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
Sodium azide is a widely used inorganic compound. Besides the commonly used method of ＂Wislicenus process＂ which uses ammonia, nitrous and sodium as materials, the hydrazine hydrate route is also employed for the pr...Sodium azide is a widely used inorganic compound. Besides the commonly used method of ＂Wislicenus process＂ which uses ammonia, nitrous and sodium as materials, the hydrazine hydrate route is also employed for the preparation of sodium azide particularly in laboratory. However, because many species are involved in the reaction system, the reaction details for the hydrazine hydrate route are still unclear. A comprehensive understanding of the reaction mechanism may provide meaningful help for optimizing the production process. In this work, the reaction mechanism for the synthesis of sodium azide by hydrazine hydrate route has been studied using density function theory（DFT） method. On the basis of our calculations, the reaction details, including the energetics of ten elementary steps, the structures of intermediates and transition states as well as the influence of inorganic acids and alcohols, were illuminated at the atomistic level. Both the two steps, the generation of key intermediate（NH2-NH-NO） and the trans-cistransformation of NH2-NH-NO, are suggested to be the possible rate-limiting step, corresponding to the energy barriers of 20.3 and 22.7 kcal/mol, respectively. In the early reaction steps to generate NH2-NH-NO, the main role of sulphuric acid is to donate proton, which can be replaced by nitric acid or hydrochloric acid. From the energy point of view, isopropanol has similar reactivity as methanol and ethanol.展开更多
Reduction of a series of N,N＇-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,...Reduction of a series of N,N＇-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,N＇-diaryl adipyl dihydrazine. The results show that hydrazine hydrate can selectively reduce azo bonds with other potential reducible bonds intact in the N,N＇-diaryl adipyl bis-azo compounds. The yields are high up to 92% under mild reaction conditions. According to the previous reports, this reduction process was attributed to an indirect reduction mechanism through an intermediate diimide.展开更多
Hydrazine hydrate(DH)is an important fine chemical intermediate and as fuel for rockets,however,it also has serious toxic for humans and environment.Developing novel materials and methods for sensitive detection of DH...Hydrazine hydrate(DH)is an important fine chemical intermediate and as fuel for rockets,however,it also has serious toxic for humans and environment.Developing novel materials and methods for sensitive detection of DH in water and air is an important task.In order to effectively detect DH,a novel conductive supramolecular polymer metallogel(PQ-Ag)has been constructed by the coordination of bis-5-hydroxyquinoline functionalized pillar[5]arene(PQ5)with Ag+.The metallogel PQ-Ag could realize the multi-channel sensitive detection of DH through naked-eye,fluorescence,and electrochemical methods.The lowest limit of detection(LOD)is 0.1 mg/m^(3)in air and 2.68×10^(−8)mol/L in water,which is lower than the standard of the US Environmental Protection Agency(EPA)for DH of maximum allowable concentration in drinking water.More importantly,an electronic device for DH detection based on the metallogel PQ-Ag was designed and prepared,which can realize conveniently and efficiently multi-channel detection and alert of DH through sound and light alarms not only in water but also in air.展开更多
Stable consumptiongrowth worldwideHydrazine hydrate is an organic chemi-cal raw material with extensiveapplications.The world’s capacity toproduce hydrazine hydrate hasreached more than 200 thousand t/atoday(based on...Stable consumptiongrowth worldwideHydrazine hydrate is an organic chemi-cal raw material with extensiveapplications.The world’s capacity toproduce hydrazine hydrate hasreached more than 200 thousand t/atoday(based on 100% hydrazinecontent).The capacity is divided nearlyequally between Europe,Asia andAmerica(35%,34% and 30%,respectively),with only 1% in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supported by the National Natural Science Foundation of China(21773138)
文摘Sodium azide is a widely used inorganic compound. Besides the commonly used method of ＂Wislicenus process＂ which uses ammonia, nitrous and sodium as materials, the hydrazine hydrate route is also employed for the preparation of sodium azide particularly in laboratory. However, because many species are involved in the reaction system, the reaction details for the hydrazine hydrate route are still unclear. A comprehensive understanding of the reaction mechanism may provide meaningful help for optimizing the production process. In this work, the reaction mechanism for the synthesis of sodium azide by hydrazine hydrate route has been studied using density function theory（DFT） method. On the basis of our calculations, the reaction details, including the energetics of ten elementary steps, the structures of intermediates and transition states as well as the influence of inorganic acids and alcohols, were illuminated at the atomistic level. Both the two steps, the generation of key intermediate（NH2-NH-NO） and the trans-cistransformation of NH2-NH-NO, are suggested to be the possible rate-limiting step, corresponding to the energy barriers of 20.3 and 22.7 kcal/mol, respectively. In the early reaction steps to generate NH2-NH-NO, the main role of sulphuric acid is to donate proton, which can be replaced by nitric acid or hydrochloric acid. From the energy point of view, isopropanol has similar reactivity as methanol and ethanol.
基金Supported by the Science Foundation of Education Department of Heilongjiang Province(12511142)
文摘Reduction of a series of N,N＇-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,N＇-diaryl adipyl dihydrazine. The results show that hydrazine hydrate can selectively reduce azo bonds with other potential reducible bonds intact in the N,N＇-diaryl adipyl bis-azo compounds. The yields are high up to 92% under mild reaction conditions. According to the previous reports, this reduction process was attributed to an indirect reduction mechanism through an intermediate diimide.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22065031,22061039)the Top Leading Talents Project of Gansu Province,the Key R&D program of Gansu Province(No.21YF5GA066)+1 种基金Gansu Province College Industry Support Plan Project(No.2022CYZC-18)Natural Science Foundation of Gansu Province(Nos.2020-0405-JCC-630,20JR10RA088).
文摘Hydrazine hydrate(DH)is an important fine chemical intermediate and as fuel for rockets,however,it also has serious toxic for humans and environment.Developing novel materials and methods for sensitive detection of DH in water and air is an important task.In order to effectively detect DH,a novel conductive supramolecular polymer metallogel(PQ-Ag)has been constructed by the coordination of bis-5-hydroxyquinoline functionalized pillar[5]arene(PQ5)with Ag+.The metallogel PQ-Ag could realize the multi-channel sensitive detection of DH through naked-eye,fluorescence,and electrochemical methods.The lowest limit of detection(LOD)is 0.1 mg/m^(3)in air and 2.68×10^(−8)mol/L in water,which is lower than the standard of the US Environmental Protection Agency(EPA)for DH of maximum allowable concentration in drinking water.More importantly,an electronic device for DH detection based on the metallogel PQ-Ag was designed and prepared,which can realize conveniently and efficiently multi-channel detection and alert of DH through sound and light alarms not only in water but also in air.
文摘Stable consumptiongrowth worldwideHydrazine hydrate is an organic chemi-cal raw material with extensiveapplications.The world’s capacity toproduce hydrazine hydrate hasreached more than 200 thousand t/atoday(based on 100% hydrazinecontent).The capacity is divided nearlyequally between Europe,Asia andAmerica(35%,34% and 30%,respectively),with only 1% in
