Sulphur-containing aromatic amines were prepared efficiently in good to excellent yields by reduction of the corresponding sulphur-containing aromatic nitro compounds with hydrazine hydrate in the presence of iron（Ⅲ...Sulphur-containing aromatic amines were prepared efficiently in good to excellent yields by reduction of the corresponding sulphur-containing aromatic nitro compounds with hydrazine hydrate in the presence of iron（Ⅲ） oxide-MgO catalyst. The catalyst exhibited high activity and stability for the reduction of sulphur-containing aromatic nitro compounds. The yields of sulphur-containing aromatic amines were up to 91-99 % at 355 K after reduction for 1-4 h over this catalyst.展开更多
By using the density functional theory （B3LYP） and four highly accurate complete basis set （CBS-Q, CBS-QB3, CBS-Lq, and CBS-4M）ab initio methods, the X（C, N, O）-NO2 bond dissociation energies （BDEs） for CH3NO2...By using the density functional theory （B3LYP） and four highly accurate complete basis set （CBS-Q, CBS-QB3, CBS-Lq, and CBS-4M）ab initio methods, the X（C, N, O）-NO2 bond dissociation energies （BDEs） for CH3NO2, C2H3NO2, C2H5NO2, HONO2, CH3ONO2, C2H5ONO2, NH2NO2 （CH3）2NNO2 are computed. By comparing the computed BDEs and experimental results, it is found that the B3LYP method is unable to predict satisfactorily the results of bond dissociation energy （BDE）; however, all four CBS models are generally able to give reliable predication of the X（C, N, O）-NO2 BDEs for these nitro compounds. Moreover, the CBS-4M calculation is the least computationally demanding among the four CBS methods considered, Therefore, we recommend CBS-4M method as a reliable method of computing the BDEs for this nitro compound system.展开更多
Sulphur-containing aromatic nitro compounds were rapidly reduced to the corresponding amines in high yields by employing hydrazine hydrate as a hydrogen donor in the presence of iron oxide hydroxide catalyst. It was w...Sulphur-containing aromatic nitro compounds were rapidly reduced to the corresponding amines in high yields by employing hydrazine hydrate as a hydrogen donor in the presence of iron oxide hydroxide catalyst. It was worth noting that the catalyst exhibited extremely high activity. The reduction could be completed within 20-50 min and the yields were up to 97-99 %.展开更多
Aromatic nitro compounds were reduced to the corresponding anilines by refluxing with potassium selenated borohydride (KBH2Se3) prepared from potassium borohydride and selenium in refluxed formamide.
N-Alkylhydroxylamines have been shown to undergo a stereospecific cis addition to 1-phenyl-2 -nitropropene compounds, whereas the corresponding O-alkylhydroxylamines give no diastereoselectivity. The concerted additio...N-Alkylhydroxylamines have been shown to undergo a stereospecific cis addition to 1-phenyl-2 -nitropropene compounds, whereas the corresponding O-alkylhydroxylamines give no diastereoselectivity. The concerted addition mechanism was provided to explain the difference.展开更多
Hydrogenation reactions play crucial roles on chemical synthesis and pollutant elimination.The improvement of the ability to activate reactants and increase of the contact probability between the catalysts and reactan...Hydrogenation reactions play crucial roles on chemical synthesis and pollutant elimination.The improvement of the ability to activate reactants and increase of the contact probability between the catalysts and reactants are positive to improve the catalytic performance.Herein,we have reported the design of two-dimensional porous Ni-Ni_(3)N-Ni Mo N heterojunction sheets(2D Mo-Ni based nanosheets)for efficient catalytic hydrogenation of the aromatic nitro-compounds.The heterojunction interfaces provide plentiful active sites to improve the activating ability of the catalyst on the reactants.Additionally,the 2D porous structure facilitates not only the contact of catalytic sites with reactants but also mass transfer and diffusion,both of which are favorable to accelerating the hydrogenation process.As a result,the optimized sample of 2D Mo-Ni sheet exhibits good activity for the hydrogenation of aromatic nitro-compounds by converting 0.2 mmol/L(30 mL)of p-nitrophenol to p-aminophenol within 45 s with good recyclability.The activation energy and the reaction rate at 25℃ is 31.11 k J/mol and 0.0796 s^(-1),respectively,both of which surpass most of reported non-noble metal catalysts and rivals with most noble metal-based catalysts.The combination of late and early transition metals provides an innovative way to obtain outstanding catalysts for the hydrogenation.展开更多
