4-Hydroxybenzaldehyde → 4-{[tert-Butyl(dimethyl)silyl]oxy}benzaldehyde

HRID 1295422Notes

Reaction equation

HRID 1295422 reaction equation
N1C=CN=C1.[OH:6][C:7]1[CH:14]=[CH:13][C:10]([CH:11]=[O:12])=[CH:9][CH:8]=1.[Si:15](Cl)([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16].O>C1COCC1>[Si:15]([O:6][C:7]1[CH:14]=[CH:13][C:10]([CH:11]=[O:12])=[CH:9][CH:8]=1)([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16]

Participants

6

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 795ImidazoleHCID 962WaterHCID 28928tert-Butyldimethylsilyl chloride

Product 1

HCID 108791334-{[tert-Butyl(dimethyl)silyl]oxy}benzaldehydeYield 94.7%

Reagents, catalysts & solvents 1

HCID 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. customp-OSi-St chain transfer agent was synthesized in two steps
  2. customIn a 500 ml flask equipped with a magnetic stirring bar
  3. customThe organic layer was separated
  4. extractionextracted with ether
  5. dry with materialdried with magnesium sulfate

Sources & evidence

ORD record
ord-380c83b5cb22484598c1d4d21a891ba9
Source dataset
uspto-grants-2007_07
Patent number
US07241829B2

Reaction notes

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