Tri-o-tolylphosphine → 3-[2-Chloro-5-(methylsulfonyl)-3-pyridinyl]-1-(3,4-dichlorophenyl)propan-1-one

HRID 280196Notes

Reaction equation

HRID 280196 reaction equation
[Cl:1][C:2]1[C:7](I)=[CH:6][C:5]([S:9]([CH3:12])(=[O:11])=[O:10])=[CH:4][N:3]=1.[CH:13]([CH:15]([C:17]1[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([Cl:24])[CH:18]=1)[OH:16])=[CH2:14].C(N(CC)C(C)C)(C)C.CC1C(P(C2C(C)=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.IC1C=CC=CN=1>C([O-])(=O)C.C([O-])(=O)C.[Pd+2].CN(C)C=O>[Cl:1][C:2]1[C:7]([CH2:14][CH2:13][C:15]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([Cl:24])[CH:18]=2)=[O:16])=[CH:6][C:5]([S:9]([CH3:12])(=[O:11])=[O:10])=[CH:4][N:3]=1

Participants

8

Reactant 5

HCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 2211262-IodopyridineHCID 135677651-(3,4-Dichlorophenyl)prop-2-en-1-olHCID 13567772HCID 13567772, compound

Product 1

HCID 135677733-[2-Chloro-5-(methylsulfonyl)-3-pyridinyl]-1-(3,4-dichlorophenyl)propan-1-one

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 0.95 g of 2-chloro-3-iodo-5-(methylsulfonyl)pyridine, 0.91 g of α-ethenyl-3,4-dichlorobenzenemethanol, 0.77 g of N,N-diisopropylethylamine, 0.04 g of tri-o-tolyphosphine, 0.02 g of palladium diacetate and 3 ml of dimethylformamide was heated to 100° C. under nitrogen. The mixture was heated at this temperature for 20 minutes and then at 116° C. for an additional 20 minutes at which point thin layer chromatography showed no iodopyridine starting material. The mixture was then cooled and partitioned between 1N hydrochloric acid and methyl acetate. The ethyl acetate layer was washed twice with aqueous saturated sodium chloride solution, dried over magnesium sulfate and filtered and the filtrate was concentrated to a dark solid residue. Column chromatography of this residue (silica gel, 1:1 ethyl acetate/hexane) gave a pale yellow solid. This was recrystallized from ethanol/ethyl acetate to give 3-[2-chloro-5-(methylsulfonyl)-3-pyridinyl]-1-(3,4-dichlorophenyl)propan-1-one melting at about 128.5°-130.5° C.

Workup

  1. temperatureThe mixture was heated at this temperature for 20 minutes
  2. temperatureThe mixture was then cooled
  3. custompartitioned between 1N hydrochloric acid and methyl acetate
  4. washThe ethyl acetate layer was washed twice with aqueous saturated sodium chloride solution
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated to a dark solid residue
  8. customColumn chromatography of this residue (silica gel, 1:1 ethyl acetate/hexane) gave a pale yellow solid
  9. customThis was recrystallized from ethanol/ethyl acetate

Sources & evidence

ORD record
ord-ce77784759be48a6b84093ab7095fa00
Source dataset
uspto-grants-1986_05
Patent number
US04588733

Reaction notes

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