Sodium Dithionite → HCID 178453048, compound

HRID 416708Notes

Reaction equation

HRID 416708 reaction equation
[NH2:1][C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([N:11]2[CH2:16][CH2:15][N:14]([CH2:17][C:18]([NH:20][C:21]3[S:22][CH:23]=[CH:24][N:25]=3)=[O:19])[CH2:13][CH2:12]2)[C:5]([Br:26])=[CH:4][N:3]=1.[CH:27]([C:29]1[CH:30]=[C:31]([CH:41]=[CH:42][CH:43]=1)[CH2:32][NH:33][C:34](=[O:40])[O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=O.[O-]S(S([O-])=O)=O.[Na+].[Na+]>C(O)C>[C:36]([O:35][C:34](=[O:40])[NH:33][CH2:32][C:31]1[CH:41]=[CH:42][CH:43]=[C:29]([C:27]2[NH:1][C:2]3=[N:3][CH:4]=[C:5]([Br:26])[C:6]([N:11]4[CH2:16][CH2:15][N:14]([CH2:17][C:18](=[O:19])[NH:20][C:21]5[S:22][CH:23]=[CH:24][N:25]=5)[CH2:13][CH2:12]4)=[C:7]3[N:8]=2)[CH:30]=1)([CH3:39])([CH3:38])[CH3:37]

Participants

5

Reactant 3

HCID 24489Sodium Dithionite2×HCID 2794834tert-Butyl 3-formylbenzylcarbamate2×HCID 468678032-(4-(2-amino-5-bromo-3-nitropyridin-4-yl)piperazin-1-yl)-N-(thiazol-2-yl)acetamide

Product 1

HCID 178453048HCID 178453048, compoundYield 27.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To 2-[4-(2-Amino-5-bromo-3-nitro-pyridin-4-yl)-piperazin-1-yl]-N-thiazol-2-yl-acetamide (0.1 g, 0.22 mmol) in ethanol (5 ml) was added tert-butyl N-(3 formylbenzyl)carbamate (69 mg, 0.29 mmol) and 1M aq. Na2S2O4 (900 μL, 0.9 mmol). The reaction mixture was stirred at 80° C. for 16 h. tert-Butyl N-(3 formylbenzyl)carbamate (20 mg, 0.08 mmol) and 1M aq. Na2S2O4 (200 μL, 0.2 mmol) were added and the reaction mixture was stirred for another 5 h. The reaction mixture was concentrated in vacuo. The crude product was purified by chromatography on silica gel (100% dichloromethane to dichloromethane/ethyl acetate 1:1+1% methanol to 2% methanol in ethyl acetate). The isolated product was further triturated in ether, filtered, and dried in vacuo to give the title compound as a pale yellow solid (0.038 g, 27%); 1H-NMR (500 MHz, DMSO-d6) 1.39 (s, 9H, CH3 Boc), 2.78 (broad s, 4H, piperazine N(CH2)2), 3.40 (s, 2H, CH2CO), 3.70 (broad s, 4H, piperazine N(CH2)2), 4.22 (d, J=6.23 Hz, 2H, CH2NHBOC), 7.24 (d, 1H, J=3.60 Hz, thiazole 4-H or 5-H), 7.37 (d, J=7.21 Hz, 1H) and 8.02 (d, J=7.21 Hz, 1H) (4-ArH, and 6-ArH), 7.47 (m, 1H, 5-ArH), 7.49 (d, J=4.12 Hz, 1H, thiazole 4-H or 5-H), 8.11 (s, 1H, imidazo[4,5-b]pyridine 5-H), 11.89 (s, 1H, CONH), 13.54 (s, 1H, imidazo[4,5-b]pyridine NH);

Workup

  1. additionwere added
  2. concentrationThe reaction mixture was concentrated in vacuo
  3. customThe crude product was purified by chromatography on silica gel (100% dichloromethane to dichloromethane/ethyl acetate 1:1+1% methanol to 2% methanol in ethyl acetate)
  4. customThe isolated product was further triturated in ether
  5. filtrationfiltered
  6. customdried in vacuo

Sources & evidence

ORD record
ord-ac0a897c5fdb459ca48c7fd21f8d82fe
Source dataset
uspto-grants-2012_01
Patent number
US08088761B2

Reaction notes

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