Arylamines constitute a fundamental class of organic compounds critical to pharmaceuticals,dyes,and advanced materials.The direct synthesis of arylamines from nitro compounds demonstrates significant advantages in ste...Arylamines constitute a fundamental class of organic compounds critical to pharmaceuticals,dyes,and advanced materials.The direct synthesis of arylamines from nitro compounds demonstrates significant advantages in step economy,cost efficiency,and functional group compatibility.However,conventional methodologies frequently necessitate transition metal catalysts or excessive reducing agents,limiting their practical applicability.Herein,we introduce a highly efficient photochemical protocol for the synthesis of arylamines from readily accessible nitro compounds and Grignard reagents under purple light(390—395 nm)irradiation,eliminating the requirement for transition metal catalysts or external reducing agents.This protocol exhibits exceptional tolerance to sterically hindered substrates and sensitive functional groups.Preliminary mechanistic investigations suggest the involvement of nitrosoarenes and diarylamine nitrogen radicals as key intermediates in the reaction pathway.展开更多
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China The differently substituted aromatic nitro compounds were chemoselect...bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China The differently substituted aromatic nitro compounds were chemoselectively reduced by Sm/HOAc system in an ionic liquid medium to afford aromatic amines. Under these conditions the other substituents, such as -X, -CHO, -COOH, -CN, -NHTos and -alkyl, remained intact. The notable advantages of this reaction are its mild conditions, simple operation, short reaction time, high yields and easy recycling of ionic liquid.展开更多
The Michael addition reactions of fluorinated nitro compounds with electron deficient olefins to give γ-fiuoro-γ-nitro-esters, nitriles and ketones which bear a fluorinated quaternary carbon center were reported. Th...The Michael addition reactions of fluorinated nitro compounds with electron deficient olefins to give γ-fiuoro-γ-nitro-esters, nitriles and ketones which bear a fluorinated quaternary carbon center were reported. The reactions were promoted by TMG, affording the desired adducts in acceptable to good yields.展开更多
Development of the economic, environmentally friendly synthesis of amines from nitro compounds remains important and challenging. In this work, the graphene shell encapsulated none noble Ni-based catalysts were succes...Development of the economic, environmentally friendly synthesis of amines from nitro compounds remains important and challenging. In this work, the graphene shell encapsulated none noble Ni-based catalysts were successfully designed and synthesized via an environmentally friendly method using H2O or Et OH as solvent. These fresh and recycling catalysts were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. For the nitro compounds hydrogenation, Ni@C-600-H2O exhibits the best catalytic activity to achieve 100 mol/mol conversions of nitrobenzene and 99% selectivity of aniline under mild reaction conditions of 1.0 MPa H2and 60°C.Many halogen-substituted, olefin substituted nitro compounds and aliphatic nitro compounds were investigated and desired products were obtained in excellent selectivity. What is more, the catalyst had excellent stability and could be recycled 13 times without any significant loss in selectivity and activity. Furthermore, we also reported the methodology for tertiary amines synthesis using Ni-based catalyst via one-pot, cost-effective tandem combination reaction with nitrobenzene hydrogenation and amines N-methylation.展开更多
The intermolecular reductive cyclization of o-nitrobenzene-sulfonamides with aliphatic ketones induced by TiCl4/Sm system was studied and a series of 3, 3-disubstituted-3,4-dihydro(2H)-1,2, 4-benzothiadiazine-1,1-diox...The intermolecular reductive cyclization of o-nitrobenzene-sulfonamides with aliphatic ketones induced by TiCl4/Sm system was studied and a series of 3, 3-disubstituted-3,4-dihydro(2H)-1,2, 4-benzothiadiazine-1,1-dioxides were synthesized in moderate to high yields under mild and neutral conditions.展开更多
Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for...Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.展开更多
Nitro-aromatic compounds can be photocatalytically reduced into the corresponding amine-aromatic com- pounds using TiO2 as a photocatalyst in the UV/TiO2/holes scavenger and Vis/TiO2/dye-sensitized systems. In the UV/...Nitro-aromatic compounds can be photocatalytically reduced into the corresponding amine-aromatic com- pounds using TiO2 as a photocatalyst in the UV/TiO2/holes scavenger and Vis/TiO2/dye-sensitized systems. In the UV/TiO2/holes scavenger system, reaction substrate alcohols such as methanol could be used as the holes scavengers, and in the Vis/TiO2/dye-sensitized system, substrate alcohols could be oxidized to the corresponding aldehydes with high selectivity. When methanol was used as the holes scavengers and the illumination time was 6 h, 87.2% ofp-nitrotoluene could be photocatalytically reduced into p-toluidine. In the Vis/TiO2/dye-sensitized system, the effect of aromatic alcohols for the photocatalytic reduction of nitrobenzene was better than that of other alcohols At the same time, aromatic alcohols can be easily oxidized, and the production efficiencies of the corresponding aldehydes were higher than those of other alcohols. The possible reaction mechanisms were also proposed.展开更多
