Hydrazine hydrate (1:1) → HCID 21864862, compound

HRID 856927Notes

Reaction equation

HRID 856927 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:9]=[CH:10][C:11]([N+:18]([O-])=O)=[C:12]3[C:17]=2[N:16]=[CH:15][CH:14]=[CH:13]3)[CH2:4][CH2:3]1.O.NN>C1COCC1.CCO.[Ni]>[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:9]=[CH:10][C:11]([NH2:18])=[C:12]3[C:17]=2[N:16]=[CH:15][CH:14]=[CH:13]3)[CH2:4][CH2:3]1

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 2829619HCID 2829619, compound

Product 1

HCID 21864862HCID 21864862, compoundYield 100.1%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 21873804Tetrahydrofuran ethanolSolvent

Procedure

To a solution of 8-(4-methyl-1-piperazinyl)-5-nitroquinoline (0.379 g, 1.39 mmol) in THF:EtOH 1:4 solvent system was added Raney-Ni (1.0 mL suspension in EtOH) followed by hydrazine hydrate (0.348 g, 6.95 mmol). The mixture was stirred vigorously at room temperature for 16 hours and then filtered through celite pretreated with water. The filtrate was concentrated, and the residue was purified by column chromatography (SiO2, CHCl3/MeOH/NH3 9:1:0.4%) to give 0.337 g of 8-(4-methyl-1-piperazinyl)-5-quinolinylamine. The amine was dissolved in CH2Cl2 (6.0 mL) and pyridine (0.785 mL, 9.73 mmol) and benzenesulfonyl chloride (0.178 mL, 1.39 mmol) was added. The reaction mixture was stirred at room temperature for 16 hours and then washed with saturated aqueous NaHCO3. The organic phase was dried with Na2SO4, filtered and concentrated. The crude product was purified by column chromatography (SiO2, CHCl3/MeOH/NH3 9:1:0.4%) to give 0.130 g of the free base which was converted to its HCl-salt: 1H NMR (DMSO-d6) δ; 11.09 (br s, 1H), 10.32 (s, 1H), 8.94–8.89 (m, 1H), 8.55–8.48 (m, 1H), 7.68–7.65 (m, 2H), 7.64–7.57 (m, 2H), 7.54–7.49 (m, 2H), 7.27–7.22 (m, 1H), 7.12–7.08 (m, 1H), 3.95–3.84 (m, 2H), 3.55–3.49 (m, 2H), 3.45–3.35 (m, 2H), 3.26–3.16 (m, 2H), 2.85–2.82 (m, 3); MS (posESI) m/z 383 (M+H).

Workup

  1. filtrationfiltered through celite
  2. concentrationThe filtrate was concentrated
  3. customthe residue was purified by column chromatography (SiO2, CHCl3/MeOH/NH3 9:1:0.4%)

Sources & evidence

ORD record
ord-0f45b346ae0548fa974ae0b41850e0f6
Source dataset
uspto-grants-2006_12
Patent number
US07144883B2

Reaction notes

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