Hydrochloric Acid → 1-Methyl-4-[4-({4-[(6-nitro-4-quinolinyl)amino]anilino}carbonyl)anilino]pyridinium chloride

HRID 547533Notes

Reaction equation

HRID 547533 reaction equation
[Cl:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([N+:12]([O-:14])=[O:13])[CH:10]=2)[N:5]=[CH:4][CH:3]=1.[Cl-].[NH2:16][C:17]1[CH:39]=[CH:38][C:20]([NH:21][C:22]([C:24]2[CH:37]=[CH:36][C:27]([NH:28][C:29]3[CH:34]=[CH:33][N+:32]([CH3:35])=[CH:31][CH:30]=3)=[CH:26][CH:25]=2)=[O:23])=[CH:19][CH:18]=1.Cl.CO.CCOC(C)=O>CO.CCOC(C)=O>[Cl-:1].[CH3:35][N+:32]1[CH:31]=[CH:30][C:29]([NH:28][C:27]2[CH:26]=[CH:25][C:24]([C:22]([NH:21][C:20]3[CH:19]=[CH:18][C:17]([NH:16][C:2]4[C:11]5[C:6](=[CH:7][CH:8]=[C:9]([N+:12]([O-:14])=[O:13])[CH:10]=5)[N:5]=[CH:4][CH:3]=4)=[CH:39][CH:38]=3)=[O:23])=[CH:37][CH:36]=2)=[CH:34][CH:33]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 2872104-Chloro-6-nitroquinoline2×HCID 21584119Ethylacetate methanolHCID 672001654-{4-[(4-Aminoanilino)carbonyl]anilino}-1-methylpyridinium chloride

Product 1

HCID 671997341-Methyl-4-[4-({4-[(6-nitro-4-quinolinyl)amino]anilino}carbonyl)anilino]pyridinium chloride

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

To a suspension of 4-chloro-6-nitroquinoline (70 mg, 0.33 mmol) in MeOH (10 mL) was added compound D5 (100 mg, 0.28 mmol), and the mixture was stirred at 20° C. for 1 h (until a clear solution obtained). A drop of c.HCl was then added, and refluxing was continued for a further 20 h. TLC analysis (eluting with the top phase of a 5:4:1 mixture of n-BuOH:H2O:AcOH) showed some D5 remained, so more 4-chloro-6-nitroquinoline (35 mg, 0.16 mmol) was added and refluxing was continued for a further 4 h. The reaction mixture was then diluted with EtOAc and the resulted precipitate was filtered and washed sequentially with EtOAc, CH2Cl2 and diisopropylether, and finally crystallized from MeOH EtOAc to give Cpd. N1 (111 mg, 75%), mp (MeOH/EtOAc)>300° C.; 1H NMR [(CD3)2SO] δ14.50 (br, 1 H, N+H); 11,42, (br s, 1 H, NH), 11.10 (s, 1 H, NH), 10.58 (s, 1 H, NH), 9.82 (d, J=2.1 Hz, 1 H, ArH), 8.72 (dd, J=9.3, 2.2 Hz, 1 H, ArH), 8.60 (d, J=7.0 Hz, 1 H, ArH), 8.42 (d, J=7.4 Hz, 2 H, ArH), 8.24 (d, J=8.6 Hz, 1 H, ArH), 8.15 (d, J=8.6 Hz, 2 H, ArH), 8.04 (d, J=8.8 Hz, 2 H, ArH), 7.51 (t, J=8.3 Hz, 4 H, ArH), 7.34 (d, J=7.5 Hz, 2 H, ArH), 6.91 (d, J=7.0 Hz, 1 H, ArH), 4.01 (s, 3 H, N+CH3); LCMS 489+ve.

Workup

  1. customobtained)
  2. temperaturerefluxing
  3. waitwas continued for a further 20 h
  4. washTLC analysis (eluting with the top phase of a 5:4:1 mixture of n-BuOH
  5. temperaturerefluxing
  6. waitwas continued for a further 4 h
  7. filtrationthe resulted precipitate was filtered
  8. washwashed sequentially with EtOAc, CH2Cl2 and diisopropylether
  9. customfinally crystallized from MeOH EtOAc
  10. customto give Cpd

Sources & evidence

ORD record
ord-6756e6cf50f6455a832c723ebda240e5
Source dataset
uspto-grants-2011_05
Patent number
US07939546B2

Reaction notes

Loading…