Benzenesulfonyl chloride → HCID 59564712, compound

HRID 520554Notes

Reaction equation

HRID 520554 reaction equation
[Cl:1][C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][NH:8]2)=[C:4]([I:11])[CH:3]=1.[OH-].[Na+].[C:14]1([S:20](Cl)(=[O:22])=[O:21])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1>[Cl:1][C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][N:8]2[S:20]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)(=[O:22])=[O:21])=[C:4]([I:11])[CH:3]=1

Participants

6

Reactant 3

HCID 7369Benzenesulfonyl chlorideHCID 14798Sodium HydroxideHCID 247281316-Chloro-4-iodo-1H-indazole

Product 1

HCID 59564712HCID 59564712, compound

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
15 °C

Procedure

6-Chloro-4-iodo-1H-indazole (1.0 eq., 1 wt, 50 g), sodium hydroxide (2.25 eq., 0.324 wt, 16.16 g) and tetrabutylammonium hydrogensulphate (0.05 eq., 0.061 wt, 3.05 g) are stirred in THF (9.5 vols, 475 ml) at 20±3° C. under a nitrogen atmosphere for 1 hr. The mixture is cooled to 15±3° C. and benzenesulfonyl chloride (1.10 eq., 0.51 vols, 25.5 ml) was added dropwise over 20 mins maintaining the reaction temperature at <25° C. and is washed in with THF (0.5 vols, 25 ml). The resulting mixture is then stirred under a nitrogen atmosphere at 20±3° C. for at least 1 hr before checking for completion by HPLC. The reaction mixture is then added to 0.25 M hydrochloric acid solution (18 vols, 900 ml) cooled to 0±3° C. over 15 minutes maintaining the temperature of the aqueous suspension at <20° C. This is washed in with 0.25M hydrochloric acid solution (2 vols, 100 ml). The resulting orange suspension is then stirred at 2±3° C. for at least 1 hr. The solid is filtered, washed with water (2×3 vols, 2×150 ml) and sucked dry for 20 mins, then dried under high vacuum at 40° C. (±3° C.) to constant probe temperature to afford 6-chloro-4-iodo-1-(phenylsulfonyl)-1H-indazole as an orange solid.

Workup

  1. temperaturemaintaining the reaction temperature at <25° C.
  2. washis washed in with THF (0.5 vols, 25 ml)
  3. additionThe reaction mixture is then added to 0.25 M hydrochloric acid solution (18 vols, 900 ml)
  4. temperaturecooled to 0±3° C. over 15 minutes
  5. temperaturemaintaining the temperature of the aqueous suspension at <20° C
  6. washThis is washed in with 0.25M hydrochloric acid solution (2 vols, 100 ml)
  7. stirringThe resulting orange suspension is then stirred at 2±3° C. for at least 1 hr
  8. filtrationThe solid is filtered
  9. washwashed with water (2×3 vols, 2×150 ml)
  10. customsucked dry for 20 mins
  11. customdried under high vacuum at 40° C. (±3° C.) to constant probe temperature

Sources & evidence

ORD record
ord-5788727f6afd49a5bee601309eef6aae
Source dataset
uspto-grants-2016_05
Patent number
US09326987B2

Reaction notes

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