Sodium Chloride → Benzene, dichlorotrifluoro-

HRID 865491Notes

Reaction equation

HRID 865491 reaction equation
S([O-])([O-])=O.[Na+].[Na+].[Cl-:7].[Na+].[Cl:9][C:10]1[C:16]([F:17])=[C:15]([F:18])[C:14]([F:19])=[CH:13][C:11]=1N.[Cl:20][C:21]1[C:22]([F:30])=[C:23]([F:29])[C:24]([F:28])=[C:25]([CH:27]=1)N.N([O-])=O.[K+].[OH-].[Na+]>O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2]>[Cl:20][C:11]1[CH:13]=[C:14]([F:19])[C:15]([F:18])=[C:16]([F:17])[C:10]=1[Cl:9].[Cl:7][C:25]1[CH:27]=[C:21]([Cl:20])[C:22]([F:30])=[C:23]([F:29])[C:24]=1[F:28]

Participants

9

Reactant 5

HCID 5234Sodium ChlorideHCID 14798Sodium HydroxideHCID 24437Sodium SulfiteHCID 516910Potassium nitriteHCID 86749930HCID 86749930, compound

Product 2

HCID 190295Benzene, dichlorotrifluoro-HCID 19020328HCID 19020328, compound

Reagents, catalysts & solvents 2

HCID 24463Copper sulfate pentahydrateCatalystHCID 962WaterSolvent

Conditions

Temperature
10 °C

Procedure

20 g (0.16 mol) of sodium sulfite and 40 g of sodium chloride are added to a solution of 82 g (0.2 mol) of copper sulfate pentahydrate to precipitate copper(I) chloride, which is dissolved in 100 ml of concentrated hydrochloric acid. 48.3 g (0.266 mol) of 2-chloro-3,4,5trifluoroaniline/5-chloro-2,3,4-trifluoroaniline (ratio 78:22 according to NMR) are added to this solution with stirring. The mixture is cooled to 10° C., and a solution of 30 g (0.352 mol) of potassium nitrite in 60 g of water is added dropwise. During the addition, the temperature of the mixture is maintained below 20° C. After the end of the metered addition, stirring is continued for 1 hour and then the mixture is heated at 80° C. for 30 min, then cooled and rendered alkaline with sodium hydroxide solution. The mixture of products is prepurified by steam distillation. The oily phase which separates out in the distillate is separated off and subjected to fractional distillation (41 g). 32.3 g (0,161 mol, 60%) are obtained of a 75:25 mixture of 1,2-dichloro-3,4,5-trifluorobenzene and 1,5-dichloro-2,3,4-trifluorobenzene.

Workup

  1. customto precipitate copper(I) chloride, which
  2. dissolutionis dissolved in 100 ml of concentrated hydrochloric acid
  3. additionDuring the addition
  4. temperaturethe temperature of the mixture is maintained below 20° C
  5. additionAfter the end of the metered addition
  6. stirringstirring
  7. temperaturethe mixture is heated at 80° C. for 30 min
  8. temperaturecooled
  9. additionThe mixture of products
  10. distillationis prepurified by steam distillation
  11. customis separated off
  12. distillationsubjected to fractional distillation (41 g)

Sources & evidence

ORD record
ord-785b5817dacb4ddeb86449ffc7747224
Source dataset
uspto-grants-1996_10
Patent number
US05565612

Reaction notes

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