Ethanol → HCID 178521209, compound

HRID 416950Notes

Reaction equation

HRID 416950 reaction equation
[NH2:1][C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([N:11]2[CH2:16][CH2:15][N:14]([CH2:17][C:18]([NH:20][C:21]3[S:22][CH:23]=[CH:24][N:25]=3)=[O:19])[CH2:13][CH2:12]2)[C:5]([Cl:26])=[CH:4][N:3]=1.CCO.[O:30]=[S:31]1(=[O:45])[CH2:36][CH2:35][N:34]([C:37]2[CH:44]=[CH:43][C:40]([CH:41]=O)=[CH:39][CH:38]=2)[CH2:33][CH2:32]1.[O-]S(S([O-])=O)=O.[Na+].[Na+]>C(Cl)Cl.N.CN(C=O)C>[Cl:26][C:5]1[C:6]([N:11]2[CH2:16][CH2:15][N:14]([CH2:17][C:18]([NH:20][C:21]3[S:22][CH:23]=[CH:24][N:25]=3)=[O:19])[CH2:13][CH2:12]2)=[C:7]2[N:8]=[C:41]([C:40]3[CH:39]=[CH:38][C:37]([N:34]4[CH2:33][CH2:32][S:31](=[O:45])(=[O:30])[CH2:36][CH2:35]4)=[CH:44][CH:43]=3)[NH:1][C:2]2=[N:3][CH:4]=1

Participants

8

Reactant 4

HCID 702EthanolHCID 24489Sodium DithioniteHCID 435816154-(1,1-Dioxo-1lambda~6~,4-thiazinan-4-yl)benzaldehydeHCID 468678042-(4-(2-amino-5-chloro-3-nitropyridin-4-yl)piperazin-1-yl)-N-(thiazol-2-yl)acetamide

Product 1

HCID 178521209HCID 178521209, compoundYield 13.1%

Reagents, catalysts & solvents 3

HCID 222AmmoniaCatalystHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
85 °C

Procedure

To a mixture of 2-(4-(2-amino-5-chloro-3-nitropyridin-4-yl)piperazin-1-yl)-N-(thiazol-2-yl)acetamide (0.050 g, 0.13 mmol, 1 eq), EtOH (2.2 mL) and DMF (0.29 mL), 4-(1,1-dioxothiomorpholino)benzaldehyde (0.033 g, 0.14 mmol, 1.1 eq) was added followed by a freshly prepared aqueous solution of Na2S2O4 (1M; 0.38 mL, 0.38 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) and washed with DCM/MeOH (1 mL, 1/1) to give the title compound as a pale yellow solid (0.010 g, 13%); 1H-NMR (500 Mz, DMSO-d6): 2.72-2.83 (m, 4H, piperazine N(CH2)2), 3.08-3.17 (m, 4H, piperazine N(CH2)2), 3.40 (s, 2H, NCH2CO), 3.66-3.77 (m, 4H, dithioxomorpholino SO2(CH2)2), 3.85-3.95 (m, 4H, dithioxomorpholino SO2(CH2)2), 7.17 (d, J=8.5 Hz, 2H, ArH C6H4), 7.23 (d, J=3.5 Hz, 1H) and 7.49 (d, J=3.5 Hz, 1H) (thiazole H-4, H-5), 8.08 (s, 1H, imidazo[4,5-b]pyridine 5-H), 8.12 (d, J=8.5 Hz, 1H, ArH, C6H4), 11.88 (br s, 1H, NHCO), 13.31 (br s, 1H, imidazo[4,5-b]pyridine N—H); LC (Method B)-MS (ESI, m/z) 2.47 min—541/543 [(M+H)+, Cl isotopic pattern].

Workup

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

Sources & evidence

ORD record
ord-ed38b3e1e5d947b0b2e7c35f7cefb9c9
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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