Nitric Acid → 1-Nitroanthraquinone

HRID 1578749Notes

Reaction equation

HRID 1578749 reaction equation
[CH:1]1[C:14]2[C:13](=[O:15])[C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[C:6](=[O:16])[C:5]=2[CH:4]=[CH:3][CH:2]=1.[N+:17]([O-])([OH:19])=[O:18].S(=O)(=O)(O)O>C(Cl)Cl>[N+:17]([C:8]1[C:7]2[C:6](=[O:16])[C:5]3[C:14](=[CH:1][CH:2]=[CH:3][CH:4]=3)[C:13](=[O:15])[C:12]=2[CH:11]=[CH:10][CH:9]=1)([O-:19])=[O:18]

Participants

5

Reactant 3

HCID 944Nitric Acid2×HCID 1118Sulfuric AcidHCID 6780Anthraquinone

Product 1

HCID 67041-Nitroanthraquinone

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

A suspension of 250 g. of anthraquinone in 200 ml. of methylene chloride is treated under reflux conditions, over the course of about 3 hours, with a nitration acid of 68.4 ml. of 98% strength nitric acid and 85.2 ml. of 100% strength sulphuric acid. The mixture is stirred for a further 4 hours at this temperature and cooled to 20°C. After 700 ml. of methylene chloride have been added, 190 ml. of 98% strength nitric acid are allowed to run in at 20°C. After stirring for about 30 minutes longer, the upper, organic phase is withdrawn and clarified by passing it through a frit, and the filter residue is rinsed with a mixture of 95 ml. of methylene chloride and 5 ml. of 98% strength nitric acid. The clear filtrate is decomposed with 500 ml. of water and the mixture is stirred for a further hour at about 20°C. The lemon-yellow precipitate is then filtered off and is washed successively with 2 × 100 ml. of methylene chloride and 2 × 100 ml. of 1% strength aqueous di-sec.-butylnaphthalene-sulphonate solution and finally with water until neutral. After drying at about 100°C, the yield is 229 g. The product contains 89% of 1-nitroanthraquinone and inter alia contains 0.25% of anthraquinone, <0.25% of 2-nitroanthraquinone and 1.4% of 1,5-dinitroanthraquinone. To remove the remaining subsidiary components, the 1-nitroanthraquinone obtained is stirred with 1,850 ml. of 2.5% strength sodium sulphite solution for 4 hours under reflux conditions, then filtered off hot, washed and dried. 204 g. of 1-nitroanthraquinone are obtained, containing 95% of 1-nitroanthraquinone, 0.25% of anthraquinone, <0.25% of 2-nitroanthraquinone and 0.9% of 1,5-dinitroanthraquinone. A further fraction of 12 g. of 1-nitroanthraquinone and 2 g. of anthraquinone remains in the methylene chloride mother liquor and can, after evaporation of the solvent, be reintroduced into the next nitration batch.

Workup

  1. additionA suspension of 250 g
  2. customto run in at 20°C
  3. stirringAfter stirring for about 30 minutes longer
  4. customthe upper, organic phase is withdrawn
  5. washthe filter residue is rinsed with a mixture of 95 ml
  6. stirringof water and the mixture is stirred for a further hour at about 20°C
  7. filtrationThe lemon-yellow precipitate is then filtered off
  8. washis washed successively with 2 × 100 ml
  9. customAfter drying at about 100°C
  10. customTo remove the remaining subsidiary components

Sources & evidence

ORD record
ord-c8d255b489a745dbac4b0a2525c568e8
Source dataset
uspto-grants-1976_02
Patent number
US03939185

Reaction notes

Loading…