반응 #2467997

반응 방정식

7-Chloro-9H-3-thia-9-aza-benzo[f]azulene-4,10-dione

toluene

phosphorus oxychloride

→

title compound

7-Chloro-10-methoxy-3-thia-9-aza-benzo[f]azulen-4-one

용매

dimethylformamide

반응 조건

후처리

1. 1
   기타A 4-necked, round-bottomed flask, equipped with a mechanical stirrer
2. 2
   workup.ADDITIONdigital thermometer, addition funnel and a condenser with nitrogen inlet-outlet
3. 3
   기타The pipes are flushed with toluene (774 g)
4. 4
   온도Then the mixture is cooled to −5° C.
5. 5
   workup.ADDITIONa 30% solution of sodium methylate (1.43 kg) is added over 30 min at −5° C
6. 6
   workup.ADDITIONAfter addition the mixture
7. 7
   온도is warmed to 40° C. over an hour
8. 8
   workup.DISTILLATIONthe solvent is distilled at 20-45° C. under reduced pressure
9. 9
   workup.ADDITIONTo the residue deionized water (6.7 kg) is added
10. 10
    농축the mixture is concentrated under reduced pressure to 7 L
11. 11
    workup.ADDITIONThen heptane (3.06 kg) is added
12. 12
    온도the temperature is raised to 70° C. over 1 hour
13. 13
    workup.STIRRINGby additional stirring of 10 min
14. 14
    온도The suspension is then cooled to 0° C.
15. 15
    여과the solid is collected by filtration
16. 16
    세척washed with heptane (2×383 g) and deionized water (2×1.1 kg)
17. 17
    기타dried under vacuum at 65° C.

실험 절차

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.

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