Sodium Dithionite → HCID 178481242、化合物

HRID 416943ノート

反応式

HRID 416943 の反応式
[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][C:19]3[N:23]([CH3:24])[CH:22]=[N:21][CH:20]=3)[CH2:14][CH2:13]2)=[C:4]([N+:9]([O-])=O)[C:5]([NH2:8])=[N:6][CH:7]=1.[C:25]([O:29][C:30]([N:32]1[CH2:37][CH2:36][N:35]([CH2:38][C:39]2[CH:44]=[CH:43][C:42]([CH:45]=O)=[CH:41][CH:40]=2)[CH2:34][CH2:33]1)=[O:31])([CH3:28])([CH3:27])[CH3:26].[O-]S(S([O-])=O)=O.[Na+].[Na+]>CCO.CN(C=O)C.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[N:23]([CH3:24])[CH:22]=[N:21][CH:20]=3)[CH2:14][CH2:13]2)=[C:4]2[N:9]=[C:45]([C:42]3[CH:41]=[CH:40][C:39]([CH2:38][N:35]4[CH2:34][CH2:33][N:32]([C:30]([O:29][C:25]([CH3:26])([CH3:28])[CH3:27])=[O:31])[CH2:37][CH2:36]4)=[CH:44][CH:43]=3)[NH:8][C:5]2=[N:6][CH:7]=1

参加物

8

反応物 3

HCID 24489Sodium DithioniteHCID 2795517tert-Butyl 4-(4-formylbenzyl)piperazine-1-carboxylateHCID 578972865-Bromo-4-(4-((1-methyl-1H-imidazol-5-yl)methyl)piperazin-1-yl)-3-nitropyridin-2-amine

生成物 1

HCID 178481242HCID 178481242、化合物収率 39%

試薬・触媒・溶媒 4

HCID 222Ammonia触媒HCID 702Ethanol溶媒HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
85 °C

実験手順

To a mixture of 5-bromo-4-(4-((1-methyl-1H-imidazol-5-yl)methyl)piperazin-1-yl)-3-nitropyridin-2-amine (0.050 g, 0.13 mmol, 1 eq) in EtOH (2.2 mL) and DMF (0.3 mL), tert-butyl-4-(4-formylbenzyl)piperazine-1-carboxylate (0.042 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) to give the title compound as a solid (0.032 g, 39%); 1H-NMR (500 Mz, DMSO-d6): 1.39 (s, 9H, C(CH3)3), 2.34 (t, J=5.0 Hz, 4H), 2.56-2.62 (m, 4H), 3.29-3.35 (m, 4H), 3.54 (s, 2H, NCH2), 3.55 (s, 2H, NCH2), 3.61-3.66 (m, 4H), 3.68 (s, 3H, CH3), 6.80 (s, 1H, imidazole 4-H), 7.46 (d, J=8.0 Hz, 2H, ArH, C6H4), 7.57 (s, 1H, imidazole 2-H), 8.14 (d, J=8.5 Hz, 2H, ArH, C6H4), 8.23 (s, 1H, imidazo[4,5-b]pyridine 5-H); LC (Method B)-MS (ESI, m/z) 2.33 min—650/652 [(M+H)+], Br isotopic pattern]. ESI-HRMS: Found: 650.2565, calculated for C31H41BrN9O2 (M+H)+: 650.2567.

後処理

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

出典と根拠

ORDレコード
ord-408af10d786744b8addb811bba5eacbe
出典データセット
uspto-grants-2012_01
特許番号
US08088761B2

反応ノート

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