【作者】 周飞；

【导师】 聂进； 张正波；

【作者基本信息】 华中科技大学 ， 有机化学， 2007， 硕士

【摘要】 本文首次利用了一种新型的Br?nsted酸催化剂-含有全氟丁基磺酰亚胺基团的聚苯乙烯(PPFSI)作为高效的多相催化剂,催化合成多种酚类烷基化产物,例如:2-叔丁基对苯二酚、2,4-叔丁基苯酚和4-叔丁基苯酚等,研究了反应温度、反应时间、溶剂等因素对反应的影响,实验工作内容主要如下:1.研究了PPFSI催化合成2-叔丁基对苯二酚反应的条件,最佳反应条件为:当对苯二酚加入量为0.330 g (3.0 mmol)时,烷基化试剂为0.332 mL (3.6 mmol)的叔丁醇,反应温度为130℃,反应时间5 h,溶剂1,2-二氯乙烷用量为3.0 mL,催化剂PPFSI用量5 mol%,本文在最佳反应条件基础上进行了反应,反应目标产物TBHQ收率为65.8%,而对苯二酚的转化率和TBHQ的选择性分别为76.7%和85.9%,均优于文献报道。2.研究了PPFSI催化合成2,4-叔丁基苯酚反应的条件,最佳反应条件为:当苯酚加入量为0.282 g时,反应温度为100℃,反应时间4 h,正庚烷用量为3.0 mL,催化剂PPFSI用量1 mol%,苯酚和叔丁醇摩尔比为1:2左右。本文在最佳反应条件基础上进行了反应,反应结果收率为67.8%,2,4-叔丁基苯酚选择性为69.0%,苯酚转化率为98.3%。3.研究了全氟磺酰亚胺基团的聚苯乙烯催化下叔丁醇和苯酚反应生成4-叔丁基苯酚的条件,最佳反应条件为:当苯酚加入量为0.282 g时,反应温度为1200C,反应时间3 h,1,2-二氯乙烷用量为3.0 mL,PPFSI催化剂用量3 mol%,叔丁醇与苯酚摩尔比为1.5:1。本文在最佳反应条件基础上进行了反应,苯酚转化率为94.0%,4-叔丁基苯酚的选择性为58.9%,反应结果收率为55.4%。更多还原

【Abstract】 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%.更多还原