Water → STK377473

HRID 1680654Notes

Reaction equation

HRID 1680654 reaction equation
[C:1]1([OH:11])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.[OH-].[K+].O.[Cl:15][C:16]1[CH:17]=[C:18]([N+:23]([O-:25])=[O:24])[CH:19]=[CH:20][C:21]=1Cl>C1(C)C(C)=CC=CC=1.[Cu]>[C:1]1([O:11][C:21]2[CH:20]=[CH:19][C:18]([N+:23]([O-:25])=[O:24])=[CH:17][C:16]=2[Cl:15])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 962WaterHCID 70051-NaphtholHCID 74431,2-Dichloro-4-nitrobenzeneHCID 14797Potassium Hydroxide

Product 1

HCID 4257839STK377473

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 7237O-XyleneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 144 g (1 mol) of α-naphthol in 1 liter of xylene were added 65 g (1 mol) of finely powdered 88% potassium hydroxide. The mixture thus obtained was boiled under N2 -atmosphere in an apparatus equipped with an effective water trap under constant stirring until no water was separating any more and the head temperature had risen to 137° C. Then, 500 ml of dimethylformamide were added, The solution thus obtained was boiled for a further two hours under nitrogen in the apparatus equippped with an effective water trap; then, 500 ml of solvent were distilled therefrom. The residue was allowed to cool off under nitrogen to 100° C., and 211 g (1 mol) of 3,4-dichloronitrobenzene and 1 g of copper powder were added. Then it was refluxed under nitrogen while stirring for 8 hours (approx. 140° C. bottom temperature). Afterwards it was allowed to cool off to ~50° C., approx. 30 g of kieselguhr were added, the mixture thus obtained was stirred, and the undissolved substance was removed by suction filtration and washed with xylene. The filtrate united with the wash liquid was evaporated in vacuo to dryness. The residue was dissolved in warm toluene. The obtained solution was extracted thrice with separate portions of 500 ml of 1 N sodium hydroxide solution and, subsequently, twice with separate portions of 500 ml of water. Then, the toluene phase was evaporated to dryness in vacuo (crude yield: 290 g, 96% of theory). The residue was stirred with 1.7 liter of gasoline (boiling range 80°-110° C.) at approx. 85° C. Most of the crude product dissolved; some resin remain undissolved. The solution decanted therefrom was allowed to cool off slowly. First, the product precipitated oily; however, by trituration at approx. 50° C., crystals were obtained. Then it was cooled for several hours to 5° C. and the crystalline product was removed by suction filtration.

Workup

  1. customThe mixture thus obtained
  2. customequipped with an effective water trap
  3. customwas separating any more and the head temperature
  4. customhad risen to 137° C
  5. additionThen, 500 ml of dimethylformamide were added
  6. customThe solution thus obtained
  7. customequippped with an effective water trap
  8. distillationthen, 500 ml of solvent were distilled
  9. temperatureThen it was refluxed under nitrogen
  10. temperatureto cool off to ~50° C.
  11. additionapprox. 30 g of kieselguhr were added
  12. customthe mixture thus obtained
  13. stirringwas stirred
  14. customthe undissolved substance was removed by suction filtration
  15. washwashed with xylene
  16. customwas evaporated in vacuo to dryness
  17. dissolutionThe residue was dissolved in warm toluene
  18. extractionThe obtained solution was extracted thrice with separate portions of 500 ml of 1 N sodium hydroxide solution
  19. customThen, the toluene phase was evaporated to dryness in vacuo (crude yield: 290 g, 96% of theory)
  20. stirringThe residue was stirred with 1.7 liter of gasoline (boiling range 80°-110° C.) at approx. 85° C
  21. dissolutionMost of the crude product dissolved
  22. customThe solution decanted
  23. temperatureto cool off slowly
  24. customFirst, the product precipitated oily
  25. customhowever, by trituration at approx. 50° C., crystals were obtained
  26. temperatureThen it was cooled for several hours to 5° C.
  27. customthe crystalline product was removed by suction filtration

Sources & evidence

ORD record
ord-88d7113b71044ee39bfeceb86368be53
Source dataset
uspto-grants-1981_06
Patent number
US04275077

Reaction notes

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