Hydrochloric Acid → 1-Methyl-4-[4-(4-{7-nitroquinolin-4-ylamino}benzamido)-phenylamino]pyridinium dichloride

HRID 547536Notes

Reaction equation

HRID 547536 reaction equation
[Cl-:1].[Cl-].[NH3+:3][C:4]1[CH:26]=[CH:25][C:7]([C:8]([NH:10][C:11]2[CH:24]=[CH:23][C:14]([NH:15][C:16]3[CH:21]=[CH:20][N+:19]([CH3:22])=[CH:18][CH:17]=3)=[CH:13][CH:12]=2)=[O:9])=[CH:6][CH:5]=1.[Cl:27][C:28]1[C:37]2[C:32](=[CH:33][C:34]([N+:38]([O-:40])=[O:39])=[CH:35][CH:36]=2)[N:31]=[CH:30][CH:29]=1.Cl>CO>[Cl-:27].[Cl-:1].[CH3:22][N+:19]1[CH:20]=[CH:21][C:16]([NH:15][C:14]2[CH:23]=[CH:24][C:11]([NH:10][C:8](=[O:9])[C:7]3[CH:25]=[CH:26][C:4]([NH:3][C:28]4[C:37]5[C:32](=[CH:33][C:34]([N+:38]([O-:40])=[O:39])=[CH:35][CH:36]=5)[N:31]=[CH:30][CH:29]=4)=[CH:5][CH:6]=3)=[CH:12][CH:13]=2)=[CH:17][CH:18]=1.[CH3:22][N+:19]1[CH:20]=[CH:21][C:16]([NH:15][C:14]2[CH:23]=[CH:24][C:11]([NH:10][C:8](=[O:9])[C:7]3[CH:25]=[CH:26][C:4]([NH:3][C:28]4[C:37]5[C:32](=[CH:33][C:34]([N+:38]([O-:40])=[O:39])=[CH:35][CH:36]=5)[N:31]=[CH:30][CH:29]=4)=[CH:5][CH:6]=3)=[CH:12][CH:13]=2)=[CH:17][CH:18]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 123225804-Chloro-7-nitroquinolineHCID 671991294-{4-[(4-Ammoniobenzoyl)amino]anilino}-1-methylpyridinium dichloride

Product 1

HCID 866216391-Methyl-4-[4-(4-{7-nitroquinolin-4-ylamino}benzamido)-phenylamino]pyridinium dichloride

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of amine B7 (1.46 g, 3.73 mmol) in dry MeOH (20 mL) were sequentially added 4-chloro-7-nitroquinoline (S1) (0.78 g, 3.73 mmol) and two drops of c.HCl, and the resulting mixture was refluxed for 4 h. After this time, the temperature was reduced to ˜40° C. and heating was continued for a further 65 h. After this time, solvent was removed under reduced pressure. The residue was re-dissolved in MeOH, and solvent was again removed under reduced pressure. This latter process was repeated once more, and the residue was then re-precipitated twice from MeOH:Et2O. Finally, a portion of the solid thus obtained was re-precipitated from MeOH:EtOAc to afford Cpd. S as an amorphous yellow-orange solid (0.070g, 3%). 1H NMR [(CD3)2SO]: 3.96 [s, 3H, R2N+CH3], 7.14 [m, 3H, ArH], 7.35 [d, J=8.85 Hz, 2H, ArH], 7.68 [d, J=8.57 Hz, 2H, ArH], 7.96 [d, J=8.85 Hz, 2H, ArH], 8.18 [d, J=8.57 Hz, 2H, ArH], 8.26 [d, J=7.37 Hz, 2H, ArH], 8.50 [dd, J=9.28, 2.23 Hz, 1H, ArH], 8.77 [d, J=6.65 Hz, 1H, ArH], 8.94 [d, J=2.23 Hz, 1H, ArH], 9.08 [d, J=9.28 Hz, 1H, ArH], 10.55 [s, 1H, ArNHAr], 10.71 [s, 1H, ArNHAr], 11.21 [br s, 1H, ArC(O)NHAr], 11.21 [v v br s, 1H, quinoline-N+H]; LCMS (APCI+): 492 (100%), 493 (30%). HPLC: 98.1%.

Workup

  1. customwas reduced to ˜40° C.
  2. temperatureheating
  3. customAfter this time, solvent was removed under reduced pressure
  4. dissolutionThe residue was re-dissolved in MeOH
  5. customsolvent was again removed under reduced pressure
  6. customthe residue was then re-precipitated twice from MeOH
  7. customFinally, a portion of the solid thus obtained
  8. customwas re-precipitated from MeOH
  9. customEtOAc to afford Cpd

Sources & evidence

ORD record
ord-922430c8ab9f48098de45e5d89d66f72
Source dataset
uspto-grants-2011_05
Patent number
US07939546B2

Reaction notes

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