Aself-accelerating three-component reaction was developed using the secondary amines,CS_(2),and sym-dibenzo-1,5-cyclooctadiene-3,7-diyne(DIBOD)as reactants.In this three-component reaction,the secondary amine reacts w...Aself-accelerating three-component reaction was developed using the secondary amines,CS_(2),and sym-dibenzo-1,5-cyclooctadiene-3,7-diyne(DIBOD)as reactants.In this three-component reaction,the secondary amine reacts with CS_(2) to form dithiocarbamate anion,which subsequently in-situ reacts with DIBOD behaving a self-accelerating reaction property.Specifically,the reaction of dithiocarbamate anion with the first alkyne of DIBOD activates the unreacted alkyne,which reacts with dithiocarbamate anion much faster than the original alkyne of DIBOD.Using the self-accelerating three-component reaction as polymerization reaction,a stoichiometric imbalance-promoted step-growth polymerization method was developed using the difunctional secondary amines,CS_(2),and DIBOD as monomer groups.This novel three-component polymerization can quickly produce high molecular weight dithiocarbamate-containing polymers under mild conditions using a slight molar excess of DIBOD to difunctional secondary amine monomer.Containing sulfur elements in the backbones,the resultant polymers hold high refractivity and may find potential applications in optical and optoelectronic fields.展开更多
Engineering metal-organic frameworks（MOF） for heterogeneous catalysts have been of extreme interest since they have large pore size within the crystalline framework and well defined pore architecture. Ni-containing ...Engineering metal-organic frameworks（MOF） for heterogeneous catalysts have been of extreme interest since they have large pore size within the crystalline framework and well defined pore architecture. Ni-containing MOF Ni2（3,5-Pydc）2（H2O）8·2H2O（1·H2O） was prepared by solvothermal method from 3,5-pyridinedicarboxylic acid, D-camphoric acid and Ni（NO3）2·6H2O in dimethylformamide（DMF）/water（volume ratio 2：1）. And two gold and silver functionalized 1·H2O catalysts were prepared by impregnation method. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF were in-depth characterized by single crystal X-ray diffraction, powder X-ray diffraction（PXRD）, thermogravimetric analysis（TGA）, transmission electron microscopy（TEM）, and inductively coupled plasma-atomic emission spectroscopy（ICP-AES）. Their catalytic performance was examined in one-pot synthesis of structurally divergent propargylamines via three component coupling of aldehyde, alkyne, and amine（A3） in 1,4-dioxane. The resuits show that the catalysts all displayed high reactivities, and a selectivity of 100% for propargylamines. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF have proved to be applicable to a wide range of substrates. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF can be easily recycled and used repetitively at least 3 times with a slight drop in activity. These features render the catalysts particularly attractive in the practice of propargylamines synthesis in an environmentally friendly manner.展开更多
Barbier allylation and Friedel-Crafts alkylation of （un）substituted benzaldehydes, allylbromide and phenols can be combined in a one-pot process in ionic liquid （BuPyC1/SnC12·2H2O） to directly synthesize 4-（...Barbier allylation and Friedel-Crafts alkylation of （un）substituted benzaldehydes, allylbromide and phenols can be combined in a one-pot process in ionic liquid （BuPyC1/SnC12·2H2O） to directly synthesize 4-（2-hydroxyphenyl）- 4-[（un）substituted phenyl]but-1-ene compounds, which were applied to the synthesis of 4-（substituted phenyl）- chromans through intramolecular cyclization reactions.展开更多
The synthesis and characterization of Zr-MCM-41 nanoreactors and their catalytic activity in the synthesis of new amino nitrile derivatives by the Strecker reaction in high yields and in short reaction times is reported.
基金This work was supported by the National Key Research and Development Program of China(No.2019YFA0210400)the National Natural Science Foundation of China(No.22071255).
文摘Aself-accelerating three-component reaction was developed using the secondary amines,CS_(2),and sym-dibenzo-1,5-cyclooctadiene-3,7-diyne(DIBOD)as reactants.In this three-component reaction,the secondary amine reacts with CS_(2) to form dithiocarbamate anion,which subsequently in-situ reacts with DIBOD behaving a self-accelerating reaction property.Specifically,the reaction of dithiocarbamate anion with the first alkyne of DIBOD activates the unreacted alkyne,which reacts with dithiocarbamate anion much faster than the original alkyne of DIBOD.Using the self-accelerating three-component reaction as polymerization reaction,a stoichiometric imbalance-promoted step-growth polymerization method was developed using the difunctional secondary amines,CS_(2),and DIBOD as monomer groups.This novel three-component polymerization can quickly produce high molecular weight dithiocarbamate-containing polymers under mild conditions using a slight molar excess of DIBOD to difunctional secondary amine monomer.Containing sulfur elements in the backbones,the resultant polymers hold high refractivity and may find potential applications in optical and optoelectronic fields.
基金Supported by the Promotive Research Fund for Young and Middle-aged Scientists of Shandong Province, China （Nos.BS2014CL021, BS2015CL012）, the Natural Science Foundation of Shandong Province, China（Nos.ZR2014BL003, ZR2015BM005）, the Project of Shandong Province Higher Educational Science and Technology Program, China（Nos.J14LC01, J 15LA09） and the Technology Research and Development Program of Weifang, China（No.201301035）.
文摘Engineering metal-organic frameworks（MOF） for heterogeneous catalysts have been of extreme interest since they have large pore size within the crystalline framework and well defined pore architecture. Ni-containing MOF Ni2（3,5-Pydc）2（H2O）8·2H2O（1·H2O） was prepared by solvothermal method from 3,5-pyridinedicarboxylic acid, D-camphoric acid and Ni（NO3）2·6H2O in dimethylformamide（DMF）/water（volume ratio 2：1）. And two gold and silver functionalized 1·H2O catalysts were prepared by impregnation method. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF were in-depth characterized by single crystal X-ray diffraction, powder X-ray diffraction（PXRD）, thermogravimetric analysis（TGA）, transmission electron microscopy（TEM）, and inductively coupled plasma-atomic emission spectroscopy（ICP-AES）. Their catalytic performance was examined in one-pot synthesis of structurally divergent propargylamines via three component coupling of aldehyde, alkyne, and amine（A3） in 1,4-dioxane. The resuits show that the catalysts all displayed high reactivities, and a selectivity of 100% for propargylamines. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF have proved to be applicable to a wide range of substrates. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF can be easily recycled and used repetitively at least 3 times with a slight drop in activity. These features render the catalysts particularly attractive in the practice of propargylamines synthesis in an environmentally friendly manner.
文摘Barbier allylation and Friedel-Crafts alkylation of （un）substituted benzaldehydes, allylbromide and phenols can be combined in a one-pot process in ionic liquid （BuPyC1/SnC12·2H2O） to directly synthesize 4-（2-hydroxyphenyl）- 4-[（un）substituted phenyl]but-1-ene compounds, which were applied to the synthesis of 4-（substituted phenyl）- chromans through intramolecular cyclization reactions.
文摘The synthesis and characterization of Zr-MCM-41 nanoreactors and their catalytic activity in the synthesis of new amino nitrile derivatives by the Strecker reaction in high yields and in short reaction times is reported.
