Sulfuric Acid → 5-bromo-1-(4-fluorophenyl)-1H-benzotriazole

HRID 244472Notes

Reaction equation

HRID 244472 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH2:16])[C:5]([NH:8][C:9]2[CH:14]=[CH:13][C:12]([F:15])=[CH:11][CH:10]=2)=[CH:6][CH:7]=1.S(=O)(=O)(O)O.[N:22]([O-])=O.[Na+].[I-].[Na+]>CS(C)=O.O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]2[N:8]([C:9]3[CH:14]=[CH:13][C:12]([F:15])=[CH:11][CH:10]=3)[N:22]=[N:16][C:4]=2[CH:3]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 5238Sodium IodideHCID 23668193Sodium NitriteHCID 431487554-bromo-N1-(4-fluorophenyl)benzene-1,2-diamine

Product 1

HCID 594372265-bromo-1-(4-fluorophenyl)-1H-benzotriazoleYield 89%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent2×

Procedure

To a stirred room temperature solution of 4-bromo-N1-(4-fluorophenyl)benzene-1,2-diamine (1.4 g, 5 mmol) in DMSO (12 mL), was added 30% sulfuric acid (12 mL). The mixture was then cooled (ice-bath) and a solution of sodium nitrite (380 mg, 5.5 mmol) in water (1 mL) was added dropwise. After 20 minutes, a solution of sodium iodide (2.4 g, 15.8 mmol) in water (2 mL) was added dropwise and the cold bath was removed. After 30 minutes, LCMS showed only a single product [MS m/z 292/294 (MH+)] consistent with the desired product. The mixture was poured into 150 mL of ice water and the resulting precipitate was filtered, washed with sodium thiosulfate solution, water and dried to afford 1.3 g of 5-bromo-1-(4-fluorophenyl)-1H-benzotriazole as a light purple solid. MS m/z 292/294 (MH+).

Workup

  1. temperatureThe mixture was then cooled (ice-bath)
  2. customthe cold bath was removed
  3. waitAfter 30 minutes
  4. additionThe mixture was poured into 150 mL of ice water
  5. filtrationthe resulting precipitate was filtered
  6. washwashed with sodium thiosulfate solution, water
  7. customdried

Sources & evidence

ORD record
ord-ebbade50747c4b0bb68d08c1289b53c4
Source dataset
uspto-grants-2014_02
Patent number
US08658637B2

Reaction notes

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