Water → 3-Nitro-2-vinylpyridine

HRID 473433Notes

Reaction equation

HRID 473433 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.O>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[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 3

HCID 962WaterHCID 796132-Chloro-3-nitropyridineHCID 81998Tributylvinyltin

Product 1

HCID 118296173-Nitro-2-vinylpyridine

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

To a solution of 2-chloro-3-nitropyridine (20 g, 126.15 mmol) in 1, 4 dioxane (378 mL) was added tributyl vinyl tin (48 g, 151.38 mmol). The reaction mixture was degassed using nitrogen for 30 min. Bis-(triphenylphosphin)palladium(II)-chloride (4.4 g, 6.3 mmol) was added to the reaction mixture. Reaction mass was stirred at 110° C. for overnight. The reaction mixture was cooled to rt. Water was added to the reaction mass and extracted with EtOAc. Organic layer was washed with brine and dried over Na2SO4. The organic layer was concentrated in vacuo and purified by column chromatography on silica gel using 0-5% EtOAc in hexane to give 3-nitro-2-vinylpyridine: 1H NMR (400 MHz, DMSO-d6) δ 5.741 (dd, J=2.0 Hz, J=10.4 Hz, 1H), 6.536 (dd, J=2.4 Hz, J=16.8 Hz, 1H), 7.134-7.202 (m, 1H), 7.593 (dd, J=4.4 Hz, J=8.4 Hz, 1H), 8.388 (dd, J=1.6 Hz, J=8.4 Hz, 1H), 8.857 (dd, J=0.8 Hz, J=4.4 Hz, 1H); LC-MS (ESI) m/z 151.1 [M+H]+.

Workup

  1. customThe reaction mixture was degassed
  2. customfor 30 min
  3. customReaction mass
  4. temperatureThe reaction mixture was cooled to rt
  5. extractionextracted with EtOAc
  6. washOrganic layer was washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationThe organic layer was concentrated in vacuo
  9. custompurified by column chromatography on silica gel using 0-5% EtOAc in hexane

Sources & evidence

ORD record
ord-57250bf45fb142ad96466b90a440baf3
Source dataset
uspto-grants-2014_01
Patent number
US08633313B2

Reaction notes

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