Ethanol → HCID 178436053, compound

HRID 416821Notes

Reaction equation

HRID 416821 reaction equation
[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH:18]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[CH3:19])[CH2:14][CH2:13]2)=[C:4]([N+:9]([O-])=O)[C:5]([NH2:8])=[N:6][CH:7]=1.CCO.[OH:29][CH:30]1[CH2:35][CH2:34][N:33]([C:36]2[CH:43]=[CH:42][C:39]([CH:40]=O)=[CH:38][CH:37]=2)[CH2:32][CH2:31]1.[O-]S(S([O-])=O)=O.[Na+].[Na+]>C(OCC)C>[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH:18]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[CH3:19])[CH2:14][CH2:13]2)=[C:4]2[N:9]=[C:40]([C:39]3[CH:38]=[CH:37][C:36]([N:33]4[CH2:34][CH2:35][CH:30]([OH:29])[CH2:31][CH2:32]4)=[CH:43][CH:42]=3)[NH:8][C:5]2=[N:6][CH:7]=1

Participants

6

Reactant 4

HCID 702EthanolHCID 24489Sodium DithioniteHCID 127174464-(4-Hydroxypiperidin-1-yl)benzaldehydeHCID 578973125-Bromo-3-nitro-4-(4-(1-phenylethyl)piperazin-1-yl)pyridin-2-amine

Product 1

HCID 178436053HCID 178436053, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 5-bromo-3-nitro-4-[4-(1-phenyl-ethyl)-piperazin-1-yl]-pyridin-2-ylamine (0.036 g, 0.09 mmol) and EtOH (4.5 ml) was added 4-(4-hydroxy-piperidin-1-yl)-benzaldehyde (0.025 g, 0.12 mmol) followed by a freshly prepared aqueous solution of Na2S2O4 (1M; 0.38 ml, 0.38 mmol). The reaction mixture was stirred at 80° C. for 22 h, then allowed to cool to room temperature, and concentrated in vacuo. The residue was absorbed on silica gel, the free-running powder was placed on a 10 g isolute silica column and elution with a gradient of methanol (0 to 5%) in ethyl acetate/dichloromethane (v:v; 1:1) afforded a yellow solid. The title compound was obtained as a white solid after trituration with diethyl ether (0.016 g, 32%); 1H-NMR (500 MHz, DMSO-d6) 1.35 (d, J=6.7 Hz, 3H, CHCH3), 1.45 (m, 2H) and 1.82 (m, 2H) (piperidine CH2), 2.54 (m, 2H), 2.62 (br s, 2H), 2.98 (t, 2H) and 3.70 (m, 3H) (piperazine N—(CH2)2, piperidine CH2 and piperidine CHOH), 3.50 (q, J=6.7 Hz, 1H, CHCH3), 3.67 (br s, 4H, piperazine N(CH2)2), 4.67 (d, J=4.1 Hz, CHOH, exchangeable with D2O), 7.03 (d, J=8.9 Hz, 2H) and 8.00 (d, J=8.8 Hz, 2H) (3,5-C6H4—N and 2,6-C6H4—N), 8.14 (s, 1H, imidazo[4,5-b]pyridine 5-H), 13.16 (br s, 1H, imidazo[4,5-b]pyridine N—H); LC (Method B)-MS (ESI, m/z): Rt=3.39 min—561, 563 [(M+H)+, Br isotopic pattern]. ESI-HRMS: Found: 561.1975, calculated for C29H34BrN6O (M+H)+: 561.1977.

Workup

  1. temperatureto cool to room temperature
  2. concentrationconcentrated in vacuo
  3. customThe residue was absorbed on silica gel
  4. washthe free-running powder was placed on a 10 g isolute silica column and elution with a gradient of methanol (0 to 5%) in ethyl acetate/dichloromethane (v:v; 1:1)
  5. customafforded a yellow solid

Sources & evidence

ORD record
ord-7397af28b8da47089f5038904282da9f
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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