Benzenesulfinic acid, sodium salt → 3-(Benzenesulfonyl)-8-nitroquinoline

HRID 883522Notes

Reaction equation

HRID 883522 reaction equation
I[C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[CH:7][C:6]=2[N+:12]([O-:14])=[O:13].[C:15]1([S:21]([O-:23])=[O:22])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[Na+]>CN(C)C=O>[N+:12]([C:6]1[CH:7]=[CH:8][CH:9]=[C:10]2[C:5]=1[N:4]=[CH:3][C:2]([S:21]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)(=[O:23])=[O:22])=[CH:11]2)([O-:14])=[O:13]

Participants

4

Reactant 2

HCID 2723840Benzenesulfinic acid, sodium saltHCID 120323673-Iodo-8-nitroquinoline

Product 1

HCID 534255033-(Benzenesulfonyl)-8-nitroquinolineYield 58%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
65 °C

Procedure

3-Iodo-8-nitroquinoline (D3) (135 g, 0.45 mol), was suspended in dimethylformamide (2.4 L) in a 5 L 3-necked flask fitted with an overhead stirrer, under an argon atmosphere. This mixture was treated successively with anhydrous sodium phenylsulfinate (99.6 g 0.608 mol), and bis-(copper (I) triflate) benzene complex (170 g, 0.338 mol). The resulting slurry was heated to 65° C. for 18 h. The mixture was cooled, filtered and the solvent evaporated in vacuo. Acetone (2.5 L) was added to the residue and the solution filtered. The filtrate was evaporated in vacuo, a further 2.5 L of acetone added and the mixture filtered again. The solvent was evaporated in vacuo and the residue dissolved in chloroform (3 L) and washed with 10% aqueous ammonia (2×2 L), and the organic phase was dried over magnesium sulphate and the solvent evaporated in vacuo. The dark brown residue was purified using a Biotage flash-150 chromatography apparatus (5 kg silica gel) eluting with hexane and increasing proportions of ethyl acetate to give the title compound (D4) (81.5 g, 58%) as a yellow solid;

Workup

  1. customfitted with an overhead stirrer, under an argon atmosphere
  2. temperatureThe mixture was cooled
  3. filtrationfiltered
  4. customthe solvent evaporated in vacuo
  5. additionAcetone (2.5 L) was added to the residue
  6. filtrationthe solution filtered
  7. customThe filtrate was evaporated in vacuo
  8. additiona further 2.5 L of acetone added
  9. filtrationthe mixture filtered again
  10. customThe solvent was evaporated in vacuo
  11. dissolutionthe residue dissolved in chloroform (3 L)
  12. washwashed with 10% aqueous ammonia (2×2 L)
  13. dry with materialthe organic phase was dried over magnesium sulphate
  14. customthe solvent evaporated in vacuo
  15. customThe dark brown residue was purified
  16. washeluting with hexane
  17. temperatureincreasing proportions of ethyl acetate

Sources & evidence

ORD record
ord-37a1c9a0c48e419c9fddc97817e27652
Source dataset
uspto-grants-2012_08
Patent number
US08236947B2

Reaction notes

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