Pyridine → HCID 131726129, compound

HRID 2100323Notes

Reaction equation

HRID 2100323 reaction equation
[N+:1]([C:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7]([N:14]2[CH2:19][CH2:18][N:17]3[CH2:20][CH2:21][CH2:22][CH:16]3[CH2:15]2)=[CH:6][CH:5]=1)([O-])=O.O.NN.N1C=CC=CC=1.[C:32]1([CH3:42])[CH:37]=[CH:36][C:35]([S:38]([Cl:41])(=[O:40])=[O:39])=[CH:34][CH:33]=1>C1COCC1.[Ni].CCO>[ClH:41].[CH2:15]1[N:14]([C:7]2[C:8]3[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=3)[C:4]([NH:1][S:38]([C:35]3[CH:36]=[CH:37][C:32]([CH3:42])=[CH:33][CH:34]=3)(=[O:40])=[O:39])=[CH:5][CH:6]=2)[CH2:19][CH2:18][N:17]2[CH2:20][CH2:21][CH2:22][CH:16]12

Participants

8

Reactant 4

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 24654Hydrazine hydrate (1:1)HCID 21864749HCID 21864749, compound2×

Product 1

HCID 131726129HCID 131726129, compoundYield 95%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (intermediate 6) 2-(4-nitro-1-naphthyl)octahydropyrrolo[1,2-a]pyrazine (0.160 g, 0.54 mmol) in 10 mL THF:EtOH (20 mL, 1:4) was added Raney-Ni (1.0 mL suspension in EtOH) followed by hydrazine hydrate (0.135 g, 2.70 mmol). The mixture was stirred vigorously at room temperature for 16 hours and then filtered through celite pretreated with water. The filtrate was concentrated and the residue was dissolved in CH2Cl2 (3 mL) and pyridine (0.35 mL, 3.78 mmol) and p-toluensulfonyl chloride (0.13 g, 0.54 mmol) were added to the solution. The reaction mixture was stirred at room temperature for 16 hours and then concentrated. The crude product was purified by column chromatography chromatography (SiO2, CHCl3/MeOH/NH3 9:1:0.4%) to give 0.217 g (95%) of the free base which was converted to its HCl-salt: 1H NMR (CD3OD) δ 8.21-8.14 (m, 1H), 7.97-7.93 (m, 1H), 7.58-7.47 (m, 3H), 7.43-7.37 (m, 1H), 7.25-7.10 (m, 4H), 4.12-4.02 (m, 1H), 3.80-3.0 (m, partly obscured by solvent signal, 8H), 2.45-2.10 (m, 3H), 2.35 (s, 3H), 1.87-1.75 (m, 1H); MS (posEI) m/z 421 (M+).

Workup

  1. filtrationfiltered through celite
  2. concentrationThe filtrate was concentrated
  3. dissolutionthe residue was dissolved in CH2Cl2 (3 mL)
  4. stirringThe reaction mixture was stirred at room temperature for 16 hours
  5. concentrationconcentrated
  6. customThe crude product was purified by column chromatography chromatography (SiO2, CHCl3/MeOH/NH3 9:1:0.4%)

Sources & evidence

ORD record
ord-6562cdd7adb5410f9911976b07ee6516
Source dataset
uspto-grants-2009_08
Patent number
US07572787B2

Reaction notes

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