID 131734946, compound

Product 1

HCID 131734945HCID 131734945, compoundYield 94.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Added m-CPBA 50% (1.92 gm, 5.56 mmol) in portions to an ice-cooled solution of tert-butyl (2-chloro-5-cyano-3-vinylphenyl)carbamate (Example 399A)(517 mg, 1.86 mmol) in DCM (30 mL). The bath was removed and the reaction was left stirring at room temperature overnight. Added additional 50% MCPBA (0.6 gm) and left stirring overnight. Added 20 mL of 0.5 M NaHCO3 solution and left stirring for 4 hr. The aqueous phase was separated and washed with DCM. The combined organic phases were washed three times with 1 N Na2CO3 solution. After drying with sodium sulfate, the solvents were removed to leave crude tert-butyl (2-chloro-5-cyano-3-(oxiran-2-yl)phenyl)carbamate (516 mg, 94% yield). This was dissolved in a mixture of DCE (12 mi) and MeOH (6 mL) in a microwave vial. Ethanolamine (2.12 mL, 35.0 mmol) was added and the vial was sealed and heated at 60° C. overnight. The solvent was removed and the residue was taken up in DCM and washed with water (2×) and brine. After drying with sodium sulfate, the solvent was removed and radial silica gel chromatography eluting with DCM containing 0 to 14% MeOH and then 10% 2N NH3 in MeOH afforded tert-butyl (2-chloro-5-cyano-3-(1-hydroxy-2-((2-hydroxyethyl)amino)ethyl)phenyl)carbamate (337 mg).

Workup

  1. customThe bath was removed
  2. waitthe reaction was left
  3. additionAdded additional 50% MCPBA (0.6 gm)
  4. waitleft
  5. stirringstirring overnight
  6. additionAdded 20 mL of 0.5 M NaHCO3 solution
  7. waitleft
  8. stirringstirring for 4 hr
  9. customThe aqueous phase was separated
  10. washwashed with DCM
  11. washThe combined organic phases were washed three times with 1 N Na2CO3 solution
  12. dry with materialAfter drying with sodium sulfate
  13. customthe solvents were removed

Sources & evidence

ORD record
ord-efbf5baa90484378bc227e80e6218c00
Source dataset
uspto-grants-2016_03
Patent number
US09273057B2

Reaction notes

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