A new one-pot neat synthesis of some 5-aryl-2,4-dihydro-3H- 1,2,4-triazol-3-ones through cyclocondensation of ethyl carbazate with aryl nitriles catalyzed by DMAP as an efficient and basic nucleophilic catalyst is des...A new one-pot neat synthesis of some 5-aryl-2,4-dihydro-3H- 1,2,4-triazol-3-ones through cyclocondensation of ethyl carbazate with aryl nitriles catalyzed by DMAP as an efficient and basic nucleophilic catalyst is described.展开更多
The nitrile functionality is a key building block in synthetic chemistry, and has wide applications in pharmaceuticals. However, traditional methodologies for the synthesis of nitriles are limited to harsh reaction co...The nitrile functionality is a key building block in synthetic chemistry, and has wide applications in pharmaceuticals. However, traditional methodologies for the synthesis of nitriles are limited to harsh reaction conditions. Herein, we report a new and efficient access to aryl nitriles by an electrochemical synthesis. Compared with the conventional synthetic methods, this electrochemical synthesis is more environmentally friendly and easier to handle.展开更多
A series of novel poly(aryl ether nitrile)s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers (I) with 2,6-difluorobenzonitrile. The inherent vis...A series of novel poly(aryl ether nitrile)s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers (I) with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly(aryl ether nitrile)s including solubility and crystallinity were also studied.展开更多
In order to effectively improve the properties of anion exchange membrane(AEM)materials,a series of novel poly(aryl ether nitrile)s with flexible side-chain-type quaternary phosphonium cations(PAEN-TPP-x)were designed...In order to effectively improve the properties of anion exchange membrane(AEM)materials,a series of novel poly(aryl ether nitrile)s with flexible side-chain-type quaternary phosphonium cations(PAEN-TPP-x)were designed and prepared on the basis of considering the influences of polymer backbone,cationic group species and the connection way between the cations and polymer chains.The synthetic method,structure and ion-exchange capacity,water absorption,swelling,hydroxide conductivity and alkaline stability of the obtained AEMs were studied.A comparative study with other reported AEMs was also performed for further exploration of the relationship between the structure and properties.These AEMs with flexible side-chain-type quaternary phosphonium cations displayed good comprehensive properties.Their water uptakes and swelling ratios were in the range of 11.6%–22.7%and 4.4%–7.8%at 60℃,respectively.They had hydroxide conductivity in the range of 28.6–45.8 mS cm^-1 at 60℃.Moreover,these AEMs also exhibited improved alkaline stability,and the hydroxide conductivity for PAEN-TPP-0.35 could remain 82.1%and 80.6%of its initial value at 60 and 90℃in 2 mol L^-1 NaOH solution for480 h,respectively.展开更多
The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles.Despite tremendous advances,cyanating an aryl halide in a facile and benign fashion has generall...The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles.Despite tremendous advances,cyanating an aryl halide in a facile and benign fashion has generally been unsuccessful.The challenge in this significant transformation is the strong affinity of cyanide for metals,which hampers oxidative addition(OD)and reductive elimination(RE)making organometallic catalysis elusive.Herein,we demonstrate for the first time that photoredox-nickel-catalyzed cyanations of aryl halides are readily enabled by visible light,in which Ni(Ⅱ)species are transiently oxidized to Ni(Ⅲ)species,thereby facilitating subsequent cyanide transfer and RE.Using this dual catalysis strategy,we cyanated aryl and alkenyl halides at room temperature in a highly benign manner(30 examples,53-93% yield)by avoiding the use of air-sensitive ligands,Ni(0)precursors,and hypertoxic cyanation reagents,while also limiting excess metal waste.Computational studies were also used to help understand the present transformation.展开更多
A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich an...A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and defi- cient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halo- gen-free Cu20 as catalysts make the protocol an appealing option for aryl cyanations.展开更多
