Tributylvinyltin → HCID 70496887, compound

HRID 244320Notes

Reaction equation

HRID 244320 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6](Cl)[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[CH:3]=1.[CH2:14]([Sn](CCCC)(CCCC)C=C)[CH2:15]CC>ClC(Cl)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]([F:8])=[C:6]([CH:14]=[CH2:15])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[CH:3]=1

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 86668302Methyl 4-amino-6-chloro-5-fluoropicolinate

Product 1

HCID 70496887HCID 70496887, compoundYield 49.4%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 63651,1-DichloroethaneSolvent

Conditions

Temperature
140 °C

Procedure

Methyl 4-amino-6-chloro-5-fluoropicolinate (1.9 g, 9.29 mmol) and bis(triphenylphosphine)palladium(II) dichloride (0.326 g, 0.464 mmol) were combined in dichloroethane (30 ml) and tributyl(vinyl)stannane (3.26 ml, 11.14 mmol) was added. The reaction mixture was heated in a microwave reactor at 140° C. for 2 hrs. The cooled reaction mixture was purified by flash chromatography (SiO2, 0-40% THF:Hex gradient) to provide the title compound as a white solid (0.9 g, 4.59 mmol, 49.4% yield): 1H NMR (400 MHz, DMSO-d6) δ 3.83 (s, 3H), 5.57 (dd, J=10.9, 2.2 Hz, 1H), 6.28 (dd, J=17.3, 2.2 Hz, 1H), 6.54 (s, 2H), 6.84-6.97 (m, 1H), 7.37 (d, J=6.7 Hz, 1H); 19F NMR (376 MHz, DMSO-d6) δ −148.25; ESIMS m/z 197 ([M+H]+), 195 ([M−H]−).

Workup

  1. customThe cooled reaction mixture
  2. customwas purified by flash chromatography (SiO2, 0-40% THF:Hex gradient)

Sources & evidence

ORD record
ord-065ecedc3db1462eb5d5343f0b907d5a
Source dataset
uspto-grants-2014_02
Patent number
US08658568B2

Reaction notes

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