Water → 22133-98-8

HRID 2292829Notes

Reaction equation

HRID 2292829 reaction equation
O.[Cl:2][C:3]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[C:6]([Cl:13])[C:4]=1[NH2:5].[C:14](Cl)(Cl)=[S:15].CN(C)C=O>C1(C)C=CC=CC=1>[Cl:2][C:3]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[C:6]([Cl:13])[C:4]=1[N:5]=[C:14]=[S:15]

Participants

6

Reactant 4

HCID 962WaterHCID 6228DimethylformamideHCID 74302,6-Dichloro-4-nitroanilineHCID 10040Thiophosgene

Product 1

HCID 1263558922133-98-8

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A 12-L, 3-neck, round bottom flask equipped with a mechanical stirrer, a thermometer and a condenser connected to a 6-L water trap was charged sequentially with 2,6-dichloro-4-nitroaniline (500 g, 2.42 mol), toluene (5 L), thiophosgene (500 g, 4.35 mol), and dimethylformamide (5 mL, 0.065 mol). The mixture was heated to reflux over 1 hour and maintained at reflux for 4 hours. The black solution obtained was cooled over 15 hours to 23° C. The solvent was removed by rotary evaporation and the residual black oil was triturated with hexane (2 L), causing crystallization. After chilling for an hour, the rust-colored solid was collected by filtration, washed with hexane (1 L), and dried in the air at ambient temperature to a constant weight of 437 g (73%) of (1). (This material was of adequate purity to be used in the subsequent reaction; however, (1) can also be recrystallized in high yield from hexane.) The hexane filtrate was evaporated and the residue was dried under high vacuum for 15 hours, causing partial crystallization. The material was triturated with hexane (1 L) and collected by filtration. Recrystallization from hexane provided a second crop of (1) weighing 88.5 g. The total yield was 525.5 g (87%).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux over 1 hour
  3. temperaturemaintained
  4. temperatureat reflux for 4 hours
  5. customThe black solution obtained
  6. temperaturewas cooled over 15 hours to 23° C
  7. customThe solvent was removed by rotary evaporation
  8. customthe residual black oil was triturated with hexane (2 L)
  9. customcrystallization
  10. temperatureAfter chilling for an hour
  11. filtrationthe rust-colored solid was collected by filtration
  12. washwashed with hexane (1 L)
  13. dry with materialdried in the air at ambient temperature to a constant weight of 437 g (73%) of (1)
  14. customto be used in the subsequent reaction
  15. customhowever, (1) can also be recrystallized
  16. customin high yield from hexane
  17. custom) The hexane filtrate was evaporated
  18. customthe residue was dried under high vacuum for 15 hours
  19. customcrystallization
  20. customThe material was triturated with hexane (1 L)
  21. filtrationcollected by filtration
  22. customRecrystallization from hexane

Sources & evidence

ORD record
ord-77ab808cb4324052a5f370cf9beecb8f
Source dataset
uspto-grants-1997_11
Patent number
US05684156

Reaction notes

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