Toluene → 2-Chloro-6-(1-ethoxyvinyl)-isonicotinic acid methyl ester

HRID 732405Notes

Reaction equation

HRID 732405 reaction equation
Cl[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([Cl:12])[N:11]=1)[C:5]([O:7][CH3:8])=[O:6].C1(C)C=CC=CC=1.C([Sn](CCCC)(CCCC)[C:25]([O:27][CH2:28][CH3:29])=[CH2:26])CCC>C(OCC)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:8][O:7][C:5](=[O:6])[C:4]1[CH:3]=[C:2]([C:25]([O:27][CH2:28][CH3:29])=[CH2:26])[N:11]=[C:10]([Cl:12])[CH:9]=1

Participants

6

Reactant 3

HCID 1140TolueneHCID 93237Methyl 2,6-dichloroisonicotinateHCID 619414Stannane, tributyl(1-ethoxyethenyl)-

Product 1

HCID 866150002-Chloro-6-(1-ethoxyvinyl)-isonicotinic acid methyl ester

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 3283Diethyl EtherSolvent

Procedure

Add methyl 2,6-dichloroisonicotinate (2.06 g, 10 mmol), tetrakis(triphenylphosphine)palladium (0) (578 mg, 0.5 mmol), triphenyhlphosphine (263 mg, 1 mmol) and toluene (25 mL) in a previously nitrogen filled sealed vessel. Flush the reactants with nitrogen again. Add tributyl(1-ethoxyvinyl)tin (4.05 mL, 12.0 mmol) under nitrogen and heat the sealed mixture at 100° C. overnight with vigorous stirring. Cool the reaction to room temperature, dilute with diethyl ether and filter through a filtering agent. Wash the organic filtrate with saturated aqueous ammonium chloride, saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride respectively. Dry (magnesium sulfate), concentrate and purify (silica gel chromatography, eluting with 5:95 to 10:90 ethyl acetate:hexanes) to give the title compound.

Workup

  1. additionfilled
  2. customsealed vessel
  3. customFlush the reactants with nitrogen again
  4. temperatureCool
  5. customthe reaction to room temperature
  6. filtrationfilter through a filtering agent
  7. washWash the organic filtrate with saturated aqueous ammonium chloride, saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride respectively
  8. dry with materialDry (magnesium sulfate)
  9. concentrationconcentrate
  10. custompurify
  11. wash(silica gel chromatography, eluting with 5:95 to 10:90 ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-e1189a77053e41c9847f3decff0e0a3c
Source dataset
uspto-grants-2009_09
Patent number
US07585885B2

Reaction notes

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