Polystyrene With Pendent Perfluorobutylsulfonylimide Group As Catalyst For Tert-butylations Of Phenol And Hydroquinone

In this paper, we used polystyrene with pendent perfluoroalkylsulfonylimide groups polymer (PPFSI) as a strong Br?nsted acid catalyst in several tert-butylation reactions.The expected productions are 2-tert-butylhydroquinone (TBHQ), 2,4-ditert-butylphenol and 4-butylphenol, which are valuable organic materials and intermediates in chemical industry to produce drugs and additives.The tert-butylation reactions were studied under the various conditions.Our work was described as follows:1.The reaction conditions were investigated in detail for the tert-butylation of hydroquinone with tert-butanol (TBA) in the presence of PPFSI, an optimized result was obtained when 0.330 g (3.0 mmol) hydroquinone reacts with 1:1.2 equiv. tert-butanol at 130℃for 5 h in 3 mL 1,2-dichloroethane in the presence of 5 mol% PPFSI. The high yield of 65.8% and selectivity of 85.9% of TBHQ were obtained respectively. The conversion of phenol was as high as 76.7%, which was much better compared with the reported results.2. The reaction conditions were investigated in detail for the tert-butylation of phenol with tert-butanol (TBA) in the presence of PPFSI, an optimized result was obtained when 0.282 g (3.0 mmol) phenol reacts with 1:2 equiv. tert-butanol at 100℃for 4 h in 3.0 mL n-heptane in the presence of 1 mol% PPFSI. The high yield of 67.8% and selectivity of 69.0% of 2,4-DTBP were obtained respectively. The conversion of phenol was as high as 98.3%.3. The reaction conditions were investigated in detail for the tert-butylation of phenol with tert-butanol (TBA) in the presence of PPFSI, a optimized result was obtained when 0.282 g (3.0 mmol) phenol reacts with 1:1.5 equiv. tert-butanol at 120℃for 3 h in 3.0 mL 1,2-dichloroethane in the presence of 3 mol% PPFSI. The high yield of 55.4% and selectivity of 58.9% of 4-TBP were obtained respectively. The conversion of phenol was as high as 94.0%.