Acetic Acid → 8-Amino-3-phenylsulfonylquinoline methanesulfonic acid salt

HRID 2116528Notes

Reaction equation

HRID 2116528 reaction equation
C(O)(=O)C.[N+:5]([C:8]1[CH:9]=[CH:10][CH:11]=[C:12]2[C:17]=1[N:16]=[CH:15][C:14]([S:18]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)(=[O:20])=[O:19])=[CH:13]2)([O-])=O.C1(C)C=CC=CC=1.[CH3:34][S:35]([OH:38])(=[O:37])=[O:36]>C1COCC1.O.[Fe]>[CH3:34][S:35]([OH:38])(=[O:37])=[O:36].[NH2:5][C:8]1[CH:9]=[CH:10][CH:11]=[C:12]2[C:17]=1[N:16]=[CH:15][C:14]([S:18]([C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)(=[O:20])=[O:19])=[CH:13]2

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 1140TolueneHCID 6395Methanesulfonic AcidHCID 534255033-(Benzenesulfonyl)-8-nitroquinoline

Product 1

HCID 858693348-Amino-3-phenylsulfonylquinoline methanesulfonic acid salt

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

A suspension of iron powder (26.7 g, 5 eq, 325 mesh) in THF (300 ml, 10 vol), water (30 ml, 1 vol) and acetic acid (19.2 ml, 3.5 eq) was heated to 50° C. 8-Nitro-3-phenylsulfonylquinoline (D4) (30 g, 1 wt) was added portionwise to the mixture over 30 min, keeping the temperature below 60° C. The reaction mixture was stirred at 50 to 55° C. for 60 min. Toluene (240 ml, 8 vol) was added, followed by water (60 ml, 2 vol) before cooling to 40° C. and filtering the mixture through a silica gel plug. The silica plug was washed with toluene (2×60 ml, 2 vol). The layers of the combined filtrate were separated and the organic layer concentrated in vacuo to ca 10 volumes. The reaction mixture was warmed to 77° C. then treated with methanesulfonic acid (7.42 ml, 1.2 eq) added over 15 min maintaining the temperature at 75 to 80° C. The resulting orange suspension was cooled slowly to ambient, stirred at ambient temperature for ca 2 h, then the product filtered and washed with toluene (3×60 ml). The resulting pink solid (D8) was dried in vacuo at ca 45° C. to constant weight. Yield: 34.17 g, 94%.

Workup

  1. customthe temperature below 60° C
  2. temperaturebefore cooling to 40° C.
  3. filtrationfiltering the mixture through a silica gel plug
  4. washThe silica plug was washed with toluene (2×60 ml, 2 vol)
  5. customThe layers of the combined filtrate were separated
  6. concentrationthe organic layer concentrated in vacuo to ca 10 volumes
  7. temperatureThe reaction mixture was warmed to 77° C.
  8. additionadded over 15 min
  9. temperaturemaintaining the temperature at 75 to 80° C
  10. temperatureThe resulting orange suspension was cooled slowly to ambient,
  11. stirringstirred at ambient temperature for ca 2 h
  12. filtrationthe product filtered
  13. washwashed with toluene (3×60 ml)
  14. dry with materialThe resulting pink solid (D8) was dried in vacuo at ca 45° C. to constant weight

Sources & evidence

ORD record
ord-30efc7f1d1574ec5975c1de5b05a2189
Source dataset
uspto-grants-2008_10
Patent number
US07439244B2

Reaction notes

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