Ethanol → HCID 178432931, compound

HRID 416936Notes

Reaction equation

HRID 416936 reaction equation
[Cl:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][C:19]3[N:20]=[C:21]([CH3:24])[S:22][CH:23]=3)[CH2:14][CH2:13]2)=[C:4]([N+:9]([O-])=O)[C:5]([NH2:8])=[N:6][CH:7]=1.CCO.[C:28]([O:32][C:33]([N:35]1[CH2:40][CH2:39][N:38]([CH2:41][C:42]2[CH:47]=[CH:46][C:45]([CH:48]=O)=[CH:44][CH:43]=2)[CH2:37][CH2:36]1)=[O:34])([CH3:31])([CH3:30])[CH3:29].[O-]S(S([O-])=O)=O.[Na+].[Na+]>C(Cl)Cl.N.CN(C=O)C>[Cl:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][C:19]3[N:20]=[C:21]([CH3:24])[S:22][CH:23]=3)[CH2:14][CH2:13]2)=[C:4]2[N:9]=[C:48]([C:45]3[CH:44]=[CH:43][C:42]([CH2:41][N:38]4[CH2:37][CH2:36][N:35]([C:33]([O:32][C:28]([CH3:29])([CH3:31])[CH3:30])=[O:34])[CH2:40][CH2:39]4)=[CH:47][CH:46]=3)[NH:8][C:5]2=[N:6][CH:7]=1

Participants

8

Reactant 4

HCID 702EthanolHCID 24489Sodium DithioniteHCID 2795517tert-Butyl 4-(4-formylbenzyl)piperazine-1-carboxylateHCID 578971255-Chloro-4-(4-((2-methylthiazol-4-yl)methyl)piperazin-1-yl)-3-nitropyridin-2-amine

Product 1

HCID 178432931HCID 178432931, compoundYield 19%

Reagents, catalysts & solvents 3

HCID 222AmmoniaCatalystHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
85 °C

Procedure

To a mixture of 5-chloro-4-(4-((2-methylthiazol-4-yl)methyl)piperazin-1-yl)-3-nitropyridin-2-amine (0.028 g, 0.076 mmol), EtOH (1.3 mL) and DMF (0.18 mL), tert-butyl-4-(4-formylbenzyl)piperazine-1-carboxylate (0.025 g, 0.083 mmol) was added followed by a freshly prepared aqueous solution of Na2S2O4 (1M; 0.23 mL, 0.23 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; 92:8) to give the title compound as a solid (0.009 g, 18%); 1H-NMR (500 Mz, DMSO-d6): δ 1.39 (s, 9H, C(CH3)3), 2.34 (t, J=5.0 Hz, 4H), 2.62-2.70 (m, 7H), 3.29-3.35 (m, 4H), 3.55 (s, 2H, NCH2), 3.64 (s, 2H, NCH2), 3.67-3.74 (m, 4H), 7.32 (s, 1H, thiazole 5-H), 7.46 (d, J=8.0 Hz, 2H, ArH, C6H4), 8.10 (s, 1H, imidazo[4,5-b]pyridine 5-H), 8.13 (d, J=8.0 Hz, 2H, ArH, C6H4), 13.44 (br s, 1H, imidazo[4,5-b]pyridine N—H); LC (Method B)-MS (ESI, m/z) 2.66 min—623/625 [(M+H)+, Cl isotopic pattern]. ESI-HRMS: Found: 623.2680, calculated for C31H40ClN8O2S (M+H)+: 623.2683.

Workup

  1. additionwas added
  2. temperatureto cool to room temperature
  3. washeluted with DCM/MeOH (v/v; 92:8)

Sources & evidence

ORD record
ord-5a0a412ffcfe47aca618373daef41dce
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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