Sulfuric Acid → 4-(3-Ethynylphenoxy)-1,2-dinitrobenzene

HRID 2397517Notes

Reaction equation

HRID 2397517 reaction equation
[OH-].[Na+].[N+:3]([C:6]1[CH:7]=[C:8]([CH:21]=[CH:22][C:23]=1[N+:24]([O-:26])=[O:25])[O:9][C:10]1[CH:11]=[C:12]([CH:18]=[CH:19][CH:20]=1)[CH:13]=[C:14](Cl)C=O)([O-:5])=[O:4].S(=O)(=O)(O)O>O1CCOCC1>[C:13]([C:12]1[CH:11]=[C:10]([CH:20]=[CH:19][CH:18]=1)[O:9][C:8]1[CH:21]=[CH:22][C:23]([N+:24]([O-:26])=[O:25])=[C:6]([N+:3]([O-:5])=[O:4])[CH:7]=1)#[CH:14]

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 537336452-Chloro-3-[3-(3,4-dinitrophenoxy)phenyl]prop-2-enal

Product 1

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

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To 50 ml of refluxing 1N sodium hydroxide solution, under a nitrogen atmosphere, was added a solution containing 10 g (0.028 mole) of m-(3,4-dinitrophenoxy)-α-chlorocinnamaldehyde dissolved in 50 ml of 1,4-dioxane. The dark mixture was refluxed for 1/2 hour at which time the solution was cooled and acidified with 10% sulfuric acid. The reaction mixture was extracted with several 50 ml portions of ether, and the combined extracts evaporated to dryness. The residue was chromatographed on a 1" × 12" dry column of silica gel. Elution of the column using 3/1 hexane/methylene chloride produced a first band of side-product. Further elution using 1/1 hexane/methylene chloride yielded a second band which contained the desired product. Evaporation of the eluate to dryness in vacuo afforded 2 g (25%) of 4-(3-ethynylphenoxy)-o-dinitrobenzene as light yellow crystals, m.p. 68°-69° C.

Workup

  1. additionunder a nitrogen atmosphere, was added a solution
  2. temperatureThe dark mixture was refluxed for 1/2 hour at which time the solution
  3. temperaturewas cooled
  4. extractionThe reaction mixture was extracted with several 50 ml portions of ether
  5. customthe combined extracts evaporated to dryness
  6. customThe residue was chromatographed on a 1" × 12"
  7. customdry column of silica gel
  8. washElution of the column
  9. customproduced a first band of side-product
  10. washFurther elution
  11. customyielded a second band which

Sources & evidence

ORD record
ord-87c7a18104844c368a425ce19aa32e70
Source dataset
uspto-grants-1977_05
Patent number
US04022746

Reaction notes

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