Tributylvinyltin → 2-Methylamino-5-vinyl-nicotinic acid ethyl ester

HRID 2244354Notes

Reaction equation

HRID 2244354 reaction equation
[CH2:1]([O:3][C:4](=[O:14])[C:5]1[CH:10]=[C:9](Br)[CH:8]=[N:7][C:6]=1[NH:12][CH3:13])[CH3:2].[Cl-].[Li+].[CH:17]([Sn](CCCC)(CCCC)CCCC)=[CH2:18]>CS(C)=O.[Cu]Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:3][C:4](=[O:14])[C:5]1[CH:10]=[C:9]([CH:17]=[CH2:18])[CH:8]=[N:7][C:6]=1[NH:12][CH3:13])[CH3:2]

Participants

7

Reactant 3

HCID 81998Tributylvinyltin2×HCID 433294Lithium ChlorideHCID 687024045-Bromo-2-methylamino-nicotinic acid ethyl ester

Product 1

HCID 686973712-Methylamino-5-vinyl-nicotinic acid ethyl esterYield 91%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

A solution of 5-bromo-2-methylamino-nicotinic acid ethyl ester (100 mg, 0.39 mmol), lithium chloride (98 mg, 2.32 mmol), copper(I)chloride (191 mg, 1.93 mmol), vinyl tributyl tin (151 mg, 0.46 mmol), and tetrakis(triphenylphosphine)palladium(0) (45 mg, 39 μmol) in methyl sulfoxide (3.1 mL) was stirred at 65° C., then after 4 h another portion of vinyl tributyl tin (141 mg, 0.46 mmol) was added, and stirring was continued for 18 h. After cooling, the reaction mixture was partitioned between sat. aq. ammonium chloride solution and diethyl ether, the organic layer was washed with water, dried (MgSO4), and evaporated. Chromatography (SiO2, heptane-ethyl acetate gradient) afforded the title compound (72 mg, 91%). Yellow liquid, MS (ISP): 207.1 (M+H)+.

Workup

  1. temperatureAfter cooling
  2. customthe reaction mixture was partitioned between sat. aq. ammonium chloride solution and diethyl ether
  3. washthe organic layer was washed with water
  4. dry with materialdried (MgSO4)
  5. customevaporated

Sources & evidence

ORD record
ord-4cf46e7d474e49d5a06558f9b773212e
Source dataset
uspto-grants-2010_03
Patent number
US07678818B2

Reaction notes

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