3-Bromo-2-chloro-5-nitropyridine → 3-Bromo-2-methyl-5-nitropyridine

HRID 365917Notes

Reaction equation

HRID 365917 reaction equation
[Br:1][C:2]1[C:3](Cl)=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.O[C:13]1C=CC([N+]([O-])=O)=CN=1.[Na].C(C(CC)(C([O-])=O)C([O-])=O)C>>[Br:1][C:2]1[C:3]([CH3:13])=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1

Participants

5

Reactant 4

HCID 2308893-Bromo-2-chloro-5-nitropyridineHCID 5360545SodiumHCID 69515632,2-DiethylpropanedioateHCID 178526703HCID 178526703, compound

Product 1

HCID 184588223-Bromo-2-methyl-5-nitropyridineYield 75%

Procedure

3-Bromo-2-chloro-5-nitropyridine (25 g, 105 mmol; prepared from 2-hydroxy-5-nitropyridine according to the procedure of V. Koch and S. Schnatterer, Synthesis 1990, 499-501) was treated with the sodium salt of diethylmalonate (17.6 mL, 116 mmol) according to the procedure of Odashima et al Bull Chem Soc Jpn 1993, 66, 797-803) to provide 17.1 g (78.8 mmol, 75%) of dark red oil: TLC Rf 0.5 (4:1 hexanes/EtOAc); 1H NMR (CDCl3, 300 MHz) δ 2.81 (s, 3H), 8.61 (d, 1H, J=2.0 Hz), 9.26 (d, 1H, J=2.0 Hz).

Workup

  1. customSchnatterer, Synthesis 1990, 499-501)

Sources & evidence

ORD record
ord-116fd7443e464ee6b00dcd5bd90fa5f5
Source dataset
uspto-grants-2000_10
Patent number
US06127386

Reaction notes

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