Assemble Of Organic Cage Compound And Its Catalytic Performance On Oxidation Of Sulfides

Organic organic cage compound is consisting of carbon-carbon bonds or other functional groups typically found in organic molecules,becoming more and more favor due to its cavity and large specific surface areas.Since the 1960s,the synthesizing ways of organic cage compound have been developed in multi-step reactions with low yield,recently,it has developing in single step with high yield.Until now,researchers have been found many ways to synthesize organic cage compound,including irreversible bond formation(amide-bond formation,nucleophilic substitutions reactions,carbon-carbon bond formation,etc.)and reversible bond formation(boronic ester condensations reactions,condensation reactions of amines and aldehydes,etc.).Among them,condensation reaction of amines and aldehydesis one of the most frequently used to synthesis organic cage compound having high thermal stability and high yield.So far,the application of organic cage compound is mainly in capture of reactive compounds,selective recognition of guest ions or molecules,adsorption and storage of gas,etc.,seldomly dabbling in the field of catalysis compared with metal organic framework.This thesis introduced M-Salen(Salen:[N,N-bis-(saliyladehyde)ethylendiamine];M is transition-metal ions)into the block of precursor to design and assemble organic cage compound with catalytic performance:synthesizing dialdehyde with M-Salen as center of catalytic from 2-tert-butyphenol,diamine,4-formylphenylboronic acid as primitive materials followed by formylation reaction,Suzuki-coupling reaction,and other reactions.And then we synthesized organic cage compound through condensation reaction of it and triamine.The results showed that,we have been successfully assembled the organic cage compound Cagel with Ni(?)-Salen(CHO)and flexible tris(2-aminoethyl)amine.On the other hand,we couldn't synthesize the organic cage compound through condensation reaction of Ni(?)-Salen(CHO)and rigid 1,3,5-tri(4'-aminephenyl)benzene.So we concluded that triamine with suitable flexible structure is the key factor of synthesizing of organic cage compound in this assemble system.Crystal structure Cagel characterized by X-ray single crystal diffractometor showed that Cagel was consist of three molecules Ni(?)-Salen(CHO)as basic skeleton with three molecules tris(2-aminoethyl)amine as cover,shaping a construction of triangular prism.Therein,dialdehyde and triamine were connected viacovalent bond-C=N-between both of them.Ni2+ ions was coordinated in the center of Salen(Br)ligand with two nitrogen atoms and two oxygen atomsfrom phenolpart,which was catalytic center.The Cage1 was used as catalyst for oxidizing sulfides to sulfoxides,with high catalytic activity.The result shows that we almost got 100%of conversion of benzyl methyl sulfide and 99%of selectivity of benzyl methyl sulfoxide,under the conditions:react temperature 25?,iodosobenzene diacetate as oxidant(1.1 equiv),methanol/water(4:1,v:v)as react solvent,Cagel as catalyst(0.001 mol%)and 10 minutes as react time.In addition,Cage1 could be recycled.Further research showed that adding excess iodosobenzene diacetate,benzyl methyl sulfoxide had not been further oxidizing to sulfone.So Cagel could be oriented the oxidation of sulfide to sulfoxide.After extending the substrate research,we found that catalytic system has wide applicability and good catalytic activity for most sulfides,although,the substituent group with electrophilic effect giving negative effect on yield of a part of sulfoxides.In addition,Cagel has large advantages among react solvent,react time,amount of catalyst,especially in selectivity of product,compared to Ni(?)-Salen(Br).From analyzing product of oxidizing of 4-fluorine benzene methyl sulfide catalyzed by both Ni(?)-Salen(Br)and Cagel,we concluded that the inner cavity of Cagel(allowing small molecule to entry)may be due to high selectivity of this reaction.In summary of this thesis,we have synthesized Cagel,which can be oriented the oxidation of sulfide to sulfoxide with high catalytic activity,wide applicability and it could be recycled many times.