Currently,many cancer patients with bone defects are still threatened by tumor recurrence,postoperative bacterial infection,and massive bone loss.Many methods have been studied to endow bone implants with biocompatibi...Currently,many cancer patients with bone defects are still threatened by tumor recurrence,postoperative bacterial infection,and massive bone loss.Many methods have been studied to endow bone implants with biocompatibility,but it is difficult to find an implant material that can simultaneously solve the problems of anticancer,antibacterial and bone promotion.Here,a multifunctional gelatin methacrylate/dopamine methacrylate adhesive hydrogel coating containing 2D black phosphorus(BP)nanoparticle protected by polydopamine(pBP)is prepared by photocrosslinking to modify the surface of poly(aryl ether nitrile ketone)containing phthalazinone(PPENK)implant.The multifunctional hydrogel coating works in conjunction with pBP,which can deliver drug through photothermal mediation and kill bacteria through photodynamic therapy at the initial phase followed by promotion of osteointegration.In this design,photothermal effect of pBP control the release of doxorubicin hydrochloride loaded via electrostatic attraction.Meanwhile,pBP can generate reactive oxygen species(ROS)to eliminate bacterial infection under 808 nm laser.In the slow degradation process,pBP not only effectively consumes excess ROS and avoid apoptosis induced by ROS in normal cells,but also degrade into PO43to promote osteogenesis.In summary,nanocomposite hydrogel coatings provide a promising strategy for treatment of cancer patients with bone defects.展开更多
A phthalazinone monomer with an allyl group, i.e. 4-(3-allyl-4-hydroxyphenyl)phthalazin-1(2H)-one, was synthesized and then copolymerized with 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one and 2,6- diflurobenzonit...A phthalazinone monomer with an allyl group, i.e. 4-(3-allyl-4-hydroxyphenyl)phthalazin-1(2H)-one, was synthesized and then copolymerized with 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one and 2,6- diflurobenzonitrile by means of aromatic nucleophilic polycondensation to provide a series of crosslinkable poly(aryl ether nitrile)s. The virgin copolymers exhibited good solubility in polar organic solvents with relative high molecular weights (Mw: 45,130-58,403, inherent viscosities: 0.58-0.75 dL/ g). After cross-linking, the thermal stability and solvent resistance of the polymer increased.展开更多
文摘A new one-pot neat synthesis of some 5-aryl-2,4-dihydro-3H- 1,2,4-triazol-3-ones through cyclocondensation of ethyl carbazate with aryl nitriles catalyzed by DMAP as an efficient and basic nucleophilic catalyst is described.
基金financially supported by the National Natural Science Foundation of China (Nos. 2127222, 91213303, 21172205, J1030412)
文摘The nitrile functionality is a key building block in synthetic chemistry, and has wide applications in pharmaceuticals. However, traditional methodologies for the synthesis of nitriles are limited to harsh reaction conditions. Herein, we report a new and efficient access to aryl nitriles by an electrochemical synthesis. Compared with the conventional synthetic methods, this electrochemical synthesis is more environmentally friendly and easier to handle.
文摘A series of novel poly(aryl ether nitrile)s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers (I) with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly(aryl ether nitrile)s including solubility and crystallinity were also studied.
基金supported by the National Natural Science Foundation of China (21404016)the Key Research Program of Jiangsu Province (BE2017645)+1 种基金the Six Talent Peaks Project of Jiangsu Province (XCL-078)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions of China
文摘In order to effectively improve the properties of anion exchange membrane(AEM)materials,a series of novel poly(aryl ether nitrile)s with flexible side-chain-type quaternary phosphonium cations(PAEN-TPP-x)were designed and prepared on the basis of considering the influences of polymer backbone,cationic group species and the connection way between the cations and polymer chains.The synthetic method,structure and ion-exchange capacity,water absorption,swelling,hydroxide conductivity and alkaline stability of the obtained AEMs were studied.A comparative study with other reported AEMs was also performed for further exploration of the relationship between the structure and properties.These AEMs with flexible side-chain-type quaternary phosphonium cations displayed good comprehensive properties.Their water uptakes and swelling ratios were in the range of 11.6%–22.7%and 4.4%–7.8%at 60℃,respectively.They had hydroxide conductivity in the range of 28.6–45.8 mS cm^-1 at 60℃.Moreover,these AEMs also exhibited improved alkaline stability,and the hydroxide conductivity for PAEN-TPP-0.35 could remain 82.1%and 80.6%of its initial value at 60 and 90℃in 2 mol L^-1 NaOH solution for480 h,respectively.