Microorganims of the bovine rumen fluid biocatalyzed the reduction of nitro-compound substrates to yield the respective amines. This enzymatic process, using ruminal contents, has rarely been reported in associa- tion...Microorganims of the bovine rumen fluid biocatalyzed the reduction of nitro-compound substrates to yield the respective amines. This enzymatic process, using ruminal contents, has rarely been reported in associa- tion with the bioreduction of nitro groups. The biotransformation reactions catalyzed by this system were de- pendent of both the electronic characteristics and the area/volume of the nitro-substrates confirming the processes are enzymatic. The semi-preparative scale biotransformation went by in good yield showing the rumen fluid may be employed in the synthesis of amines under very mild conditions and, moreover, it may have application in the bioremediation of nitro-compounds.展开更多
A new adsorbent (JN-01) was prepared by modifying resin NDA-1800 with nitro functional groups.The adsorption capacities of resins XAD-4,NDA-1800 and JN-01 were investigated,and the results indicated that the modified ...A new adsorbent (JN-01) was prepared by modifying resin NDA-1800 with nitro functional groups.The adsorption capacities of resins XAD-4,NDA-1800 and JN-01 were investigated,and the results indicated that the modified resin JN-01 was much better in adsorbing phenol,p-nitrophenol and p-cresol.The adsorption capacities of the resin JN-01 were higher than those of the resins XAD-4 and NDA-1800 within a temperature range of 283-323 K,which might be attributed to the higher surface area and the partial polarity o...展开更多
Nanoparticles have properties that can be fine-tuned by their size as well as shape.Hence,there is significant current interest in preparing nano-materials of small size dispersity and to arrange them in close-packed ...Nanoparticles have properties that can be fine-tuned by their size as well as shape.Hence,there is significant current interest in preparing nano-materials of small size dispersity and to arrange them in close-packed aggregates.This letter describes a way of synthesising silver nanoparticles and their protection to aggregate by silica gel.The combination of catalytic quantities of immobilized silver nanoparticles with reductive ability of NaBH_4 efficiently reduces aromatic nitroarenes to the corresponding amines in aqueous medium.Noteworthy is that highly chemoselective reactions were achieved in the presence of other functional groups such as halogen and carboxylic acid groups.The silver particles immobilized on silica gel are stable in the presence of oxygen for several months.展开更多
文摘Sulphur-containing aromatic amines were prepared efficiently in good to excellent yields by reduction of the corresponding sulphur-containing aromatic nitro compounds with hydrazine hydrate in the presence of iron（Ⅲ） oxide-MgO catalyst. The catalyst exhibited high activity and stability for the reduction of sulphur-containing aromatic nitro compounds. The yields of sulphur-containing aromatic amines were up to 91-99 % at 355 K after reduction for 1-4 h over this catalyst.
基金Project supported by the National Natural Science Foundation of China and China Academy of Engineering Physics （Grant Nos 10376021, 10274055）.
文摘By using the density functional theory （B3LYP） and four highly accurate complete basis set （CBS-Q, CBS-QB3, CBS-Lq, and CBS-4M）ab initio methods, the X（C, N, O）-NO2 bond dissociation energies （BDEs） for CH3NO2, C2H3NO2, C2H5NO2, HONO2, CH3ONO2, C2H5ONO2, NH2NO2 （CH3）2NNO2 are computed. By comparing the computed BDEs and experimental results, it is found that the B3LYP method is unable to predict satisfactorily the results of bond dissociation energy （BDE）; however, all four CBS models are generally able to give reliable predication of the X（C, N, O）-NO2 BDEs for these nitro compounds. Moreover, the CBS-4M calculation is the least computationally demanding among the four CBS methods considered, Therefore, we recommend CBS-4M method as a reliable method of computing the BDEs for this nitro compound system.
文摘Sulphur-containing aromatic nitro compounds were rapidly reduced to the corresponding amines in high yields by employing hydrazine hydrate as a hydrogen donor in the presence of iron oxide hydroxide catalyst. It was worth noting that the catalyst exhibited extremely high activity. The reduction could be completed within 20-50 min and the yields were up to 97-99 %.
