Tributylvinyltin → Methyl 4-amino-5,6-dichloro-3-vinylpicolinate

HRID 75091Notes

Reaction equation

HRID 75091 reaction equation
[NH2:1][C:2]1[C:7]([Cl:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[C:3]=1I.[CH:15]([Sn](CCCC)(CCCC)CCCC)=[CH2:16]>C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[C:7]([Cl:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[C:3]=1[CH:15]=[CH2:16]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 86668298HCID 86668298, compound

Product 1

HCID 57412109Methyl 4-amino-5,6-dichloro-3-vinylpicolinateYield 184.6%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Methyl 4-amino-5,6-dichloro-3-iodopicolinate (0.5 g, 1.4 mmol), vinyltributylstannane (530 μl, 0.57 mmol, 1.8 mmol), and bis(triphenylphosphine)palladium(II) chloride (0.10 g, 0.1 mmol) were combined in nitrogen-deaerated 1,2-dichloroethane (10 mL). The reaction mixture was heated at reflux for 8 hours. The cooled reaction mixture was diluted with ethyl acetate (30 mL) and stirred with 15% KHF2 solution (10 mL) for 30 minutes. The phases were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with saturated sodium chloride, dried over sodium sulfate, and concentrated under vacuum. The crude product was purified by flash chromatography (SiO2, ethyl acetate/hexane) to afford the title compound as a tan solid (0.26 g, 73%): mp 96-97° C.; 1H NMR (400 MHz, CDCl3) δ 6.85 (dd, J=18.1, 11.5 Hz, 1H), 5.72 (dd, J=11.5, 1.3 Hz, 1H), 5.53 (dd, J=18.1, 1.3 Hz, 1H), 5.19 (s, 2H), 3.91 (s, 3H); EIMS m/z 246 ([M−H)−].

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 8 hours
  3. customThe cooled reaction mixture
  4. customThe phases were separated
  5. extractionthe aqueous phase was extracted with ethyl acetate
  6. washThe combined organic phases were washed with saturated sodium chloride
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under vacuum
  9. customThe crude product was purified by flash chromatography (SiO2, ethyl acetate/hexane)

Sources & evidence

ORD record
ord-091419462fdf4cafad94a2237323b3be
Source dataset
uspto-grants-2014_09
Patent number
US08835409B2

Reaction notes

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