Water → 4-(t-butyldimethylsilyloxy)styrene

HRID 1295423Notes

Reaction equation

HRID 1295423 reaction equation
[CH2:1]([Li])CCC.[Si:6]([O:13][C:14]1[CH:21]=[CH:20][C:17]([CH:18]=O)=[CH:16][CH:15]=1)([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7].O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[Si:6]([O:13][C:14]1[CH:21]=[CH:20][C:17]([CH:18]=[CH2:1])=[CH:16][CH:15]=1)([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7]

Participants

6

Reactant 3

HCID 962WaterHCID 108791334-{[tert-Butyl(dimethyl)silyl]oxy}benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 109989514-(t-butyldimethylsilyloxy)styrene

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

p-OSi-St chain transfer agent was synthesized in two steps. In a 500 ml flask equipped with a magnetic stirring bar, 70.4 g of imidazole was mixed with 52.4 g (0.42 mol) of 4-hydroxybenzaldehyde and 77.4 g of t-butyldimethylsilyl chloride in THF solution. The mixture was stirred at ambient temperature for 4 hours before being poured into cold water. The organic layer was separated and extracted with ether, then dried with magnesium sulfate. After evaporating the solvent, 94 g of 4-(t-butyldimethylsilyloxy)benzaldehyde (90% yield), a deep yellow color liquid, was obtained. The second reaction step was performed under a nitrogen atmosphere. In a 500 ml flask equipped with a magnetic stirring bar, 123.6 g of methyltriphenylphosphonium bromide suspended in THF was treated with 149.6 ml of n-butyllithium (2.5M in hexane). After 1 hour, 80.0 g of 4-(t-butyldimethylsilyloxy)benzaldehyde was introduced dropwise into the red solution. The mixture was stirred overnight at room temperature and then poured into cold water. The organic layer was separated by ether extraction and dried with magnesium sulfate. Further purification was performed by distillation under vacuum (10 Torr) at elevated temperature (80° C.). 65 g of p-OSi-St was obtained with a yield of more than 90%. Its structure was confirmed by 1H NMR spectrum.

Workup

  1. customa deep yellow color liquid, was obtained
  2. customThe second reaction step
  3. customIn a 500 ml flask equipped with a magnetic stirring bar
  4. customThe organic layer was separated by ether extraction
  5. dry with materialdried with magnesium sulfate
  6. customFurther purification
  7. distillationwas performed by distillation under vacuum (10 Torr) at elevated temperature (80° C.)
  8. custom65 g of p-OSi-St was obtained with a yield of more than 90%

Sources & evidence

ORD record
ord-2d30877ab36b4b0cb1563d88545508d1
Source dataset
uspto-grants-2007_07
Patent number
US07241829B2

Reaction notes

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