2,6-Di-tert-butyl-4-methylphenol → HCID 22645428, compound

HRID 2414269Notes

Reaction equation

HRID 2414269 reaction equation
[CH2:1]([N:7]1[CH2:12][CH2:11][C:10]([CH3:27])([C:13]2[CH:18]=[CH:17][CH:16]=[C:15](OS(C(F)(F)F)(=O)=O)[CH:14]=2)[CH:9]([CH3:28])[CH2:8]1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6].[CH:29]([Sn](CCCC)(CCCC)CCCC)=[CH2:30].[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>[NH3:7].[CH2:1]([N:7]1[CH2:12][CH2:11][C:10]([CH3:27])([C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([CH:29]=[CH2:30])[CH:14]=2)[CH:9]([CH3:28])[CH2:8]1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6]

Participants

8

Reactant 4

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 22645393HCID 22645393, compound

Product 2

HCID 222AmmoniaHCID 22645428HCID 22645428, compoundYield 165.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 1-hexyl-3,4-dimethyl-4-(3-trifluoromethanesulfonyloxyphenyl)piperidine (Preparation 1, 1.5 g, 3.6 mmol) in 1,4-dioxan (17 mL) was de-oxygenated by evacuating and flushing with nitrogen five times. Vinyl tributyl tin (1.06 mL, 3.71 mmol) was added under stirring, followed by lithium chloride (456 mg, 10.76 mmol), tetrakis(triphenylphosphine)palladium(0) (catalytic) and 2,6-di-tert-butyl-4-methylphenol (2 crystals). The suspension was stirred under nitrogen and heated at reflux for ten hours. After cooling to room temperature the reaction mixture was quenched with aqueous ammonium hydroxide solution (50 mL, 1.0 M) and further diluted with ethyl acetate (50 mL). The phases were separated and the aqueous layer was further extracted with ethyl acetate (3×25 mL). The combined organics were dried (Na2SO4) and concentrated in vacuo. The residual oil was purified by column chromatography on silica gel (120 g) eluted with ethyl acetate:hexane:0.880 ammonia (39:60:1) to give the title compound as an oil (890 mg).

Workup

  1. customby evacuating
  2. customflushing with nitrogen five times
  3. stirringThe suspension was stirred under nitrogen
  4. temperatureheated
  5. temperatureat reflux for ten hours
  6. customwas quenched with aqueous ammonium hydroxide solution (50 mL, 1.0 M)
  7. additionfurther diluted with ethyl acetate (50 mL)
  8. customThe phases were separated
  9. extractionthe aqueous layer was further extracted with ethyl acetate (3×25 mL)
  10. dry with materialThe combined organics were dried (Na2SO4)
  11. concentrationconcentrated in vacuo
  12. customThe residual oil was purified by column chromatography on silica gel (120 g)
  13. washeluted with ethyl acetate

Sources & evidence

ORD record
ord-4a5f29d4d603484e8e803f6f5a9aeb59
Source dataset
uspto-grants-2004_11
Patent number
US06812236B2

Reaction notes

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