Ethyl Acrylate → HCID 13191793, compound

HRID 980830Notes

Reaction equation

HRID 980830 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([C:8](=[O:19])[C:9]2[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][CH:10]=2)[N:3]=1.BrC1C=CC=C(Br)N=1.C([Li])CCC.[C:33]([O:37][CH2:38][CH3:39])(=[O:36])[CH:34]=[CH2:35].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(#N)C.C(N(CC)CC)C.CCOCC>[CH2:38]([O:37][C:33](=[O:36])/[CH:34]=[CH:35]/[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([C:8](=[O:19])[C:9]2[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][CH:10]=2)[N:3]=1)[CH3:39]

Participants

10

Reactant 5

HCID 8821Ethyl AcrylateHCID 11776TriphenylphosphineHCID 122742,6-DibromopyridineHCID 13191796(6-Bromopyridin-2-yl)[4-(trifluoromethyl)phenyl]methanoneHCID 178418339Butyllithium

Product 1

HCID 13191793HCID 13191793, compound

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolventHCID 8471TriethylamineSolvent

Procedure

2-Bromo-6-(4-trifluoromethylbenzoyl)pyridine, m.p. 66°-68° C. (prepared by reacting 2,6-dibromopyridine and 4-trifluoromethylenzonitrile in dry ether in the presence of butyllithium) ethyl acrylate, triethylamine, palladium(II) acetate, triphenylphosphine and acetonitrile were heated at 150° C. in an autoclave with stirring for six hours to yield (E)-ethyl-3-[6-(4-trifluoromethylbenzoyl)-2-pyridyl]acrylate, m.p. 129°-132° C. Butyllithium was added under nitrogen to a stirred suspension of triphenyl-2-pyrrolidinoethylphosphonium bromide in dry toluene to form a Wittig reagent. After 0.5 hours, the acrylate compound prepared above, in toluene was added and the resulting suspension was heated at 75° C. with stirring for 2 hours. The cooled solution was diluted with ether and treated with hydrochloric acid (2M). The aqueous phase was separated, washed with ether, and basified with potassium carbonate (ice) and extracted with ether. The mixture of isomeric esters obtained by evaporation was dissolved in ethanol containing sodium hydroxide solution (1M) and partially evaporated on the steam bath under reduced pressure for 5 minutes. The residual aqueous solution was neutralized with sulfuric acid and evaporated to dryness. The solid residue was extracted with hot isopropanol and the extracts were concentrated until crystallization commenced. The (E)-3-{6-[3-pyrrolidino-1-(4-Trifluoromethylphenyl)prop-1E-enyl]-2-pyridyl}acrylic acid after recrystallization from isopropanol, melted at m.p. 223°-225° C. (decomp).

Sources & evidence

ORD record
ord-640b67b51dab4e04aaed337d2e353573
Source dataset
uspto-grants-1987_01
Patent number
US04639459

Reaction notes

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