Toluene → HCID 57697747, compound

HRID 2380815Notes

Reaction equation

HRID 2380815 reaction equation
[Cl:1][C:2]1[CH:17]=[CH:16][C:5]2[C:6](=[O:15])[C:7]3[S:8][CH:9]=[CH:10][C:11]=3[C:12](=[O:14])[NH:13][C:4]=2[CH:3]=1.[C:18]1(C)C=CC=CC=1.P(Cl)(Cl)(Cl)=O>CN(C)C=O>[Cl:1][C:2]1[CH:17]=[CH:16][C:5]2[C:6](=[O:15])[C:7]3[S:8][CH:9]=[CH:10][C:11]=3[C:12]([O:14][CH3:18])=[N:13][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 1140TolueneHCID 24813Phosphorus oxychlorideHCID 57697743HCID 57697743, compound

Product 1

HCID 57697747HCID 57697747, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
108 °C

Procedure

A 4-necked, round-bottomed flask, equipped with a mechanical stirrer, digital thermometer, addition funnel and a condenser with nitrogen inlet-outlet is charged with 7-Chloro-9H-3-thia-9-aza-benzo[f]azulene-4,10-dione (559.6 g), toluene (6.8 kg) and dimethylformamide (100.73 g). To the stirred suspension phosphorus oxychloride (357.2 g) is added over 5 min at 20-25° C. The pipes are flushed with toluene (774 g), then the temperature is raised to 108° C. over 1 hour and stirring continued for about 5 hours. Then the mixture is cooled to −5° C. and a 30% solution of sodium methylate (1.43 kg) is added over 30 min at −5° C. After addition the mixture is warmed to 40° C. over an hour and the solvent is distilled at 20-45° C. under reduced pressure. To the residue deionized water (6.7 kg) is added and the mixture is concentrated under reduced pressure to 7 L. Then heptane (3.06 kg) is added and the temperature is raised to 70° C. over 1 hour, followed by additional stirring of 10 min. The suspension is then cooled to 0° C. and the solid is collected by filtration, washed with heptane (2×383 g) and deionized water (2×1.1 kg) and dried under vacuum at 65° C. to yield the title compound with a melting point of >195-197° C.

Workup

  1. customA 4-necked, round-bottomed flask, equipped with a mechanical stirrer
  2. additiondigital thermometer, addition funnel and a condenser with nitrogen inlet-outlet
  3. customThe pipes are flushed with toluene (774 g)
  4. temperatureThen the mixture is cooled to −5° C.
  5. additiona 30% solution of sodium methylate (1.43 kg) is added over 30 min at −5° C
  6. additionAfter addition the mixture
  7. temperatureis warmed to 40° C. over an hour
  8. distillationthe solvent is distilled at 20-45° C. under reduced pressure
  9. additionTo the residue deionized water (6.7 kg) is added
  10. concentrationthe mixture is concentrated under reduced pressure to 7 L
  11. additionThen heptane (3.06 kg) is added
  12. temperaturethe temperature is raised to 70° C. over 1 hour
  13. stirringby additional stirring of 10 min
  14. temperatureThe suspension is then cooled to 0° C.
  15. filtrationthe solid is collected by filtration
  16. washwashed with heptane (2×383 g) and deionized water (2×1.1 kg)
  17. customdried under vacuum at 65° C.

Sources & evidence

ORD record
ord-9db21a052804466cab4b00ea945dfd76
Source dataset
uspto-grants-2012_09
Patent number
US08258128B2

Reaction notes

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