Thionyl Chloride → 5-Bromo-6-fluoro-2,1,3-benzothiadiazole

HRID 1468968Notes

Reaction equation

HRID 1468968 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH2:10])[C:5]([NH2:9])=[CH:6][C:7]=1[F:8].[S:11](Cl)(Cl)=O>C(Cl)(Cl)Cl.C(OCC)(=O)C>[Br:1][C:2]1[C:7]([F:8])=[CH:6][C:5]2=[N:9][S:11][N:10]=[C:4]2[CH:3]=1

Participants

5

Reactant 2

HCID 24386Thionyl ChlorideHCID 199585604-Bromo-5-fluoro-1,2-benzenediamine

Product 1

HCID 532168505-Bromo-6-fluoro-2,1,3-benzothiadiazoleYield 76%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8857Ethyl AcetateSolvent

Procedure

4-Bromo-5-fluorobenzene-1,2-diamine (500 mg, 2.4 mmol) was dissolved in 20 mL chloroform, treated in portions with thionyl chloride (580 mg, 4.9 mmol) and heated to reflux for 20 h. After cooling the mixture was diluted with 60 mL ethyl acetate, washed with 15 mL water, 15 mL saturated NaCl, dried (Na2SO4) and concentrated under vacuum. The material was chromatographed on silica with a 0-30% ethyl acetate-hexane gradient to give the title compound as a white solid (425 mg, 76%): mp 79-82° C.; 1H NMR (400 MHz, CDCl3) δ 8.33 (d, J=6.7 Hz, 1H), 7.72 (d, J=8.3 Hz, 1H); 19F NMR (376 MHz, CDCl3) δ −102.91; EIMS m/z 232.

Workup

  1. temperatureheated
  2. temperatureto reflux for 20 h
  3. temperatureAfter cooling the mixture
  4. washwashed with 15 mL water, 15 mL saturated NaCl
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under vacuum
  7. customThe material was chromatographed on silica with a 0-30% ethyl acetate-hexane gradient

Sources & evidence

ORD record
ord-78d1a511660b40378deceba115a73358
Source dataset
uspto-grants-2015_04
Patent number
US09006250B2

Reaction notes

Loading…