Sulfuric Acid → HCID 14677653, compound

HRID 1608095Notes

Reaction equation

HRID 1608095 reaction equation
N[C:2]1[C:7]([Br:8])=[CH:6][C:5]([Cl:9])=[CH:4][C:3]=1[C:10]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[Cl:18])=[O:11].N(OS(=O)(=O)O)=O.S(=O)(=O)(O)O.F[B-](F)(F)F.[I-:36].[K+]>O.C(OCC)(=O)C>[Br:8][C:7]1[C:2]([I:36])=[C:3]([C:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[Cl:18])=[O:11])[CH:4]=[C:5]([Cl:9])[CH:6]=1

Participants

8

Reactant 5

HCID 1118Sulfuric AcidHCID 4875Potassium IodideHCID 26255TetrafluoroborateHCID 82157Nitrosylsulfuric acidHCID 14677652(2-Amino-3-bromo-5-chlorophenyl)(2-chlorophenyl)methanone

Product 1

HCID 14677653HCID 14677653, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

An 11.4 g sample of the product of Example 1 (33 mmol) was added portionwise with stirring to a mixture of 36.5 mmol of 40% nitrosylsulfuric acid and 9 mL of concentrated sulfuric acid. The rate of addition was such that the internal temperature was maintained below 45° C. After the addition was completed, stirring was maintained at room temperature for 1.5 hours when the mixture was poured into 75 mL of ice water and filtered. To the filtrate, a solution of 2.2 g of sodium tetrafluoroborate in 15 mL of water was slowly added. The resulting mixture was refrigerated overnight, filtered and the precipitate washed with 12 mL of ice water. The precipitated tetrafluoroborate salt was then stirred in a mixture of 70 mL of water and 25 mL of ethyl acetate while a solution of 11 g (66 mmol) of potassium iodide in 40 mL of water was added over a 20 minute period. The resulting mixture was extracted with three 50 mL portions of methylene chloride which were combined and in turn extracted with 25 mL of 5% sodium thiosulfate solution. The organic extract was concentrated in vacuo to a residual solid which was dissolved in ether and refrigerated overnight. Impurities (mainly bromo-dichlorofluorenone, m.p. 183°-184° C.) were removed by filtration and the filtrate crystallized by concentration to the product which was then recrystallized from ether to produce (3-bromo-5-chloro-2-iodopheny)(2-chlorophenyl)-methanone having a m.p. of 86°-87° C.

Workup

  1. additionThe rate of addition
  2. temperaturewas maintained below 45° C
  3. additionAfter the addition
  4. filtrationfiltered
  5. additionTo the filtrate, a solution of 2.2 g of sodium tetrafluoroborate in 15 mL of water was slowly added
  6. filtrationfiltered
  7. washthe precipitate washed with 12 mL of ice water
  8. additionwas added over a 20 minute period
  9. extractionThe resulting mixture was extracted with three 50 mL portions of methylene chloride which
  10. extractionextracted with 25 mL of 5% sodium thiosulfate solution
  11. extractionThe organic extract
  12. concentrationwas concentrated in vacuo to a residual solid which
  13. dissolutionwas dissolved in ether and refrigerated overnight
  14. customImpurities (mainly bromo-dichlorofluorenone, m.p. 183°-184° C.) were removed by filtration
  15. customthe filtrate crystallized by concentration to the product which
  16. customwas then recrystallized from ether

Sources & evidence

ORD record
ord-6aa72193972a49f4baa3e3873905fa2a
Source dataset
uspto-grants-1989_09
Patent number
US04869895

Reaction notes

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