Pyridine → HCID 21091632, compound

HRID 1348562Notes

Reaction equation

HRID 1348562 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=2)[CH:5]=[CH:6][CH:7]=1.N1C=CC=CC=1.[S:20]([O:27]S(C(F)(F)F)(=O)=O)([C:23]([F:26])([F:25])[F:24])(=[O:22])=[O:21]>CN(C)C1C=CN=CC=1.C(OCC)(=O)C>[F:24][C:23]([F:26])([F:25])[S:20]([OH:27])(=[O:22])=[O:21].[OH:1][C:2]1[CH:3]=[C:4]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=2)[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 1049PyridineHCID 67749Trifluoromethanesulfonic anhydrideHCID 1509134280653-80-1

Product 1

HCID 21091632HCID 21091632, compound

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

2.5 g (0.015 mol) of 4-(3-hydroxyphenyl)pyridine and 40 ml of pyridine and 2.3 g of 4-(dimethylamino)pyridine (DMAP) are cooled to 0° C. 3.2 ml of triflic anhydride are added thereto dropwise. The mixture is stirred at 0° C. for one hour and at ambient temperature overnight. It is poured into a water/ice mixture, extraction is carried out with ethyl acetate, the organic phase is dried and the solvent is evaporated under reduced pressure. The crude product is purified by chromatography on a column of silica gel, elution being carried out with a cyclohexane/ethyl acetate=8/2 mixture. 4-(3-Hydroxyphenyl)pyridine trifluoromethanesulfonate is obtained in the form of an oil. 2.26 g of this product are mixed with 112 ml of anhydrous dimethylformamide, 38 g of palladium acetate, 2.5 ml of anhydrous triethylamine and 2 g of N,N-dimethylethanolamine vinyl ether. The mixture is heated at 80° C. for 48 hours. The solvent is evaporated under reduced pressure. The residue is purified by flash chromatography on a column of silica gel, elution being carried out with ethyl acetate, to remove the first product, and subsequently with an ethyl acetate/methanol=1/1 mixture. 2-[2-[3-(4-Pyridyl)-phenyl)ethenyl)oxy)]-N,N-dimethyl-1-ethanamine is obtained. 0.53 g of this product, dissolved in 35 ml of methanol, is treated with 20 ml of water and 5 ml of 96% sulfuric acid. The mixture is heated at 60° C. for 6 hours and is poured into ice, a saturated aqueous NaHCO3 solution is added thereto and extraction is carried out with ethyl acetate. The organic phase is dried and the solvent is evaporated under reduced pressure. 3-(4-Pyridyl)phenylacetaldehyde dimethyl acetal is obtained. Its N-oxide derivative is prepared by reaction with m-chloroperbenzoic acid in methylene chloride and the aldehyde is subsequently released by reaction with a mixture of trifluoroacetic acid, water and methylene chloride. The title compound is thus obtained.

Workup

  1. customthe organic phase is dried
  2. customthe solvent is evaporated under reduced pressure
  3. customThe crude product is purified by chromatography on a column of silica gel, elution

Sources & evidence

ORD record
ord-245993c6035b4eff89f7a8c522254f21
Source dataset
uspto-grants-2007_05
Patent number
US07211578B2

Reaction notes

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