Sodium Dithionite → HCID 178419430, compound

HRID 416901Notes

Reaction equation

HRID 416901 reaction equation
[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][C:19]3[S:20][CH:21]=[CH:22][N:23]=3)[CH2:14][CH2:13]2)=[C:4]([N+:9]([O-])=O)[C:5]([NH2:8])=[N:6][CH:7]=1.[O:24]1[CH2:29][CH2:28][N:27]([CH2:30][C:31]2[CH:38]=[CH:37][C:34]([CH:35]=O)=[CH:33][CH:32]=2)[CH2:26][CH2:25]1.[O-]S(S([O-])=O)=O.[Na+].[Na+]>CCO.C(Cl)Cl.N>[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][C:19]3[S:20][CH:21]=[CH:22][N:23]=3)[CH2:14][CH2:13]2)=[C:4]2[N:9]=[C:35]([C:34]3[CH:33]=[CH:32][C:31]([CH2:30][N:27]4[CH2:28][CH2:29][O:24][CH2:25][CH2:26]4)=[CH:38][CH:37]=3)[NH:8][C:5]2=[N:6][CH:7]=1

Participants

7

Reactant 3

HCID 24489Sodium DithioniteHCID 27954984-[(Morpholin-4-yl)methyl]benzaldehydeHCID 57897270HCID 57897270, compound

Product 1

HCID 178419430HCID 178419430, compoundYield 40.2%

Reagents, catalysts & solvents 3

HCID 222AmmoniaCatalystHCID 702EthanolSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
85 °C

Procedure

To a mixture of 5-bromo-3-nitro-4-(4-(thiazol-2-ylmethyl)piperazin-1-yl)pyridin-2-amine (0.088 g, 0.22 mmol) and EtOH (2.5 mL), 4-(morpholinomethyl)-benzaldehyde (0.045 g, 0.24 mmol) in EtOH (2.5 mL) was added, followed by a freshly prepared aqueous solution of Na2S2O4 (1M; 0.66 mL, 0.66 mmol). The reaction mixture was heated at 85° C. for 24 h, then allowed to cool to room temperature and diluted with DCM and a few drops of aqueous NH3 until complete dissolution was observed. This solution was deposited on two preparative silica TLC plates and eluted with DCM/MeOH (v/v; 96:4) to give the title compound as a solid (0.049 g, 40%); 1H-NMR (500 Mz, DMSO-d6): δ 2.33-2.43 (m, 4H), 2.72-2.79 (m, 4H), 3.54 (s, 2H, NCH2), 3.59 (t, J=4.5 Hz, 4H), 3.70 (t, J=4.5 Hz, 4H), 3.95 (s, 2H, NCH2), 7.48 (d, J=8.5 Hz, 2H, ArH), 7.69 (d, J=3.5 Hz, 1H, thiazole 5-H), 7.75 (d, J=3.0 Hz, 1H, thiazole 4-H), 8.15 (d, J=8.0 Hz, 2H, ArH), 8.24 (s, 1H, imidazo[4,5-b]pyridine 5-H), 13.49 (br s, 1H, imidazo[4,5-b]pyridine N—H); LC (Method B)-MS (ESI, m/z) 2.37 min—554/556 [(M+H)+, Br isotopic pattern]. ESI-HRMS: Found: 554.1341, calculated for C25H29BrN7OS (M+H)+: 554.1338.

Workup

  1. additionwas added
  2. temperatureto cool to room temperature
  3. washeluted with DCM/MeOH (v/v; 96:4)

Sources & evidence

ORD record
ord-17b320759406430eafa9bccdac703a33
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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