基金the National Science Foundation of China(nos.21822103,21820102003,21822303,21772052,21772053,and 91956201)the Program of Introducing Talents of Discipline to Universities of China(111 Program,B17019)the Natural Science Foundation of Hubei Province(no.2017AHB047).
文摘The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles.Despite tremendous advances,cyanating an aryl halide in a facile and benign fashion has generally been unsuccessful.The challenge in this significant transformation is the strong affinity of cyanide for metals,which hampers oxidative addition(OD)and reductive elimination(RE)making organometallic catalysis elusive.Herein,we demonstrate for the first time that photoredox-nickel-catalyzed cyanations of aryl halides are readily enabled by visible light,in which Ni(Ⅱ)species are transiently oxidized to Ni(Ⅲ)species,thereby facilitating subsequent cyanide transfer and RE.Using this dual catalysis strategy,we cyanated aryl and alkenyl halides at room temperature in a highly benign manner(30 examples,53-93% yield)by avoiding the use of air-sensitive ligands,Ni(0)precursors,and hypertoxic cyanation reagents,while also limiting excess metal waste.Computational studies were also used to help understand the present transformation.
文摘A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and defi- cient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halo- gen-free Cu20 as catalysts make the protocol an appealing option for aryl cyanations.
基金supported by Ningbo Key Research and Development Program(No.2022Z143)National Natural Science Foundation of China(No.U1837205)the Fundamental Research Funds for the Central University(No.DUT22LAB605).
文摘Currently,many cancer patients with bone defects are still threatened by tumor recurrence,postoperative bacterial infection,and massive bone loss.Many methods have been studied to endow bone implants with biocompatibility,but it is difficult to find an implant material that can simultaneously solve the problems of anticancer,antibacterial and bone promotion.Here,a multifunctional gelatin methacrylate/dopamine methacrylate adhesive hydrogel coating containing 2D black phosphorus(BP)nanoparticle protected by polydopamine(pBP)is prepared by photocrosslinking to modify the surface of poly(aryl ether nitrile ketone)containing phthalazinone(PPENK)implant.The multifunctional hydrogel coating works in conjunction with pBP,which can deliver drug through photothermal mediation and kill bacteria through photodynamic therapy at the initial phase followed by promotion of osteointegration.In this design,photothermal effect of pBP control the release of doxorubicin hydrochloride loaded via electrostatic attraction.Meanwhile,pBP can generate reactive oxygen species(ROS)to eliminate bacterial infection under 808 nm laser.In the slow degradation process,pBP not only effectively consumes excess ROS and avoid apoptosis induced by ROS in normal cells,but also degrade into PO43to promote osteogenesis.In summary,nanocomposite hydrogel coatings provide a promising strategy for treatment of cancer patients with bone defects.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK2012142)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.11KJD150005)
文摘A phthalazinone monomer with an allyl group, i.e. 4-(3-allyl-4-hydroxyphenyl)phthalazin-1(2H)-one, was synthesized and then copolymerized with 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one and 2,6- diflurobenzonitrile by means of aromatic nucleophilic polycondensation to provide a series of crosslinkable poly(aryl ether nitrile)s. The virgin copolymers exhibited good solubility in polar organic solvents with relative high molecular weights (Mw: 45,130-58,403, inherent viscosities: 0.58-0.75 dL/ g). After cross-linking, the thermal stability and solvent resistance of the polymer increased.