Studies On High-Efficient Scavengers And Recyclable Catalysts Based On Functionalized Ionic Liquids

Several non-supported or silica gel-supported amino-or sulfo-functionalized ionic liquids (ILs) were synthesized through the structure derivation of functional groups and binding to the support with chemical bonds. The designed silica gel-supported functionalized ILs demonstrated high potential either as efficient scavengers in the purification of parallel synthesis products, or as convenient recyclable catalysts in chemical reactions.1、Silica gel-supported amino-or sulfo-functionalized ILs were synthesized and characterized by FT-IR. The loads of sulfonic acid or amino group were determined through the acid-base titration. TGA analysis demonstrated that these ILs exhibited good thermal stability and no obvious conversion in crystal structure of silica gel was observed with XRD analysis.2、Nine bis(substituted benzylidene)cycloalkanones were synthesized with short reaction times (2-6h) and high product yields (80-92%) through Aldol condensation between aromatic aldehydes and cyclanones catalyzed by amino-functionalized IL1-aminoethyl-3-methyl-imidazole tetrafluoborate ([2-Aemim][BF4]). The catalyst could be reused at least3times without significant lose in catalytic activity. The Knoevenagel condensation between aromatic aldehydes and malononitrile or ethyl cyanacetate was also successfully catalized by the silica gel-supported amino-functionalized IL (Si-[AeSipim][PF6]) coated with IL1-butyl-3-methyl-imidazole hexafluorophosphate. Nineteen products were obtained with high product yields (80-94%). The silica-gel-supported catalyst could be recycled simply by filtration for3times and without significant decrease in product yield.3、Pd complex with silica gel-supported amine functionalized IL (Pd@Si-[AeSipim][PF6]) was prepared through coordination and reduction. The load of Pd was0.039mmol/g determined by ICP-AES. Fourteen biphenyl compounds were synthesized through Pd-catalized Suzuki reaction. It was found that (Pd@Si-[AeSipim][PF6]) could efficiently catalyzed Suzuki reaction of various iodo-or bromo-benzenes with phenyloboricacid. The catalysts Pd@Si-[AeSipim][PF6] could be recovered simply by filtration and reused for at least3times without significant loss of activity.4、Silica gel-supported sulfo-functionalized ILs (Si-[SbSipim][PF6]-[bmim][PF6]) was found to be an efficient acidic scavenger in parallel synthesis to quench alkaline reagents. A series of amides were prepared with high yield (≥96%) and purity (≥97.6%) in parallel synthesis. The scavenger could be regenerated by hydrolyzing and reused at least three times without significant decrease in product yield and purity.5、As potential insecticidal compounds acting on5-hydroxytryptamine (5-HT) receptor of pests, forty seven novel piperdinols were synthesized in parallel with silica gel-supported functionalized ILs (Si-[SbSipim][PF6]-[bmim][PF6] and Si-[AeSipim][PF6]-[bmim][PF6]) as scavengers. The parralle synthesis products were obtained in the yield over79%and with the purity of greater than82.6%. Some of the target compounds exhibited good insecticidal activity. The scavengers could be easily regenerated and reused for at least three times.