Hydrochloric Acid → 3-Bromo-4-fluorobenzene-1-sulfonyl chloride

HRID 2216225Notes

Reaction equation

HRID 2216225 reaction equation
[ClH:1].[Br:2][C:3]1[CH:4]=[C:5](N)[CH:6]=[CH:7][C:8]=1[F:9].C(O[N+]([O-])=O)(C)(C)C.[S:19](=[O:21])=[O:20]>C(Cl)Cl.CO.[Cu](Cl)Cl>[Br:2][C:3]1[CH:4]=[C:5]([S:19]([Cl:1])(=[O:21])=[O:20])[CH:6]=[CH:7][C:8]=1[F:9]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 1119Sulfur DioxideHCID 164756Nitric acid, 1,1-dimethylethyl esterHCID 27792863-Bromo-4-fluoroaniline

Product 1

HCID 218867333-Bromo-4-fluorobenzene-1-sulfonyl chlorideYield 59%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 21226129Dichloromethane methanolSolvent2×

Conditions

Temperature
-5 °C

Procedure

Concentrated HCl (1.93 mL, 23.16 mmol) was added to a solution of 3-bromo-4-fluoro-phenylamine ((Example 265: part a) 2.2 g, 11.58 mmol) in 18 mL of 2:1 DCM/MeOH. A precipitate appeared and another 9 mL of 2:1 DCM/MeOH was added. The solution was cooled to −5° C. and tert-butylnitrate (2.71 mL, 23.16 mmol) was added dropwise over 8 min. After stirring for 15 min, sulfur dioxide (˜5 mL) was condensed into the reaction, followed by addition of copper (II) chloride (592 mg, 3.47 mmol) (gas evolution). The solvent was removed in vacuo and the residue was purified by SiO2 flash column chromatography to yield the title compound (1.9 g, 59%). 1H-NMR (CDCl3): δ 8.31 (dd, 1H, J=2.3, 5.8 Hz), 8.04 (ddd, 1H, J=2.6, 4.1, 8.8 Hz), 7.39 (dd, 1H, J=7.7, 8.8 Hz).

Workup

  1. customcondensed
  2. custominto the reaction
  3. customThe solvent was removed in vacuo
  4. customthe residue was purified by SiO2 flash column chromatography

Sources & evidence

ORD record
ord-ed4da9165836405aa8b153108852e1b1
Source dataset
uspto-grants-2006_09
Patent number
US07109354B2

Reaction notes

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