Hydrochloric Acid → HCID 13442313, compound

HRID 1902573Notes

Reaction equation

HRID 1902573 reaction equation
[N+]([C:4]1[CH:12]=[C:11]([N+:13]([O-:15])=[O:14])[CH:10]=[C:6]([C:7]([OH:9])=O)[C:5]=1[C:16]([OH:18])=[O:17])([O-])=O.C(OC(=O)C)(=O)C.[CH3:26][C:27]1[CH:32]=[CH:31][C:30]([SH:33])=[CH:29][CH:28]=1.[OH-].[K+].Cl.[OH-].[Na+]>C1(C)C=CC=CC=1.C(Cl)Cl.[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.CC(C)=O.O>[CH3:26][C:27]1[CH:32]=[CH:31][C:30]([S:33][C:4]2[CH:12]=[C:11]([N+:13]([O-:15])=[O:14])[CH:10]=[C:6]3[C:7]([O:18][C:16](=[O:17])[C:5]=23)=[O:9])=[CH:29][CH:28]=1

Participants

12

Reactant 6

HCID 313Hydrochloric AcidHCID 78114-Methylbenzenethiol2×HCID 7918Acetic Anhydride3×HCID 14797Potassium HydroxideHCID 14798Sodium HydroxideHCID 13442312HCID 13442312, compound

Product 1

HCID 13442313HCID 13442313, compound

Reagents, catalysts & solvents 5

HCID 66133Benzyl triethylammonium chlorideCatalyst2×HCID 180AcetoneSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

46.05 g (0.180 mol) of 3,5-dinitrophthalic acid are kept under reflux with 26 g (0.25 mol) of acetic anhydride in 210 ml of toluene for one hour. The mixture is filtered hot and the filtrate is evaporated. The residue is dissolved under reflux together with 27.4 g (0.221 mol) of p-thiocresol and 34.7 g (0.34 mol) of acetic anhydride in 4.6 liters of methylene chloride. This solution is added dropwise, at 20°-27° C., with vigorous stirring, to a solution of 1.9 g (8.5 mmols) of benzyltriethylammonium chloride in 190.4 g of 50% potassium hydroxide solution (1.7 mols). After the dropwise addition (135 minutes), the mixture is stirred thoroughly for 90 minutes and acidified with concentrated hydrochloric acid, with cooling. The mixture is converted to two clear phases with the addition of water and acetone; the organic phase is separated off, dried over sodium sulfate and evaporated. The residue is heated under reflux with 36.7 g of acetic anhydride in 200 ml of toluene, the mixture is filtered hot and the filtrate is evaporated. The above reaction is repeated with the residue, using 21.8 g (0.214 mol) of acetic anhydride, 19.9 g (0.161 mol) of p-thiocresol, 2.4 g of benzyltriethylammonium chloride and 285 g of 30% NaOH solution. After thorough stirring, the mixture is acidified and the organic phase is separated off, dried over sodium sulfate and evaporated. The residue is converted to the anhydride with 52.1 g of acetic anhydride and 250 ml of toluene. After recrystallisation from methylene chloride/n-pentane, 20.83 g (39% of theory) of 3-(p-methylphenylthio)-5-nitrophthalic anhydride are obtained; melting point: 180°-2° C.

Workup

  1. filtrationThe mixture is filtered hot
  2. customthe filtrate is evaporated
  3. dissolutionThe residue is dissolved
  4. additionAfter the dropwise addition (135 minutes)
  5. temperaturewith cooling
  6. customthe organic phase is separated off
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. temperatureThe residue is heated
  10. temperatureunder reflux with 36.7 g of acetic anhydride in 200 ml of toluene
  11. filtrationthe mixture is filtered hot
  12. customthe filtrate is evaporated
  13. customThe above reaction
  14. customthe organic phase is separated off
  15. dry with materialdried over sodium sulfate
  16. customevaporated
  17. customAfter recrystallisation from methylene chloride/n-pentane, 20.83 g (39% of theory) of 3-(p-methylphenylthio)-5-nitrophthalic anhydride
  18. customare obtained

Sources & evidence

ORD record
ord-58f644734cbb4cc3b0d6e39a57403049
Source dataset
uspto-grants-1982_12
Patent number
US04363917

Reaction notes

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