文摘Aromatic nitro compounds were reduced to the corresponding anilines by refluxing with potassium selenated borohydride (KBH2Se3) prepared from potassium borohydride and selenium in refluxed formamide.
文摘N-Alkylhydroxylamines have been shown to undergo a stereospecific cis addition to 1-phenyl-2 -nitropropene compounds, whereas the corresponding O-alkylhydroxylamines give no diastereoselectivity. The concerted addition mechanism was provided to explain the difference.
基金the support of this research by the National Natural Science Foundation of China(No.91961111)the Natural Science Foundation of Heilongjiang Province(No.ZD2021B003)Fundamental Research Funds for the Central Universities(No.2572022BU05)。
文摘Hydrogenation reactions play crucial roles on chemical synthesis and pollutant elimination.The improvement of the ability to activate reactants and increase of the contact probability between the catalysts and reactants are positive to improve the catalytic performance.Herein,we have reported the design of two-dimensional porous Ni-Ni_(3)N-Ni Mo N heterojunction sheets(2D Mo-Ni based nanosheets)for efficient catalytic hydrogenation of the aromatic nitro-compounds.The heterojunction interfaces provide plentiful active sites to improve the activating ability of the catalyst on the reactants.Additionally,the 2D porous structure facilitates not only the contact of catalytic sites with reactants but also mass transfer and diffusion,both of which are favorable to accelerating the hydrogenation process.As a result,the optimized sample of 2D Mo-Ni sheet exhibits good activity for the hydrogenation of aromatic nitro-compounds by converting 0.2 mmol/L(30 mL)of p-nitrophenol to p-aminophenol within 45 s with good recyclability.The activation energy and the reaction rate at 25℃ is 31.11 k J/mol and 0.0796 s^(-1),respectively,both of which surpass most of reported non-noble metal catalysts and rivals with most noble metal-based catalysts.The combination of late and early transition metals provides an innovative way to obtain outstanding catalysts for the hydrogenation.
基金supported by the National Natural Science Foundation of China(22171174)the Fundamental Research Funds for the Central Universities(GK202304033,GK202406026)+2 种基金the Innovation Capability Support Program of Shaanxi(2023-CX-TD-28)the Shaanxi Fundamental Science Research Project for Chemistry&Biology(22JHZ002)the Natural Science Foundation of Shaanxi Province(2023-JC-YB-100).
文摘Arylamines constitute a fundamental class of organic compounds critical to pharmaceuticals,dyes,and advanced materials.The direct synthesis of arylamines from nitro compounds demonstrates significant advantages in step economy,cost efficiency,and functional group compatibility.However,conventional methodologies frequently necessitate transition metal catalysts or excessive reducing agents,limiting their practical applicability.Herein,we introduce a highly efficient photochemical protocol for the synthesis of arylamines from readily accessible nitro compounds and Grignard reagents under purple light(390—395 nm)irradiation,eliminating the requirement for transition metal catalysts or external reducing agents.This protocol exhibits exceptional tolerance to sterically hindered substrates and sensitive functional groups.Preliminary mechanistic investigations suggest the involvement of nitrosoarenes and diarylamine nitrogen radicals as key intermediates in the reaction pathway.
基金theNationalNaturalScienceFoundationofChina (No .2 9872 0 10 )theNaturalScienceFoundationofZhejiangProvinceChina (No .2 0 0 72 0 33)
文摘bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China The differently substituted aromatic nitro compounds were chemoselectively reduced by Sm/HOAc system in an ionic liquid medium to afford aromatic amines. Under these conditions the other substituents, such as -X, -CHO, -COOH, -CN, -NHTos and -alkyl, remained intact. The notable advantages of this reaction are its mild conditions, simple operation, short reaction time, high yields and easy recycling of ionic liquid.
文摘The Michael addition reactions of fluorinated nitro compounds with electron deficient olefins to give γ-fiuoro-γ-nitro-esters, nitriles and ketones which bear a fluorinated quaternary carbon center were reported. The reactions were promoted by TMG, affording the desired adducts in acceptable to good yields.
