Hydrochloric Acid → N-benzyl-2-nitro-N-(4-hydroxy-3-oxobutyl)benzenesulfonamide

HRID 526724Notes

Reaction equation

HRID 526724 reaction equation
[CH2:1]([N:8]([CH2:21][CH2:22][C:23](=[O:26])[CH2:24]Br)[S:9]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[N+:18]([O-:20])=[O:19])(=[O:11])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O-])(=[O:29])C.[K+].Cl.C(Cl)Cl>C(O)(=O)C>[CH2:1]([N:8]([CH2:21][CH2:22][C:23](=[O:26])[CH2:24][OH:29])[S:9]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[N+:18]([O-:20])=[O:19])(=[O:11])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 517044Potassium AcetateHCID 71502814N-benzyl-N-(4-bromo-3-oxobutyl)-2-nitrobenzenesulfonamide

Product 1

HCID 71152063N-benzyl-2-nitro-N-(4-hydroxy-3-oxobutyl)benzenesulfonamideYield 96.1%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
112.5 °C

Procedure

A mixture of N-benzyl-N-(4-bromo-3-oxobutyl)-2-nitrobenzenesulfonamide (16 g, 36.3 mmol) and potassium acetate (8.90 g, 91 mmol) in acetic acid (130 ml) was heated to 110-115° C. (slow reflux visible) and stirred for 1 hour (complete by HPLC). Cooled, acetic acid (80 ml) removed under reduced pressure, the residue distributed between DCM (120 ml) and water (120 ml). The organic phase was washed with water, evaporated to half of the volume, diluted with 2-propanol (65.0 ml), the rest of DCM removed. Water (18.20 ml) was added followed by concentrated hydrochloric acid (2.102 ml, 25.4 mmol), residual DCM was distilled off at atmospheric pressure until head temperature reached 77° C., then stirred under reflux for 3 hours. Diluted with water (65 ml), 2-propanol removed at 60° C./180 mbar, to the biphasic residue EA (80 ml) was added followed by sodium bicarbonate with stirring until evolution of gas stopped. The organic phase was dried (MgSO4), evaporated to dryness to give N-benzyl-N-(4-hydroxy-3-oxobutyl)-2-nitrobenzenesulfonamide (13.2 g, 34.9 mmol, 96% yield).

Workup

  1. temperature(slow reflux visible)
  2. temperatureCooled
  3. customacetic acid (80 ml) removed under reduced pressure
  4. washThe organic phase was washed with water
  5. customevaporated to half of the volume
  6. additiondiluted with 2-propanol (65.0 ml)
  7. customthe rest of DCM removed
  8. additionWater (18.20 ml) was added
  9. distillationwas distilled off at atmospheric pressure until head temperature
  10. customreached 77° C.
  11. stirringstirred
  12. temperatureunder reflux for 3 hours
  13. additionDiluted with water (65 ml), 2-propanol
  14. customremoved at 60° C./180 mbar
  15. additionto the biphasic residue EA (80 ml) was added
  16. stirringwith stirring until evolution of gas
  17. dry with materialThe organic phase was dried (MgSO4)
  18. customevaporated to dryness

Sources & evidence

ORD record
ord-98fe2f9365dc4a0fa3109194162d6e9f
Source dataset
uspto-grants-2016_05
Patent number
US09346751B2

Reaction notes

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