Ethyl Acrylate → HCID 13191793, compound

HRID 1381056Notes

Reaction equation

HRID 1381056 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.FC(F)(F)C1C=CC(C#N)=CC=1.C([Li])CCC.[C:45]([O:49][CH2:50][CH3:51])(=[O:48])[CH:46]=[CH2:47].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(N(CC)CC)C>[CH2:50]([O:49][C:45](=[O:48])/[CH:46]=[CH:47]/[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)[CH3:51]

Participants

10

Reactant 6

HCID 8821Ethyl AcrylateHCID 11776TriphenylphosphineHCID 122742,6-DibromopyridineHCID 67995Benzonitrile, 4-(trifluoromethyl)-HCID 13191796(6-Bromopyridin-2-yl)[4-(trifluoromethyl)phenyl]methanoneHCID 178418339Butyllithium

Product 1

HCID 13191793HCID 13191793, compound

Reagents, catalysts & solvents 3

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

Conditions

Temperature
150 °C

Procedure

2-Bromo-6-(4-trifluoromethylbenzoyl)pyridine, m.p. 66°-68° C. (prepared by reacting 2,6-dibromopyridine and 4-trifluoromethylbenzonitrile in dry ether in the presence of butyllithium) ethyl acrylate, triethylamine, palladium(II) acetate, triphenylphosphine and acetronitrile 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-6297f266170247d69583e0d6034bf1ed
Source dataset
uspto-grants-1986_04
Patent number
US04584382

Reaction notes

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