基金National Key R&D Program of China(2019YFD1100601)National Natural Science Foundation of China(Project 51976225)Dalian National Laboratory Cooperation Foundation,Chinese Academy of Sciences(Project DNL201916)for financial support。
文摘Development of the economic, environmentally friendly synthesis of amines from nitro compounds remains important and challenging. In this work, the graphene shell encapsulated none noble Ni-based catalysts were successfully designed and synthesized via an environmentally friendly method using H2O or Et OH as solvent. These fresh and recycling catalysts were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. For the nitro compounds hydrogenation, Ni@C-600-H2O exhibits the best catalytic activity to achieve 100 mol/mol conversions of nitrobenzene and 99% selectivity of aniline under mild reaction conditions of 1.0 MPa H2and 60°C.Many halogen-substituted, olefin substituted nitro compounds and aliphatic nitro compounds were investigated and desired products were obtained in excellent selectivity. What is more, the catalyst had excellent stability and could be recycled 13 times without any significant loss in selectivity and activity. Furthermore, we also reported the methodology for tertiary amines synthesis using Ni-based catalyst via one-pot, cost-effective tandem combination reaction with nitrobenzene hydrogenation and amines N-methylation.
基金Project supported by the National Natural Science Foundation of China (No. 29872010)Natural Science Foundation of Zhejiang Province, China
文摘The intermolecular reductive cyclization of o-nitrobenzene-sulfonamides with aliphatic ketones induced by TiCl4/Sm system was studied and a series of 3, 3-disubstituted-3,4-dihydro(2H)-1,2, 4-benzothiadiazine-1,1-dioxides were synthesized in moderate to high yields under mild and neutral conditions.
基金supported by the fundamental research funds of Zhejiang Sci-Tech University(No.22212286-Y)the Natural Science Foundation of Zhejiang Province(No.LQ24B040003)。
文摘Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.
基金Project supported by the National Natural Science Foundation of China （Nos. 20673042, 20973071） and the Key Project of Science and Technology Research of Ministry of Education of China （208062）.
文摘Nitro-aromatic compounds can be photocatalytically reduced into the corresponding amine-aromatic com- pounds using TiO2 as a photocatalyst in the UV/TiO2/holes scavenger and Vis/TiO2/dye-sensitized systems. In the UV/TiO2/holes scavenger system, reaction substrate alcohols such as methanol could be used as the holes scavengers, and in the Vis/TiO2/dye-sensitized system, substrate alcohols could be oxidized to the corresponding aldehydes with high selectivity. When methanol was used as the holes scavengers and the illumination time was 6 h, 87.2% ofp-nitrotoluene could be photocatalytically reduced into p-toluidine. In the Vis/TiO2/dye-sensitized system, the effect of aromatic alcohols for the photocatalytic reduction of nitrobenzene was better than that of other alcohols At the same time, aromatic alcohols can be easily oxidized, and the production efficiencies of the corresponding aldehydes were higher than those of other alcohols. The possible reaction mechanisms were also proposed.
文摘Microorganims of the bovine rumen fluid biocatalyzed the reduction of nitro-compound substrates to yield the respective amines. This enzymatic process, using ruminal contents, has rarely been reported in associa- tion with the bioreduction of nitro groups. The biotransformation reactions catalyzed by this system were de- pendent of both the electronic characteristics and the area/volume of the nitro-substrates confirming the processes are enzymatic. The semi-preparative scale biotransformation went by in good yield showing the rumen fluid may be employed in the synthesis of amines under very mild conditions and, moreover, it may have application in the bioremediation of nitro-compounds.
基金supported by the National Nature Science Fund (No.50778088)Resources Special Subject of National High Technology Research & Development Project (863 Project No.2006AA06Z383),China.
文摘A new adsorbent (JN-01) was prepared by modifying resin NDA-1800 with nitro functional groups.The adsorption capacities of resins XAD-4,NDA-1800 and JN-01 were investigated,and the results indicated that the modified resin JN-01 was much better in adsorbing phenol,p-nitrophenol and p-cresol.The adsorption capacities of the resin JN-01 were higher than those of the resins XAD-4 and NDA-1800 within a temperature range of 283-323 K,which might be attributed to the higher surface area and the partial polarity o...
基金supports for this work by Shahid Chamran University Research Council
文摘Nanoparticles have properties that can be fine-tuned by their size as well as shape.Hence,there is significant current interest in preparing nano-materials of small size dispersity and to arrange them in close-packed aggregates.This letter describes a way of synthesising silver nanoparticles and their protection to aggregate by silica gel.The combination of catalytic quantities of immobilized silver nanoparticles with reductive ability of NaBH_4 efficiently reduces aromatic nitroarenes to the corresponding amines in aqueous medium.Noteworthy is that highly chemoselective reactions were achieved in the presence of other functional groups such as halogen and carboxylic acid groups.The silver particles immobilized on silica gel are stable in the presence of oxygen for several months.
