Sodium Dithionite → 6-Bromo-2-[4-(4-methyl-piperazin-1-yl)-phenyl]-7-[4-(1-phenyl-ethyl)-piperazin-1-yl]-3H-imidazo[4,5-b]pyridine

HRID 416800Notes

Reaction equation

HRID 416800 reaction equation
[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH:18]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[CH3:19])[CH2:14][CH2:13]2)=[C:4]([N+:9]([O-])=O)[C:5]([NH2:8])=[N:6][CH:7]=1.[CH3:26][N:27]1[CH2:32][CH2:31][N:30]([C:33]2[CH:40]=[CH:39][C:36]([CH:37]=O)=[CH:35][CH:34]=2)[CH2:29][CH2:28]1.[O-]S(S([O-])=O)=O.[Na+].[Na+]>CCO>[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH:18]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[CH3:19])[CH2:14][CH2:13]2)=[C:4]2[N:9]=[C:37]([C:36]3[CH:35]=[CH:34][C:33]([N:30]4[CH2:29][CH2:28][N:27]([CH3:26])[CH2:32][CH2:31]4)=[CH:40][CH:39]=3)[NH:8][C:5]2=[N:6][CH:7]=1

Participants

5

Reactant 3

HCID 24489Sodium DithioniteHCID 7365334-(4-Methylpiperazin-1-yl)benzaldehydeHCID 578973125-Bromo-3-nitro-4-(4-(1-phenylethyl)piperazin-1-yl)pyridin-2-amine

Product 1

HCID 1784360546-Bromo-2-[4-(4-methyl-piperazin-1-yl)-phenyl]-7-[4-(1-phenyl-ethyl)-piperazin-1-yl]-3H-imidazo[4,5-b]pyridine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 5-bromo-3-nitro-4-[4-(1-phenyl-ethyl)-piperazin-1-yl]-pyridin-2-ylamine (0.065 g, 0.16 mmol) and EtOH (7.5 ml) was added 4-(4-methyl-piperazin-1-yl)-benzaldehyde (0.042 g, 0.20 mmol) followed by a freshly prepared aqueous solution of Na2S2O4 (1M; 0.65 ml, 0.65 mmol). The reaction mixture was stirred at 80° C. for 20 h, then allowed to cool to room temperature, and concentrated in vacuo. The residue was absorbed on silica gel, the free-running powder was placed on a 10 g isolute silica column which was eluted first with 2% methanol in ethyl acetate/dichloromethane (v:v; 1:1) and then a gradient of methanol (2 to 8%) in chloroform. The titled compound was obtained as a brown solid after trituration with diethyl ether a (0.007 g, 8%). 1H-NMR (500 MHz, CD3OD) 1.55 (d, J=6.4 Hz, 3H, CHCH3), 2.50 (s, 3H, N—CH3), 2.80 (br s, 6H), 2.90 (br s, 2H), 3.42 (br s, 4H) and 3.80 (br s, 4H) (8× piperazine N(CH2)2), 3.70 (m, 1H, CHCH3), 7.10 (d, J=8.9 Hz, 2H) and 8.02 (d, J=8.7 Hz, 2H) (3,5-C6H4—N and 2,6-C6H4—N), 7.31 (t, J=7.2 Hz, 1H, PhH), 7.39 (t, J=7.6 Hz, 2H, PhH), 7.37 (d, J=7.2 Hz, 2H) (PhH), 8.20 (s, 1H, imidazo[4,5-b]pyridine 5-H);

Workup

  1. temperatureto cool to room temperature
  2. concentrationconcentrated in vacuo
  3. customThe residue was absorbed on silica gel
  4. washwas eluted first with 2% methanol in ethyl acetate/dichloromethane (v:v; 1:1)

Sources & evidence

ORD record
ord-137e125137f04c25b210d98b6ddf599f
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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