From the standpoint of chemical structures,the organic backbones of energetic materials can be classified into aromatic rings,nonaromatic rings,and open chains.Although the category of aromatic energetic compounds exh...From the standpoint of chemical structures,the organic backbones of energetic materials can be classified into aromatic rings,nonaromatic rings,and open chains.Although the category of aromatic energetic compounds exhibits several advantages in the regulation of energetic properties,the nonaromatic heterocycles,assembling nitramino explosophores with simple alkyl bridges,still have prevailed in benchmark materials.The methylene bridge plays a pivotal role in the constructions of the classic nonaromatic heterocycle-based energetic compounds,e.g.,hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX)and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),whereas ethylene bridge is the core moiety of state-of-the-art explosive 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20).In this context,it is of great interest to employ simple and practical bridges to assemble aromatic and nonaromatic nitrogen-rich heterocycles,thereby expanding the structural diversity of energetic materials,e.g.,bridged and fused nitrogen-rich poly-heterocycles.Furthermore,alkyl-bridged poly-heterocycles highlight the potential for the open chain type of energetic materials.In this review,the development of alkyl bridges in linking nitrogen-rich heterocycles is presented,and the perspective of the newly constructed energetic backbones is summarized for the future design of advanced energetic materials.展开更多
The fused heterocyclic compounds 2 : imidazo [1.2-a] pyriding 2a-c and pyrido [ 1 .2-a] pyrimidine 2d were obtained from the reaction of α-cinnamoyl ketene dibenzylthio acetals 1 with diamine. When α-cinnamoyl -a...The fused heterocyclic compounds 2 : imidazo [1.2-a] pyriding 2a-c and pyrido [ 1 .2-a] pyrimidine 2d were obtained from the reaction of α-cinnamoyl ketene dibenzylthio acetals 1 with diamine. When α-cinnamoyl -a'-benzoyl ketene N. N-acetals 3a-b were treated by t-BuONa/t- BuOH Solution. 8- benzoyl-pyrido[1.2-a] pyrimidine 4 was produced.展开更多
Using cation exchange resin(D72,Amberlyst-15) as catalyst, Mannich-type reaction of 5-amino-1,2,4-triazole 1, containing guanidine substructure, provides an efficient synthesis of a new kind of bicyclic P- and N-conta...Using cation exchange resin(D72,Amberlyst-15) as catalyst, Mannich-type reaction of 5-amino-1,2,4-triazole 1, containing guanidine substructure, provides an efficient synthesis of a new kind of bicyclic P- and N-containing compounds, 6-phospha-4,5,6-trihydroimidazolo [2,3-e] 1,2,4-triazole 4.展开更多
A Convenient method for the synthesis of fused phosphorusheterocycle 1,3,2-oxazaphosphorin-[3.2-a]-8-oxo-10-thio(or seleno)-[1,3,2]-benzodiazaphosphorines was carried out in one pot by the reaction of Tris(diethylamin...A Convenient method for the synthesis of fused phosphorusheterocycle 1,3,2-oxazaphosphorin-[3.2-a]-8-oxo-10-thio(or seleno)-[1,3,2]-benzodiazaphosphorines was carried out in one pot by the reaction of Tris(diethylamino)phosphine with multifunctional compounds 2-(N-(beta or gamma-hydroxyl) alkylene) amino-benzamides 1. When PCL3 was used, only chlorinated product was obtained.展开更多
long-term carbon fixation and possible carbon revitalization if introduced with functionality.Yet,such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO_(2).I...long-term carbon fixation and possible carbon revitalization if introduced with functionality.Yet,such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO_(2).In this work,we establish an efficient CuCl/Ph_(3)P-catalyzed multicomponent polymerization of CO_(2),diynes,and dihalides under mild conditions of rt—60◦C and atmospheric pressure.The polymerization shows great monomer universality,producing diverse poly(alkynoate)s in yields up to 99%with weight-average molecular weights up to 94000.Poly(alkynoate)s containing tetraphenylethylene(TPE)moieties show typical aggregation-induced emission features,and can specifically and sensitively detect Fe3+ions with a low limit of detection(LOD)of 1.79×10−7 M.Notably,owing to lots of activated triple bonds in the main chain of poly(alkynoate)s,N-hydroxyphthalimide derivatives are facilely introduced into this polymerization in situ to establish a‘one-pot,two-step,four-component’tandem polymerization to produce poly(3a-hydroxyisoxazolo[3,2-a]isoindol-8(3aH)-ones)s(PHIIOs)with 100%grafting ratio.Interestingly,the fused heterocyclic PHIIO containing TPE could realize the specific and sensitive detection of Ag+ions with a low LOD of 4.90×10^(−6)M.This work not only innovatively achieves the direct chemical fixation of CO_(2)into functional polymeric materials under relatively low temperatures with low-cost catalysts,but also obtains a series of polymers with controllable structure-function,which can be realized for a wide range of applications.展开更多
