Potassium Iodide → 7-Bromo-5-iodo-benzo[d]isothiazole

HRID 389471Notes

Reaction equation

HRID 389471 reaction equation
O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[Br:13][C:14]1[C:22]2[S:21][N:20]=[CH:19][C:18]=2[CH:17]=[C:16](N)[CH:15]=1.N([O-])=O.[Na+].[I-:28].[K+].C(=O)(O)[O-].[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(#N)C.O>[Br:13][C:14]1[C:22]2[S:21][N:20]=[CH:19][C:18]=2[CH:17]=[C:16]([I:28])[CH:15]=1

Participants

9

Reactant 6

HCID 4875Potassium IodideHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 23668193Sodium NitriteHCID 667606927-Bromo-benzo[d]isothiazol-5-ylamine

Product 1

HCID 667603867-Bromo-5-iodo-benzo[d]isothiazoleYield 50.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent

Conditions

Temperature
12.5 °C

Procedure

To a solution of p-toluenesulfonic acid monohydrate (1.36 g, 7.2 mmol) in acetonitrile (8.5 mL) was added 7-bromo-benzo[d]isothiazol-5-ylamine (400 mg, 1.74 mmol). The resulting suspension was cooled to 10 to 15° C. and a solution of sodium nitrite (331 mg, 4.8 mmol) and potassium iodide (996 mg, 6 mmol) in water (1.5 mL) was added gradually. The reaction mixture was stirred for 10 min and then allowed to come to RT and stirred for 16 h. The reaction mixture was treated with water (5 mL) and aqueous 1.0 N sodium bicarbonate solution (15 mL), and aqueous 2.0 N sodium thiosulfate solution (10 mL). The precipitate was collected by filtration and the purified by column chromatography (25% ethyl acetate:hexanes) to afford 300 mg (50%) of the title compound. 1H NMR (300 MHz, CDCl3): δ 8.9 (s, 1H), 8.37 (d, J=1.2 Hz, 1H), 7.91 (d, J=1.5 Hz, 1H).

Workup

  1. customto come to RT
  2. stirringstirred for 16 h
  3. filtrationThe precipitate was collected by filtration
  4. customthe purified by column chromatography (25% ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-f481fbab4ed7496d81a52a1b172b26e5
Source dataset
uspto-grants-2013_02
Patent number
US08378104B2

Reaction notes

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