Acetic Acid → 1-Bromo-2-fluoro-4-iodobenzene

HRID 1707891Notes

Reaction equation

HRID 1707891 reaction equation
N([O-])=O.[Na+].C(O)(=O)C.[F:9][C:10]1[CH:16]=[C:15]([I:17])[CH:14]=[CH:13][C:11]=1N.[BrH:18]>S(=O)(=O)(O)O.[Cu](Br)Br.O>[Br:18][C:11]1[CH:13]=[CH:14][C:15]([I:17])=[CH:16][C:10]=1[F:9]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 260Hydrogen BromideHCID 1856942-Fluoro-4-iodoanilineHCID 23668193Sodium Nitrite

Product 1

HCID 27250061-Bromo-2-fluoro-4-iodobenzene

Reagents, catalysts & solvents 3

HCID 24611Copper bromide (CuBr2)CatalystHCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Procedure

Sodium nitrite (51.2 g) was dissolved in sulfuric acid (390 ml), and then acetic acid (454 ml) was added thereto at 10° C. or lower. The mixed solution was kept at 20° to 25° C., and 2-fluoro-4-iodoaniline (124 g) was added for 1 hour, followed by stirring for 2 hours. The reaction solution was added dropwise to a mixed solution of copper bromide (130 g) with 48% hydrobromic acid (390 ml), and stirred overnight. Then, water (1000 ml) was added to the solution, and the resulting solution was extracted with chloroform, followed by washing with water 3 times. After distilling off chloroform, the resultant was distilled under reduced pressure (b.p. 120° to 125° C./13 mmHg), and then recrystallized from methanol to give 1-bromo-2-fluoro-4-iodobenzene (114 g).

Workup

  1. customat 10° C.
  2. customwas kept at 20° to 25° C.
  3. stirringstirred overnight
  4. extractionthe resulting solution was extracted with chloroform
  5. washby washing with water 3 times
  6. distillationAfter distilling off chloroform
  7. distillationthe resultant was distilled under reduced pressure (b.p. 120° to 125° C./13 mmHg)
  8. customrecrystallized from methanol

Sources & evidence

ORD record
ord-5598ffa1125d4c47849e367fd12142a1
Source dataset
uspto-grants-1994_10
Patent number
US05356558

Reaction notes

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