Sodium Carbonate → (E)-3-chloro-5-styrylpicolinonitrile

HRID 1259097Notes

Reaction equation

HRID 1259097 reaction equation
[Cl:1][C:2]1[C:3]([C:9]#[N:10])=[N:4][CH:5]=[C:6](Cl)[CH:7]=1.CC1(C)C(C)(C)OB(/[CH:19]=[CH:20]/[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)O1.C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.C(O)C.C(OCC)(=O)C.O>[Cl:1][C:2]1[C:3]([C:9]#[N:10])=[N:4][CH:5]=[C:6](/[CH:19]=[CH:20]/[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:7]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27696993,5-Dichloro-2-cyanopyridineHCID 57084134,4,5,5-tetramethyl-2-((E)-2-phenylethenyl)-1,3,2-dioxaborolane

Product 1

HCID 66875239(E)-3-chloro-5-styrylpicolinonitrile

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 21863594Toluene ethanolSolvent

Procedure

A solution of 3,5-dichloropicolinonitrile (1.0 eq.), (E)-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane (1.0 eq.), tetrakis(triphenyl-phosphine)palladium (5 mol %), and 2N aqueous sodium carbonate solution (3.4 eq.) in toluene/ethanol (2:1, 0.04 M) was stirred at 100° C. for 2 hours, then 80° C. for 4 hours. After cooling to ambient temperature, the reaction content was diluted with ethyl acetate and water. The two phases were separated, and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated en vacuo. The crude product was purified by flash chromatography on a COMBIFLASH® system (ISCO) using 0-80% ethyl acetate in hexane to give a white solid.

Workup

  1. customThe two phases were separated
  2. extractionthe aqueous layer was extracted twice with ethyl acetate
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over anhydrous MgSO4
  5. concentrationconcentrated en vacuo
  6. customThe crude product was purified by flash chromatography on a COMBIFLASH® system (ISCO)
  7. customto give a white solid

Sources & evidence

ORD record
ord-e9f24410111a429fb8c9c46691cc9ce0
Source dataset
uspto-grants-2013_06
Patent number
US08466167B2

Reaction notes

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