2,6-Di-tert-butyl-4-methylphenol → 4-Vinylbenzaldehyde

HRID 2307838Notes

Reaction equation

HRID 2307838 reaction equation
C([C:5]1[CH:10]=[C:9](C)[CH:8]=[C:7]([C:12]([CH3:15])(C)C)[C:6]=1O)(C)(C)C.BrC1C=CC([CH:22]=[O:23])=CC=1.C([Sn](CCCC)(CCCC)C=C)CCC.F.[NH+]1C=CC=CC=1>C1(C)C=CC=CC=1.O1CCCC1.C(OCC)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N1C=CC=CC=1>[CH:12]([C:7]1[CH:6]=[CH:5][C:10]([CH:22]=[O:23])=[CH:9][CH:8]=1)=[CH2:15]

Participants

10

Reactant 4

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 707414-BromobenzaldehydeHCID 81998TributylvinyltinHCID 22053267HCID 22053267, compound

Product 1

HCID 393894-VinylbenzaldehydeYield 81.3%

Reagents, catalysts & solvents 5

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1049PyridineSolventHCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A few crystals of 2,6-di-tert-butyl-4-methylphenol (BHT), 4-Bromobenzaldehyde (2.00 g, 10.8 mmol), and tetrakis(triphenylphosphine) palladium(0) (250 mg, 2 mol %) are dissolved in toluene (20 mL). Tri-n-butyl-vinyl tin(IV) (3.47 mL, 3.77 g, 11.9 mmol) is added and the mixture is heated to reflux for 3 hr. After cooling to room temperature, the dark green/black reaction mixture is treated as follows: pyridine (4.4 mL) is added, then 9.3 mL of pyridinium hydrofluoride in tetrahydrofuran (˜1.2N, made by adding 0.88 g of pyridinium polyhydrofluoride into 20 mL dry THF containing 3.13 g of pyridine); the mixture is then stirred at room temperature overnight. The treated reaction mixture is diluted with diethyl ether (200 mL), washed with water (50 mL), 10% aqueous hydrochloric acid (2×50 mL), saturated aqueous NaHCO3 (50 mL), and then dried over MgSO4. Concentration in vacuo gives a crude oil, which is purified by flash chromatography (silica, 10% ethyl acetate/hexanes) to give pure 4-vinylbenzaldehyde as a pale yellow oil (1.16 g, 81.3%).

Workup

  1. temperaturethe mixture is heated
  2. temperatureto reflux for 3 hr
  3. additionthe dark green/black reaction mixture is treated
  4. customThe treated reaction mixture
  5. washwashed with water (50 mL), 10% aqueous hydrochloric acid (2×50 mL), saturated aqueous NaHCO3 (50 mL)
  6. dry with materialdried over MgSO4
  7. concentrationConcentration in vacuo
  8. customgives a crude oil, which
  9. customis purified by flash chromatography (silica, 10% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-476c417f6f5c49bdb6972249360bdb02
Source dataset
uspto-grants-2004_12
Patent number
US06833274B2

Reaction notes

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