4-Bromo-1-but-3-ynyloxy-2-nitro-benzene → 5-Bromo-2-but-3-ynyloxy-phenylamine

HRID 886070Notes

Reaction equation

HRID 886070 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH2:10][C:11]#[CH:12])=[C:4]([N+:13]([O-])=O)[CH:3]=1>[Fe].O.O.O.O.O.O.[Fe](Cl)(Cl)Cl.C(O)(=O)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH2:10][C:11]#[CH:12])=[C:4]([NH2:13])[CH:3]=1

Participants

5

Reactant 1

HCID 582050294-Bromo-1-but-3-ynyloxy-2-nitro-benzene

Product 1

HCID 582049095-Bromo-2-but-3-ynyloxy-phenylamineYield 89.3%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 16211236Trichloroiron;hexahydrateCatalystHCID 176Acetic AcidSolvent

Procedure

4-Bromo-1-but-3-ynyloxy-2-nitro-benzene (82% pure, 4.22 g, 12.5 mmol) was heated in a mixture of IMS (Industrial Methylated Spirits, 40 mL) and glacial acetic acid (2 mL) at approx. 50° C. until a solution was formed. Iron powder (5.05 g, 89.8 mmol) and iron (III) chloride hexahydrate (0.56 g, 1.56 mmol) were added and the mixture was heated under reflux for 18 h. The cooled mixture was filtered through Celite®, and washed through with ethyl acetate. The filtrate was washed with water, followed by brine, dried (Na2SO4), filtered and concentrated in vacuo. The resultant residue was subjected to flash chromatography (SiO2, gradient 10 to 20% ethyl acetate in cyclohexane) to give 5-Bromo-2-but-3-ynyloxy-phenylamine as an orange oil (2.68 g, 89%). LCMS: RT=4.10 min, M+H+=240/242.

Workup

  1. customwas formed
  2. temperaturethe mixture was heated
  3. temperatureunder reflux for 18 h
  4. filtrationThe cooled mixture was filtered through Celite®
  5. washwashed through with ethyl acetate
  6. washThe filtrate was washed with water
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d562e4b440fd461cbf595b8fddd06fe8
Source dataset
uspto-grants-2012_08
Patent number
US08242104B2

Reaction notes

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