A new and efficient cascade synthesis of polycyclic fused imidazo[2,1-b][1,3]thiazinones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--S coup...A new and efficient cascade synthesis of polycyclic fused imidazo[2,1-b][1,3]thiazinones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--S coupling reaction. The methodology is applied to a wide range of 2-iodo, 2-bromo, and 2-chloro benzoyl chlorides to yield the polycyclic fused imidazo[2,1-b][ 1,3]thiazinones in good to excellent yields.展开更多
A convenient synthesis of intermediate 4,5-diamino-3-aryl-l-phenylpyrazoles 4a--4c was reported. The different cyclization reactions were carried out with chalcone, 2-mercaptoacetic acid and p-anisialdehyde, ethyl chl...A convenient synthesis of intermediate 4,5-diamino-3-aryl-l-phenylpyrazoles 4a--4c was reported. The different cyclization reactions were carried out with chalcone, 2-mercaptoacetic acid and p-anisialdehyde, ethyl chloroformate, glyoxal and thiourea to afford different N and S containing heterocycles. The reaction conditions were compared by conventional heating and microwave irradiation. The structures of the cyclization products were de- termined by analytical and spectroscopic data. All the synthesized compounds were screened for antibacterial activities in vitro.展开更多
The development of new and efficient polymerization strategies for the synthesis of multisubstituted fused heterocyclic polymers with attractive properties is of great significance.Herein,a rhodium-catalyzed polyannul...The development of new and efficient polymerization strategies for the synthesis of multisubstituted fused heterocyclic polymers with attractive properties is of great significance.Herein,a rhodium-catalyzed polyannulation route is developed for the in situ generation of multisubstituted polyquinolines with efficient aggregate-state fluorescence.Based on the cascade C-H activation of isonicotinamides and their annulations with internal diynes,a series of high molecular weight polyquinolines are efficiently produced in high yields of up to 99%in a facile and atom-economical manner.Unlike conventional two-component stepwise polymerizations,these polyannulation reactions are tolerant to monomer non-stoichiometric conditions and proceed even more thoroughly in the presence of an excess amount of the isonicotinamide monomer.Benefiting from the unique multisubstituted polyquinoline structures,the obtained polymers show high thermal and morphological stability,useful aggregation-induced emission(AIE)properties,and tunable aggregated-state fluorescence behaviors.The AIE-active polyquinoline is demonstrated to be a good lysosome-specific fluorescent probe with low cytotoxicity and excellent photostability.展开更多
基金National Natural Science Foundation of China(Grant Nos.22075023,22205022,and 22235003)to provide fund for conducting experiments。
文摘From the standpoint of chemical structures,the organic backbones of energetic materials can be classified into aromatic rings,nonaromatic rings,and open chains.Although the category of aromatic energetic compounds exhibits several advantages in the regulation of energetic properties,the nonaromatic heterocycles,assembling nitramino explosophores with simple alkyl bridges,still have prevailed in benchmark materials.The methylene bridge plays a pivotal role in the constructions of the classic nonaromatic heterocycle-based energetic compounds,e.g.,hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX)and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),whereas ethylene bridge is the core moiety of state-of-the-art explosive 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20).In this context,it is of great interest to employ simple and practical bridges to assemble aromatic and nonaromatic nitrogen-rich heterocycles,thereby expanding the structural diversity of energetic materials,e.g.,bridged and fused nitrogen-rich poly-heterocycles.Furthermore,alkyl-bridged poly-heterocycles highlight the potential for the open chain type of energetic materials.In this review,the development of alkyl bridges in linking nitrogen-rich heterocycles is presented,and the perspective of the newly constructed energetic backbones is summarized for the future design of advanced energetic materials.
文摘The fused heterocyclic compounds 2 : imidazo [1.2-a] pyriding 2a-c and pyrido [ 1 .2-a] pyrimidine 2d were obtained from the reaction of α-cinnamoyl ketene dibenzylthio acetals 1 with diamine. When α-cinnamoyl -a'-benzoyl ketene N. N-acetals 3a-b were treated by t-BuONa/t- BuOH Solution. 8- benzoyl-pyrido[1.2-a] pyrimidine 4 was produced.
文摘Using cation exchange resin(D72,Amberlyst-15) as catalyst, Mannich-type reaction of 5-amino-1,2,4-triazole 1, containing guanidine substructure, provides an efficient synthesis of a new kind of bicyclic P- and N-containing compounds, 6-phospha-4,5,6-trihydroimidazolo [2,3-e] 1,2,4-triazole 4.
