【作者】 史津晖；

【导师】 项斌；

【作者基本信息】 浙江工业大学 ， 应用化学， 2011， 硕士

【摘要】 当今的化学合成工业中,大量的使用有毒、不易回收的溶剂和无机酸催化剂,从而造成严重的环境污染。功能化酸性离子液体,它完全由有机阳离子和有机或无机阴离子组成,具有溶解能力强、蒸汽压低、酸性可调变性、液体酸的高密度反应活性位等优点,在酸催化反应中起到溶剂及催化剂的双重功能,是一种能够替代传统酸催化剂的绿色催化体系。论文首先制备了离子液体前体[Bmim]Cl,再用两步法合成了氯代1-甲基-3-丁基咪唑氯化铝（[Bmim]Cl-AlCl₃）、氯代l-甲基-3-丁基咪唑氯化铁（[Bmim]Cl-FeCl₃）、氯代1-甲基-3-丁基咪唑氯化锌（[Bmim]Cl-ZnCl2）、[Bmim]BF4五种离子液体,并进行了表征。同时,以乙腈为探针分子,用红外光谱法测定了Lewis酸离子液体的酸强度,并对FeCl₃摩尔分数不同时离子液体的酸性与催化活性进行了关联。以Lewis酸离子液体为溶剂兼催化剂,合成了8种苯乙酮衍生物,收率较传统的方法高。对其中的4-甲基苯乙酮的合成条件进行了优化,确定较佳反应条件为:n（[Bmim]Cl-FeCl₃）:n（甲苯）:n（乙酰氯）=1:3:1,反应时间4h,反应温度80℃,离子液体中FeCl₃的摩尔分数x（FeCl₃）=0.67。优化条件下,产物的总收率为93.7%,邻:间:对=11:3:86,离子液体可以循环使用5次,活性基本不变。以[Bmim]BF₄离子液体为反应介质,以Cu（oft）₂为催化剂,考察了4-甲氧基二苯甲酮的合成条件,确定了较佳的反应条件: n（苯甲酰氯）:n（苯甲醚）:n（[Bmim]BF₄）:n（Cu（otf）₂）=1:4:1:0.12,反应时间1,小时反应温度80℃。优化条件下产物的总收率为86.5%,邻:间:对=8:3:89,离子液体可以重复套用6次,活性基本不变。Lewis酸离子液体的催化下合成了二苯砜、1-苯磺酰基-2,4-二甲苯、1-苯磺酰基-2,4,6-三甲苯、1-苯磺酰基-4-氯苯四种化合物,对其中的1-苯磺酰基-2,4,6-三甲苯的合成条件进行了优化。较佳的合成条件为:n（均三甲苯）:n（苯磺酰氯）:n（[Bmim]Cl-FeCl₃）=2:1:0.1,反应时间为1小时,反应温度30℃,离子液体中FeCl₃的摩尔分数x（FeCl₃）=0.67。优化条件下,产物的收率达到94.0%。更多还原

【Abstract】 These days, lots of toxic, volatile organic solvents and catalysts areused in chemical industries and result serious environmental problem.The functional ionic liquids are made of functional organic cations andfunctional inorganic anions with unique properties, such as nonvolatility,homogeneous active sites, good solvating ability and so on. They haveshown excellent catalytic activity and can be used as dual catalyst andsolvent,socanreplacetraditionalacidcatalyst.1-Butyl-3-methylimidazolium chloride （[Bmim]Cl） was preparedand used to synthesis [Bmim]Cl-AlCl₃, [Bmim]Cl-FeCl₃, [Bmim]Cl-ZnCl2 and [Bmim]BF4 by two step method. Their structures werecharacterized. Acidic sites and the strength of Lewis ionic liquids havebeenstudiedbyIRtechniqueusingacetonitrileasaprobemolecule.Eight derivatives of acetophone were obtained by Friedel-Craftsacylation, in which Lewis acidic ionic liquids were used as solvent andcatalyst. The influences of various reaction conditions on the yieldwere studied. The optimum conditions of the Friedel-Crafts acylationreaction were determined as follow: n（[Bmim]Cl-FeCl₃）/n（toluene）/ n（acetyl chloride）=1/3/1, 4h, 80℃, x（FeCl3）=0.67. Under the optimumcondition the total yield was 93.7% with aratio of o: m: p=11:3:86. Theionic liquid [Bmim]Cl-FeCl3 can be reused five times without obviousdeactivation.4-Methoxybenzophenone was obtained by Friedel-Crafts acylation,in which ionic liquid [Bmim]BF₄ was used as solvent and Cu（oft）₂ascatalyst. The optimumreaction conditionsof the Friedel-Crafts acylationreaction were determined as follow: n（benzoyl chloride）/n（anisole）/n（[Bmim]BF₄）/n(Cu（otf）₂=1/4/1/0.12, 1h, 80℃. Under the optimumcondition the total yield was 86.5% with a ratio of o: m: p=8: 3: 89. Theionic liquid [Bmim]BF₄ can be reused six times without obviousdeactivation.1,4-Dimethyl-2-（phenylsulfonyl）benzene, 1,3,5-trimethyl-2-（phenylsulfonyl）benzene, 1-chloro-4-（phenylsulfonyl）benzene andsulfonyldibenzene were obtained in which Lewis acidic ionic liquidwasusedascatalyst. Theoptimumreactionconditionsof1,3,5-trimethyl-2-（phenylsulfonyl）benzene were determined as follow: n（mesitylene）/n（benzenesulfonyl chloride）/n（[Bmim]Cl-FeCl3）=2/1/0.1, 1h, 30℃,x（FeCl3）=0.6.Undertheoptimumconditiontheyieldwas94.0%.更多还原