Tributylvinyltin → 7-chloro-4-(4-fluorophenyl)-2,2-dimethyl-3-vinyl-2H-chromen

HRID 1959132Notes

Reaction equation

HRID 1959132 reaction equation
Br[C:2]1[C:3]([CH3:21])([CH3:20])[O:4][C:5]2[C:10]([C:11]=1[C:12]1[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=1)=[CH:9][CH:8]=[C:7]([Cl:19])[CH:6]=2.[CH2:22]([Sn](CCCC)(CCCC)C=C)[CH2:23]CC.[F-].[K+]>O1CCOCC1.C(OCC)(=O)C.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>[Cl:19][C:7]1[CH:6]=[C:5]2[C:10]([C:11]([C:12]3[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=3)=[C:2]([CH:22]=[CH2:23])[C:3]([CH3:21])([CH3:20])[O:4]2)=[CH:9][CH:8]=1

Participants

7

Reactant 3

HCID 81998TributylvinyltinHCID 522689Potassium FluorideHCID 59443055HCID 59443055, compound

Product 1

HCID 594429667-chloro-4-(4-fluorophenyl)-2,2-dimethyl-3-vinyl-2H-chromen

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 3-bromo-7-chloro-4-(4-fluorophenyl)-2,2-dimethyl-2H-chromen (a compound obtained in Reference Example 8(1); 220 mg), tributyl(vinyl)tin (350 μL) and tetrakis(triphenylphosphine)palladium(0) (140 mg) in dioxane was heated under reflux for 23 hours. After cooling, the reaction solution was diluted with ethyl acetate, a saturated aqueous solution of potassium fluoride was added thereto, and the mixture was stirred at room temperature for an hour. The reaction solution was filtered through Celite and the filtrate was extracted with ethyl acetate. The organic layer was washed successively with water and brine, filtered through a column of porous diatomite (Chem Elut) and the filtrate was concentrated in vacuo. The resultant residue was purified by column chromatography on silica gel (Solvent: n-hexane/chloroform=100/0 to 95/5) to give the titled compound (157 mg) as a pale yellow viscous oil.

Workup

  1. customobtained in Reference Example 8(1)
  2. temperatureunder reflux for 23 hours
  3. temperatureAfter cooling
  4. filtrationThe reaction solution was filtered through Celite
  5. extractionthe filtrate was extracted with ethyl acetate
  6. washThe organic layer was washed successively with water and brine
  7. filtrationfiltered through a column of porous diatomite (Chem Elut)
  8. concentrationthe filtrate was concentrated in vacuo
  9. customThe resultant residue was purified by column chromatography on silica gel (Solvent: n-hexane/chloroform=100/0 to 95/5)

Sources & evidence

ORD record
ord-a188d2210c9a448e9f93bb0d864559e6
Source dataset
uspto-grants-2013_04
Patent number
US08410166B2

Reaction notes

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