2,6-Di-tert-butyl-4-methylphenol → 7-Chloro-5-(4-chlorophenyl)-2-methyl-6-vinylquinoline

HRID 931701Notes

Reaction equation

HRID 931701 reaction equation
FC(F)(F)S(O[C:7]1[C:8]([C:19]2[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][CH:20]=2)=[C:9]2[C:14](=[CH:15][C:16]=1[Cl:17])[N:13]=[C:12]([CH3:18])[CH:11]=[CH:10]2)(=O)=O.[CH2:28]([Sn](CCCC)(CCCC)C=C)[CH2:29]CC.[Cl-].[Li+].C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>O1CCOCC1.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[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:17][C:16]1[CH:15]=[C:14]2[C:9]([CH:10]=[CH:11][C:12]([CH3:18])=[N:13]2)=[C:8]([C:19]2[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][CH:20]=2)[C:7]=1[CH:28]=[CH2:29]

Participants

8

Reactant 4

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 866919727-Chloro-5-(4-chlorophenyl)-2-methylquinolin-6-yl trifluoromethanesulfonate

Product 1

HCID 666306227-Chloro-5-(4-chlorophenyl)-2-methyl-6-vinylquinolineYield 35.4%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

Pd(PPh3)4 (52 mg, 0.045 mmol) and PdCl2(PPh3)2 (32 mg, 0.045 mmol) were added to a mixture 7-chloro-5-(4-chlorophenyl)-2-methylquinolin-6-yl trifluoromethanesulfonate (1F) (194 mg, 0.45 mmol), tributyl(vinyl)stannane (0.17 mL, 0.58 mmol), lithium chloride (57 mg, 1.4 mmol) and 2,6-di-tert-butyl-4-methylphenol (cat. amount) in 1,4-dioxane (8 mL). The reaction mixture was flushed with nitrogen, heated at 80° C. for 16 hours, and then the volatile component was removed in vacuo. The residue was dissolved in ethyl acetate (100 mL), washed with a NaHCO3 solution, water and brine, dried over Na2SO4, filtered and concentrated in vacuo. The obtained residue was purified by flash chromatography to provide the desired product 1G (50 mg, 35%). LCMS-ESI+ (m/z): 314.2, 316.2 (M+H)+.

Workup

  1. customThe reaction mixture was flushed with nitrogen
  2. customthe volatile component was removed in vacuo
  3. dissolutionThe residue was dissolved in ethyl acetate (100 mL)
  4. washwashed with a NaHCO3 solution, water and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe obtained residue was purified by flash chromatography

Sources & evidence

ORD record
ord-21908698ef6f474abe00286f9140367f
Source dataset
uspto-grants-2016_03
Patent number
US09296758B2

Reaction notes

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