Phosphorus oxychloride → HCID 12519142, compound

HRID 2052701Notes

Reaction equation

HRID 2052701 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[N:7]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[NH:17][CH:18]=O)[CH2:6][CH2:5]2.P(Cl)(Cl)(Cl)=O>>[ClH:1].[Cl:1][C:2]1[CH:3]=[C:4]2[C:8]3=[C:9]([CH:10]=1)[CH:18]=[N:17][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=1[N:7]3[CH2:6][CH2:5]2

Participants

3

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 12519129HCID 12519129, compound

Product 1

HCID 12519142HCID 12519142, compound

Procedure

A mixture of 9.40 g of 5-chloro-1-(2-formamidophenyl)indoline and 45 ml of phosphorus oxychloride is stirred under nitrogen. After a short time, a purple solution results. While heating this to reflux, a solid precipitates at 60° C. During the early stages of a 6 hour reflux period a solution is obtained again followed by heavy HCl (g) evolution and separation of a solid. The mixture is cooled and 45 ml of hexane is added to give a finely divided purple solid. This is filtered, washed repeatedly with hexane and dried. For purification, the solid is slurried in absolute ethanol, and tri-n-butylamine is added until a color change, indicating liberation of the free base of the product. The mixture is warmed to produce a solution, and the base allowed to crystallize at 0° C. The base is collected, washed with ethanol and dried. To reform the HCl salt, the base is dissolved in 15 ml of dimethylformamide without heating, and to the solution is added 35 ml of ethanol saturated with HCl gas. The product of 4-chloro-1,2-dihydroindolo[1,7-ab][1,5]benzodiazepine hydrochloride crystallizes rapidly in the form of needles with m.p. 231°-233° C. dec.

Workup

  1. customAfter a short time, a purple solution results
  2. temperatureWhile heating
  3. temperaturethis to reflux
  4. customa solid precipitates at 60° C
  5. temperatureDuring the early stages of a 6 hour reflux period a solution
  6. customis obtained again
  7. customfollowed by heavy HCl (g) evolution and separation of a solid
  8. temperatureThe mixture is cooled
  9. addition45 ml of hexane is added
  10. customto give a finely divided purple solid
  11. filtrationThis is filtered
  12. washwashed repeatedly with hexane
  13. customdried
  14. customFor purification
  15. additiontri-n-butylamine is added until a color change
  16. temperatureThe mixture is warmed
  17. customto produce a solution
  18. customto crystallize at 0° C
  19. customThe base is collected
  20. washwashed with ethanol
  21. customdried
  22. dissolutionthe base is dissolved in 15 ml of dimethylformamide
  23. temperaturewithout heating
  24. additionto the solution is added 35 ml of ethanol saturated with HCl gas
  25. customThe product of 4-chloro-1,2-dihydroindolo[1,7-ab][1,5]benzodiazepine hydrochloride crystallizes rapidly in the form of needles with m.p. 231°-233° C. dec.

Sources & evidence

ORD record
ord-b7fbd13641a4460cba87fd6751275a80
Source dataset
uspto-grants-1980_01
Patent number
US04186199

Reaction notes

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