文摘A Convenient method for the synthesis of fused phosphorusheterocycle 1,3,2-oxazaphosphorin-[3.2-a]-8-oxo-10-thio(or seleno)-[1,3,2]-benzodiazaphosphorines was carried out in one pot by the reaction of Tris(diethylamino)phosphine with multifunctional compounds 2-(N-(beta or gamma-hydroxyl) alkylene) amino-benzamides 1. When PCL3 was used, only chlorinated product was obtained.
基金supported by the National Natural Science Foundation of China(nos.22479102,22001078)the Guangdong Talent Program(no.2023TQ07L822)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(no.2024A1515011716)the startup funding of Songshan Lake Materials Laboratory(no.Y1D1031H311).
文摘long-term carbon fixation and possible carbon revitalization if introduced with functionality.Yet,such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO_(2).In this work,we establish an efficient CuCl/Ph_(3)P-catalyzed multicomponent polymerization of CO_(2),diynes,and dihalides under mild conditions of rt—60◦C and atmospheric pressure.The polymerization shows great monomer universality,producing diverse poly(alkynoate)s in yields up to 99%with weight-average molecular weights up to 94000.Poly(alkynoate)s containing tetraphenylethylene(TPE)moieties show typical aggregation-induced emission features,and can specifically and sensitively detect Fe3+ions with a low limit of detection(LOD)of 1.79×10−7 M.Notably,owing to lots of activated triple bonds in the main chain of poly(alkynoate)s,N-hydroxyphthalimide derivatives are facilely introduced into this polymerization in situ to establish a‘one-pot,two-step,four-component’tandem polymerization to produce poly(3a-hydroxyisoxazolo[3,2-a]isoindol-8(3aH)-ones)s(PHIIOs)with 100%grafting ratio.Interestingly,the fused heterocyclic PHIIO containing TPE could realize the specific and sensitive detection of Ag+ions with a low LOD of 4.90×10^(−6)M.This work not only innovatively achieves the direct chemical fixation of CO_(2)into functional polymeric materials under relatively low temperatures with low-cost catalysts,but also obtains a series of polymers with controllable structure-function,which can be realized for a wide range of applications.
基金Project supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions, the National Natural Science Foundation of China （Nos. 21072168, 21102009） and Natural Science Foundation of Jiangsu Province （No. B K2011230）.
文摘A new and efficient cascade synthesis of polycyclic fused imidazo[2,1-b][1,3]thiazinones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--S coupling reaction. The methodology is applied to a wide range of 2-iodo, 2-bromo, and 2-chloro benzoyl chlorides to yield the polycyclic fused imidazo[2,1-b][ 1,3]thiazinones in good to excellent yields.
文摘A convenient synthesis of intermediate 4,5-diamino-3-aryl-l-phenylpyrazoles 4a--4c was reported. The different cyclization reactions were carried out with chalcone, 2-mercaptoacetic acid and p-anisialdehyde, ethyl chloroformate, glyoxal and thiourea to afford different N and S containing heterocycles. The reaction conditions were compared by conventional heating and microwave irradiation. The structures of the cyclization products were de- termined by analytical and spectroscopic data. All the synthesized compounds were screened for antibacterial activities in vitro.
基金supported by the National Natural Science Foundation of China(22271197,21905176)the Natural Science Foundation for Distinguished Young Scholars of Guangdong Province(2020B1515020011)+1 种基金the Science and Technology Plan of Shenzhen(JCYJ20190808142403590,JCYJ20190808153415062)the Instrumental Analysis Center of Shenzhen University。
文摘The development of new and efficient polymerization strategies for the synthesis of multisubstituted fused heterocyclic polymers with attractive properties is of great significance.Herein,a rhodium-catalyzed polyannulation route is developed for the in situ generation of multisubstituted polyquinolines with efficient aggregate-state fluorescence.Based on the cascade C-H activation of isonicotinamides and their annulations with internal diynes,a series of high molecular weight polyquinolines are efficiently produced in high yields of up to 99%in a facile and atom-economical manner.Unlike conventional two-component stepwise polymerizations,these polyannulation reactions are tolerant to monomer non-stoichiometric conditions and proceed even more thoroughly in the presence of an excess amount of the isonicotinamide monomer.Benefiting from the unique multisubstituted polyquinoline structures,the obtained polymers show high thermal and morphological stability,useful aggregation-induced emission(AIE)properties,and tunable aggregated-state fluorescence behaviors.The AIE-active polyquinoline is demonstrated to be a good lysosome-specific fluorescent probe with low cytotoxicity and excellent photostability.
