Sodium Dithionite → US9447092, Comparator 2, Example 57

HRID 416784

Reaction equation

HRID 416784 reaction equation
BrC1C(N2CCN(C(NC3C=CC=CC=3)=O)CC2)=C2N=C(C3C=CC(N(C)C)=CC=3)NC2=NC=1.[Br:35][C:36]1[C:37]([N:46]2[CH2:51][CH2:50][N:49]([CH2:52][C:53]3[CH:54]=[N:55][CH:56]=[CH:57][CH:58]=3)[CH2:48][CH2:47]2)=[C:38]([N+:43]([O-])=O)[C:39]([NH2:42])=[N:40][CH:41]=1.[O-]S(S([O-])=O)=O.[Na+].[Na+].[CH3:67][N:68]1[C:72]([CH3:73])=[C:71]([CH:74]=O)[C:70]([CH3:76])=[N:69]1>C(O)C.CN(C=O)C>[Br:35][C:36]1[C:37]([N:46]2[CH2:51][CH2:50][N:49]([CH2:52][C:53]3[CH:54]=[N:55][CH:56]=[CH:57][CH:58]=3)[CH2:48][CH2:47]2)=[C:38]2[N:43]=[C:74]([C:71]3[C:70]([CH3:76])=[N:69][N:68]([CH3:67])[C:72]=3[CH3:73])[NH:42][C:39]2=[N:40][CH:41]=1

Participants

7

Reactant 4

HCID 24489Sodium DithioniteHCID 7365151,3,5-trimethyl-1H-pyrazole-4-carboxaldehydeHCID 468687795-Bromo-3-nitro-4-(4-(pyridin-3-ylmethyl)piperazin-1-yl)pyridin-2-amineHCID 178482685HCID 178482685, compound

Product 1

HCID 178434018US9447092, Comparator 2, Example 57Yield 34%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6228DimethylformamideSolvent

Procedure

This was prepared using the same procedure as for 4-(6-bromo-2-(4-(dimethylamino)phenyl)-3H-imidazo[4,5-b]pyridin-7-yl)-N-phenylpiperazine-1-carboxamide, but here using 5-bromo-3-nitro-4-(4-(pyridin-3-ylmethyl)piperazin-1-yl)pyridin-2-amine (75 mg, 0.19 mmol), DMF (0.85 mL), ethanol (0.15 mL), 1M Na2S2O4 (3 eq, 0.57 mmol, 0.57 mL) and 1,3,5-trimethyl-1H-pyrazole-4-carboxaldehyde (1.1 eq, 0.21 mmol, 29 mg). After 6 h, concentration in vacuo and preparation by preparative tlc (CH2Cl2-MeOH, 9:1) gave the product (31 mg, 34%) as a colourless solid; 1H-NMR (500 MHz, DMSO-d6) 2.36 (s, 3H, CH3), 2.49 (s, 3H, CH3), 2.60 (s, br, 4H, piperazine N(CH2)2), 3.61 (s, 2H, CH2), 3.64 (t, J=4.2 Hz, 4H, piperazine N(CH2)2), 3.74 (s, 3H, NCH3), 7.38 (dd, J=7.7, 4.8 Hz, 1H, pyridine H-5), 7.77 (dt, J=7.8, 1.5 Hz, 1H, pyridine H-4), 8.19 (s, 1H, imidazo[4,5-b]pyridine H-5), 8.49 (dd, J=4.7, 1.4 Hz, 1H, pyridine H-6), 8.55 (d, J=1.5 Hz, 1H, pyridine H-2), 12.67 (s, br, 1H, imidazo[4,5-b]pyridine NH);

Workup

  1. customThis was prepared
  2. concentrationconcentration
  3. customin vacuo and preparation by preparative tlc (CH2Cl2-MeOH, 9:1)

Sources & evidence

ORD record
ord-52851715f0f845d5bbc1af66df249a01
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Linked notes

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