Sodium Dithionite → HCID 178436052, compound

HRID 416799

Reaction equation

HRID 416799 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.[N:26]1([CH2:32][C:33]2[CH:40]=[CH:39][C:36]([CH:37]=O)=[CH:35][CH:34]=2)[CH2:31][CH2:30][O:29][CH2:28][CH2:27]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]([CH2:32][N:26]4[CH2:31][CH2:30][O:29][CH2:28][CH2:27]4)=[CH:40][CH:39]=3)[NH:8][C:5]2=[N:6][CH:7]=1

Participants

5

Reactant 3

HCID 24489Sodium DithioniteHCID 27954984-[(Morpholin-4-yl)methyl]benzaldehydeHCID 57897312HCID 57897312, compound

Product 1

HCID 178436052HCID 178436052, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

To a mixture of 5-bromo-3-nitro-4-[4-(1-phenyl-ethyl)-piperazin-1-yl]-pyridin-2-ylamine (0.060 g, 0.15 mmol) and EtOH (6.0 ml) was added 4-morpholin-4-ylmethyl-benzaldehyde (0.039 g, 0.19 mmol) followed by a freshly prepared aqueous solution of Na2S2O4 (1M; 0.60 ml, 0.60 mmol). The reaction mixture was stirred at 70° C. for 5 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 and elution with a gradient of methanol (0 to 9%) in ethyl acetate/dichloromethane (v:v; 1:1) afforded a yellow solid which was triturated with diethyl ether. The precipitate was collected by filtration, successively washed with diethyl ether, water, diethyl ether, and dried (0.002 g, 3%). 1H-NMR (500 MHz, DMSO-d6) 1.37 (d, J=6.6 Hz, 3H, CHCH3), 2.38 (br s, 4H) and 3.59 (t, J=4.6 Hz, 4H) (morpholine N(CH2)2 and morpholine O(CH2)2), 2.54 (br s, 2H), 2.63 (br s, 2H) and 3.65 (br s, 4H) piperazine N(CH2)2), 3.50 (q, 1H, CHCH3), 3.57 (s, 2H, C6H4CH2), 7.26 (m, 1H) and 7.37 (m, 4H) (PhH), 7.47 (d, J=8.9 Hz, 2H) and 8.13 (d, J=8.2 Hz, 2H) (3,5-C6H4— and 2,6-C6H4—), 8.22 (s, 1H, imidazo[4,5-b]pyridine 5-H), 13.45 (br s, 1H, imidazo[4,5-b]pyridine N—H);

Workup

  1. temperatureto cool to room temperature
  2. concentrationconcentrated in vacuo
  3. customThe residue was absorbed on silica gel
  4. washthe free-running powder was placed on a 10 g isolute silica column and elution with a gradient of methanol (0 to 9%) in ethyl acetate/dichloromethane (v:v; 1:1)
  5. customafforded a yellow solid which
  6. customwas triturated with diethyl ether
  7. filtrationThe precipitate was collected by filtration
  8. washsuccessively washed with diethyl ether, water, diethyl ether
  9. customdried (0.002 g, 3%)

Sources & evidence

ORD record
ord-6985305c60c149c8ae2199afcf73b104
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Linked notes

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