Ethanol → HCID 178432923, Verbindung

HRID 416910Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 416910
[Br: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>[Br: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

Komponenten

8

Edukt 4

HCID 702EthanolHCID 24489Sodium DithioniteHCID 2795517tert-Butyl 4-(4-formylbenzyl)piperazine-1-carboxylateHCID 578971595-Bromo-4-(4-((2-methylthiazol-4-yl)methyl)piperazin-1-yl)-3-nitropyridin-2-amine

Produkt 1

HCID 178432923HCID 178432923, VerbindungAusbeute 33 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 222AmmoniaKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

To a mixture of 5-bromo-4-(4-((2-methylthiazol-4-yl)methyl)piperazin-1-yl)-3-nitropyridin-2-amine (0.062 g, 0.15 mmol), EtOH (2.6 mL) and DMF (0.35 mL), tert-butyl-4-(4-formylbenzyl)piperazine-1-carboxylate (0.050 g, 0.165 mmol) was added followed by a freshly prepared aqueous solution of Na2S2O4 (1M; 0.45 mL, 0.45 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 (0.033 g, 33%); 1H-NMR (500 Mz, DMSO-d6): δ 1.39 (s, 9H, C(CH3)3), 2.34 (t, J=5.0 Hz, 4H), 2.62-2.72 (m, 7H), 3.28-3.36 (m, 4H), 3.55 (s, 2H, NCH2), 3.64 (s, 2H, NCH2), 3.67 (t, J=4.0 Hz, 4H), 7.32 (s, 1H, thiazole 5-H), 7.47 (d, J=8.0 Hz, 2H, ArH, C6H4), 8.14 (d, J=8.5 Hz, 2H, ArH, C6H4), 8.23 (s, 1H, imidazo[4,5-b]pyridine 5-H), 13.47 (br s, 1H, imidazo[4,5-b]pyridine N—H); LC (Method B)-MS (ESI, m/z) 2.76 min—667/669 [(M+H)+, Br isotopic pattern]. ESI-HRMS: Found: 667.2190, calculated for C31H40BrN8O2S (M+H)+: 667.2178.

Aufarbeitung

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

Quellen und Nachweise

ORD-Eintrag
ord-255bd428c8174cf9b72ee648bc0f4914
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08088761B2

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