Triphenylphosphine → 4-Allyl-3,5-dimethyl-benzaldehyde

HRID 552280Notes

Reaction equation

HRID 552280 reaction equation
[CH:1]([C:3]1[CH:8]=[C:7]([CH3:9])[C:6](OS(C(F)(F)F)(=O)=O)=[C:5]([CH3:18])[CH:4]=1)=[O:2].[C:19]1(P(C2C=CC=CC=2)C2C=CC=CC=2)[CH:24]=CC=C[CH:20]=1.[Li+].[Cl-].C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>CN(C=O)C.C([Sn](CCCC)(CCCC)CCCC)C=C.O.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>[CH2:24]([C:6]1[C:7]([CH3:9])=[CH:8][C:3]([CH:1]=[O:2])=[CH:4][C:5]=1[CH3:18])[CH:19]=[CH2:20]

Participants

9

Reactant 4

HCID 11776TriphenylphosphineHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 433294Lithium ChlorideHCID 544771104-Formyl-2,6-dimethylphenyl trifluoromethanesulfonate

Product 1

HCID 866401704-Allyl-3,5-dimethyl-benzaldehydeYield 114.8%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 90628AllyltributylstannaneSolvent2×

Conditions

Temperature
120 °C

Procedure

To a solution of trifluoromethanesulfonic acid 4-formyl-2,6-dimethyl-phenyl ester (3.13 g, 11.1 mmol), bis(triphenylphosphine)palladium dichloride (682 mg, 0.972 mmol), triphenylphosphine (1.76 g, 6.7 mmol), LiCl (3.98 g, 93.8 mmol) and a trace of 2,6-di-tert.-butyl-4-methylphenol in DMF (30 mL), allyltributylstannane (2 mL) is added. The mixture is heated to 120° C. and stirred for 2 h before another portion of allyltributylstannane (2 mL) is added. Stirring is continued at 120° C. for 1 h. The mixture is cooled to rt, diluted with water (100 mL) and extracted with EA. The organic extract is washed with 1.5 M aq. HCl (2×100 mL), dried over MgSO4, and the solvent is evaporated. The crude product is purified by CC on silica gel eluting with heptane:EA 20:1 to give 4-allyl-3,5-dimethyl-benzaldehyde (1.34 g) as a colourless liquid; 1H NMR (CDCl3: δ 9.92 (s, 1H), 7.53 (s, 2H), 5.96-5.80 (m, 1H), 5.06-5.00 (m, 1H), 4.87-4.78 (m, 1H), 3.48-3.40 (m, 2H), 2.38 (s, 6H).

Workup

  1. additionis added
  2. temperatureThe mixture is cooled to rt
  3. extractionextracted with EA
  4. extractionThe organic extract
  5. washis washed with 1.5 M aq. HCl (2×100 mL)
  6. dry with materialdried over MgSO4
  7. customthe solvent is evaporated
  8. customThe crude product is purified by CC on silica gel eluting with heptane:EA 20:1

Sources & evidence

ORD record
ord-f0dd2adf1c1248deae2ec388110b1270
Source dataset
uspto-grants-2011_05
Patent number
US07951794B2

Reaction notes

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