Sodium Dithionite → HCID 178419420, compound

HRID 416794Notes

Reaction equation

HRID 416794 reaction equation
[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][C:19]3[CH:20]=[N:21][CH:22]=[CH:23][CH:24]=3)[CH2:14][CH2:13]2)=[C:4]([N+:9]([O-])=O)[C:5]([NH2:8])=[N:6][CH:7]=1.[N:25]1([CH2:31][C:32]2[CH:33]=[C:34]([CH:37]=[CH:38][CH:39]=2)[CH:35]=O)[CH2:30][CH2:29][O:28][CH2:27][CH2:26]1.[O-]S(S([O-])=O)=O.[Na+].[Na+]>CCO>[Br:1][C:2]1[C:3]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][C:19]3[CH:20]=[N:21][CH:22]=[CH:23][CH:24]=3)[CH2:14][CH2:13]2)=[C:4]2[N:9]=[C:35]([C:34]3[CH:37]=[CH:38][CH:39]=[C:32]([CH2:31][N:25]4[CH2:30][CH2:29][O:28][CH2:27][CH2:26]4)[CH:33]=3)[NH:8][C:5]2=[N:6][CH:7]=1

Participants

5

Reactant 3

HCID 24489Sodium DithioniteHCID 71646033-(Morpholinomethyl)benzaldehydeHCID 468687795-Bromo-3-nitro-4-(4-(pyridin-3-ylmethyl)piperazin-1-yl)pyridin-2-amine

Product 1

HCID 178419420HCID 178419420, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

To a mixture of 5-bromo-3-nitro-4-(4-pyridin-3-ylmethyl-piperazin-1-yl)-pyridin-2-ylamine (0.060 g, 0.15 mmol) and EtOH (4.5 ml) was added 3-morpholin-4-ylmethyl-benzaldehyde (0.035 g, 0.17 mmol) followed by a freshly prepared 1M aqueous solution of Na2S2O4 (0.55 ml, 0.55 mmol). The reaction mixture was stirred at 70° C. for 9 h, then allowed to cool to room temperature and concentrated in vacuo. The residue was absorbed on silica gel, and the free-running powder was placed on a 10 g isolute silica column. Elution of the column with a gradient of methanol (2 to 10%) in ethyl acetate/dichloromethane (v:v; 4:1) afforded a yellow solid which was triturated with diethyl ether. The pale yellow precipitate was collected by filtration, and was successively washed with diethyl ether, water, and diethyl, then dried in vacuo (0.003 g, 4%). 1H-NMR (500 MHz, DMSO-d6) 2.40 (br s, 4H) and 3.59 (t, J=4.50 Hz, 4H) (morpholine N(CH2)2, and morpholine O(CH2)2), 2.63 (br s, 4H, piperazine N(CH2)2), 3.68 (br s, 4H, piperazine N(CH2)2), 3.56 (s, 2H) and 3.62 (s, 2H) (NCH2-pyridyl and C6H4CH2), 7.40 (dd, J=4.5, 7.7 Hz, 1H, pyridine 5-H), 7.45 (d, J=7.7 Hz, 1H, PhH), 7.49 (t, J=7.7 Hz, 1H, PhH), 7.78 (d, J=7.8 Hz, 1H, pyridine 4-H), 8.07 (d, J=7.6 Hz, 1H, PhH), 8.14 (s, 1H, PhH), 8.23 (s, 1H, imidazo[4,5-b]pyridine 5-H), 8.50 (dd, J=1.5, 4.8 Hz, 1H, pyridine 6-H), 8.56 (d, J=1.4 Hz, 1H, pyridine 2-H), 13.48 (br s, 1H, imidazo[4,5-b]pyridine N—H);

Workup

  1. temperatureto cool to room temperature
  2. concentrationconcentrated in vacuo
  3. customThe residue was absorbed on silica gel
  4. washElution of the column with a gradient of methanol (2 to 10%) in ethyl acetate/dichloromethane (v:v; 4:1)
  5. customafforded a yellow solid which
  6. customwas triturated with diethyl ether
  7. filtrationThe pale yellow precipitate was collected by filtration
  8. washwas successively washed with diethyl ether, water, and diethyl
  9. customdried in vacuo (0.003 g, 4%)

Sources & evidence

ORD record
ord-6c1d369e9ab149e48b583d169824f3b5
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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