2-Chloro-3-nitropyridine → 3-Nitro-2-vinylpyridine

HRID 2378963Notes

Reaction equation

HRID 2378963 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1.[CH2:11]([Sn](CCCC)(CCCC)C=C)[CH2:12]CC>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(#N)C>[N+:8]([C:7]1[C:2]([CH:11]=[CH2:12])=[N:3][CH:4]=[CH:5][CH:6]=1)([O-:10])=[O:9]

Participants

6

Reactant 2

HCID 796132-Chloro-3-nitropyridineHCID 81998Tributylvinyltin

Product 1

HCID 118296173-Nitro-2-vinylpyridineYield 67%

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6342AcetonitrileSolvent

Procedure

To an oven dried 20 mL of vial, was added 2-chloro-3-nitropyridine (0.793 g, 5 mmol), tetrabutylammonium chloride (1.390 g, 5.00 mmol), and bis(triphenylphosphine) palladium(II) chloride (0.351 g, 0.500 mmol). After addition of acetonitrile (10 ml) the resulting mixture was stirred at room temperature for 30 min while it was degassed by a flow of nitrogen through a needle inserted to the bottom of the vial. Tributyl(vinyl)tin (1.754 ml, 6.00 mmol) was added and the mixture was further degassed for 5 minutes. Vial was capped and heated at 90° C. for 2 hours. All solvents were removed. The residue was dissolved in dichloromethane and washed with brine. Organic layer was dried over Na2SO4, and filtered. Solvents were removed by roto-vap. Silica gel chromatography eluting ethyl acetate-hexanes afforded the title compound as dark brown oil in 67% yield. 1H NMR (500 MHz, CHLOROFORM-D) δ ppm 8.77 (dd, J=4.58, 1.53 Hz, 1 H) 8.18 (dd, J=8.24, 1.53 Hz, 1 H) 7.06-7.57 (m, 2 H) 6.63 (dd, J=16.79, 1.83 Hz, 1 H) 5.74 (dd, J=10.68, 1.83 Hz, 1 H).

Workup

  1. customTo an oven dried 20 mL of vial,
  2. customwas degassed by a flow of nitrogen through a needle
  3. customthe mixture was further degassed for 5 minutes
  4. customVial was capped
  5. temperatureheated at 90° C. for 2 hours
  6. customAll solvents were removed
  7. dissolutionThe residue was dissolved in dichloromethane
  8. washwashed with brine
  9. dry with materialOrganic layer was dried over Na2SO4
  10. filtrationfiltered
  11. customSolvents were removed by roto-vap
  12. washSilica gel chromatography eluting ethyl acetate-hexanes

Sources & evidence

ORD record
ord-b3f88bf45715463eb97fbb1c06ca5098
Source dataset
uspto-grants-2008_12
Patent number
US07470680B2

Reaction notes

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