4-(3-Ethynylphenoxy)-1,2-dinitrobenzene → 4-(3-Ethynylphenoxy)benzene-1,2-diamine

HRID 2397518Notes

Reaction equation

HRID 2397518 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH:19]=[CH:20][CH:21]=1)[O:6][C:7]1[CH:12]=[CH:11][C:10]([N+:13]([O-])=O)=[C:9]([N+:16]([O-])=O)[CH:8]=1)#[CH:2]>[OH-].[NH4+].O1CCCC1.[Zn]>[C:1]([C:3]1[CH:4]=[C:5]([CH:19]=[CH:20][CH:21]=1)[O:6][C:7]1[CH:12]=[CH:11][C:10]([NH2:13])=[C:9]([NH2:16])[CH:8]=1)#[CH:2]

Participants

5

Reactant 1

HCID 203569524-(3-Ethynylphenoxy)-1,2-dinitrobenzene

Product 1

HCID 213262494-(3-Ethynylphenoxy)benzene-1,2-diamine

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolventHCID 14923Ammonium HydroxideSolvent2×

Procedure

To a rapidly stirred suspension of 25 g (0.38 g atom) of powdered zinc in 25 ml of concentrated ammonium hydroxide was added a solution containing 5.0 g (17.6 mmoles) of 4-(3-ethynylphenoxy)-o-dinitrobenzene dissolved in 25 ml of tetrahydrofuran. The mixture was stirred at room temperature for 1/2 hour, at which time an additional 5 ml of ammonium hydroxide was added, and the solution stirred an additional half hour. At that time, the reaction mixture was filtered by suction, and the residue was washed with several portions of tetrahydrofuran. The filtrate was extracted with several portions of ether, and the combined ether extracts washed with water. Evaporation of the organic layer in vacuo yielded a dark red oil. Chromatography of the residue on 1" × 12" dry column of silica gel afforded an initial red band (elution with methylene chloride) of side-product. Further elution using ethyl acetate produced a second band of desired product. Evaporation of solvent in vacuo yielded 3.3 g (84%) of 4-(3-ethynylphenoxy)-o-phenylenediamine as a dark orange oil.

Workup

  1. additionwas added a solution
  2. additionwas added
  3. filtrationAt that time, the reaction mixture was filtered by suction
  4. washthe residue was washed with several portions of tetrahydrofuran
  5. extractionThe filtrate was extracted with several portions of ether
  6. washthe combined ether extracts washed with water
  7. customEvaporation of the organic layer in vacuo
  8. customyielded a dark red oil
  9. customChromatography of the residue on 1" × 12" dry column of silica gel
  10. customafforded an initial
  11. washred band (elution with methylene chloride) of side-product
  12. washFurther elution

Sources & evidence

ORD record
ord-15cb924c28da4b64aca260fbd3a0ff66
Source dataset
uspto-grants-1977_05
Patent number
US04022746

Reaction notes

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