Hydrochloric Acid → 4,5-DIIODO-BENZENE-1,2-DIAMINE

HRID 426369Notes

Reaction equation

HRID 426369 reaction equation
[I:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[C:5]([N+:11]([O-])=O)=[CH:4][C:3]=1[I:14].Cl.C(N(CC(O)=O)CC(O)=O)CN(CC(O)=O)CC(O)=O.[OH-].[K+]>[Fe].CCO>[NH2:8][C:6]1[CH:7]=[C:2]([I:1])[C:3]([I:14])=[CH:4][C:5]=1[NH2:11]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6049Ethylenediaminetetraacetic AcidHCID 14797Potassium HydroxideHCID 110698251,2-diiodo-4,5-dinitrobenzene

Product 1

HCID 116101834,5-DIIODO-BENZENE-1,2-DIAMINEYield 66.4%

Reagents, catalysts & solvents 2

HCID 23925IronCatalyst2×HCID 702EthanolSolvent2×

Procedure

Following a literature procedure, a sample of 1 (17.42 g, 41.5 mmol) and a magnetic stirring bar were added to a 500 mL conical flask fitted with a jacketed condenser. EtOH (95%, 150 mL) and conc. aqueous HCl (68.6 mL, 0.83 mol) were added, and the mixture was stirred and heated to boiling. Fe (18.59 g, 0.332 mol) was added in portions, resulting in foaming of the mixture and accelerated refluxing of the EtOH, which would subside within a few minutes of each addition. The reaction was heated for an additional 45 min beyond the final addition of Fe. A hot solution of EDTA (156 g, 0.411 mol, in 300 mL H2O) was added to the reaction mixture, and KOH pellets were added until the solution was alkaline to pH paper. The hot mixture was extracted twice with ethyl acetate and the extracts were combined, washed with water, followed by brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tan needles (9.92 g, 66%): mp 135-136° C.; 1H NMR (d8-THF) δ 4.21 (brs, 4H), 7.03 (s, 2H); 13C NMR (d8-THF) δ 91.1, 124.5, 137.6; Anal. Calcd for C6H6I2N2: C, 20.02; H, 1.68; N, 7.78. Found: C, 20.19; H, 1.59, 7.71.

Workup

  1. customfitted with a jacketed condenser
  2. temperatureheated to boiling
  3. customresulting in foaming of the mixture
  4. additionwould subside within a few minutes of each addition
  5. temperatureThe reaction was heated for an additional 45 min beyond the final
  6. additionwere added until the solution
  7. extractionThe hot mixture was extracted twice with ethyl acetate
  8. washwashed with water
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated to dryness
  12. customThe residue was recrystallized (EtOH/water)

Sources & evidence

ORD record
ord-67239a0368cf49cd829a59557951e0ae
Source dataset
uspto-grants-2012_01
Patent number
US08106393B2

Reaction notes

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