Imidazole → 4-bromo-2-methoxy-5-[(E)-C-methyl-N-[(4-nitrophenyl)methoxy]carbonimidoyl]phenol

HRID 41943Notes

Reaction equation

HRID 41943 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([OH:10])=[CH:4][C:3]=1[C:11](=O)[CH3:12].Cl.[N+:15]([C:18]1[CH:26]=[CH:25][C:21]([CH2:22][O:23][NH2:24])=[CH:20][CH:19]=1)([O-:17])=[O:16].N1C=CN=C1.C(OCC)(=O)C.CCCCCC>CCO>[N+:15]([C:18]1[CH:19]=[CH:20][C:21]([CH2:22][O:23]/[N:24]=[C:11](/[C:3]2[CH:4]=[C:5]([OH:10])[C:6]([O:8][CH3:9])=[CH:7][C:2]=2[Br:1])\[CH3:12])=[CH:25][CH:26]=1)([O-:17])=[O:16]

Participants

6

Reactant 4

HCID 795ImidazoleHCID 74967Hydroxylamine, O-((4-nitrophenyl)methyl)-, hydrochloride (1:1)HCID 21226206Ethyl acetate hexaneHCID 349091311-(2-Bromo-5-hydroxy-4-methoxyphenyl)ethan-1-one

Product 1

HCID 251004124-bromo-2-methoxy-5-[(E)-C-methyl-N-[(4-nitrophenyl)methoxy]carbonimidoyl]phenol

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A magnetically stirred solution of ketone 39 (162 mg, 0.661 mmol) in EtOH (2.0 mL) was treated with compound 19 (271 mg, 1.32 mmol) and imidazole (68 mg, 0.999 mmol) then the resulting mixture stirred at reflux for 2 h before being cooled and concentrated under reduced pressure. The ensuing residue was partitioned between CH2Cl2 (10 mL) and H2O (10 mL) and the separated aqueous fraction extracted with CH2Cl2 (1×10 ml). The combined organic fractions were then dried (MgSO4), filtered and concentrated under reduced pressure. The resulting mixture was subjected to flash chromatography (15:85 v/v ethyl acetate/hexane) to afford a ca. 3:1 mixture of the E- and Z-isomeric foams of the title compound CP302108 (229 mg, 88%) as a pale-yellow solid, Rf 0.5 in 1:1 v/v ethyl acetate/hexane. Recrystallisation of this material (twice from isopropanol) afforded the major isomer, CP302108-major, as a pale-yellow solid, m.p. 136.8-138.4° C.

Workup

  1. temperatureat reflux for 2 h
  2. temperaturebefore being cooled
  3. concentrationconcentrated under reduced pressure
  4. customThe ensuing residue was partitioned between CH2Cl2 (10 mL) and H2O (10 mL)
  5. extractionthe separated aqueous fraction extracted with CH2Cl2 (1×10 ml)
  6. dry with materialThe combined organic fractions were then dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto afford

Sources & evidence

ORD record
ord-999dc851f1014564b47261f21296e38b
Source dataset
uspto-grants-2013_09
Patent number
US08536157B2

Reaction notes

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