Ph 2NH and PCl 3 interacted at a molar ratio of 1∶1 05 and slow elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H 2O to produce a very hard brown solid believed to be...Ph 2NH and PCl 3 interacted at a molar ratio of 1∶1 05 and slow elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H 2O to produce a very hard brown solid believed to be a mixture of 5,10 dihydrophenophosphazine 10 oxide(1a) and 10,10(5H,5H) spirobipenophosphazinium chloride(1b). This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10 hydroxy 5,10 dihydropheno phosphazine 10 oxide(2) with a higher yield(45%) than that of the literature(27%). When treated with excess SOCl 2, compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in 70% as treated with NaOMe in methanol. Compound 2 could also be converted to a bisanion when treated with NaH in DMF. The resulted bisanion reacted with MeI to give 5 methyl 10 hydroxy 5,10 dihydrophenophosphazine 10 oxide in a 73% yield which would be converted to 5 methyl 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in a 56% yield by the same way of synthesizing 10 methoxy 5,10 dihydrophenophosphazine 10 oxide. All these compounds obtained were identified by surveying their melting points, and spectra and elemental analysis.展开更多
For at least the past five decades,structural synthesis has been used as a main means of finding better mechanisms with some predefined function.In structural synthesis,isomorphism identification is still a problem un...For at least the past five decades,structural synthesis has been used as a main means of finding better mechanisms with some predefined function.In structural synthesis,isomorphism identification is still a problem unsolved well,and to solve this problem is very significant to the design of new mechanisms.According to the given degree of freedom（DOF） and link connection property of planar closed chain mechanisms,vertex assortment is obtained.For solving the isomorphism problem,a method of the adding sub-chains is proposed with the detailed steps and algorithms in the synthesizing process.Employing this method,the identification code and formation code of every topological structure are achieved,therefore many isomorphic structures could be eliminated in time during structural synthesis by comparing those codes among different topological graphs,resulting in the improvement of synthesizing efficiency and accuracy,and the approach for eliminating rigid sub-chains in and after the synthesizing process is also presented.Some examples are given,including how to add sub-chains,how to detect simple rigid sub-chains and how to obtain identification codes and formulation codes et al.Using the adding sub-chain method,the relative information of some common topological graphs is given in the form of table.The comparison result is coincident with many literatures,so the correctness of the adding sub-chain method is convinced.This method will greatly improve the synthesizing efficiency and accuracy,and has a good potential for application.展开更多
Hydroxy-5-methyl-5, 10- dihydrophenophosphazine 10-oxide (1) was prepared by a new technique of treating 10-methoxy-5,10-dihydrophenophosphazine 10-oxide (2) with an equivalent of NaH in anhydrous DMF, and then at 120...Hydroxy-5-methyl-5, 10- dihydrophenophosphazine 10-oxide (1) was prepared by a new technique of treating 10-methoxy-5,10-dihydrophenophosphazine 10-oxide (2) with an equivalent of NaH in anhydrous DMF, and then at 120C for 3~4 h, which not only avoided poisonous and expensive methyl iodide used in literature, but made the consumption of NaH greatly decrease as well. The possible reaction mechanism was also described. The chemical structure of 1 was confirmed by IR, NMR, and mass spectroscopy.展开更多
The title compound (1) was treated with NaH at room temperature in anhydrous DMF to give a sodium salt (containing nitrogen anion) which could shift the methyl group from oxygen to nitrogen atom to form N-methyl phosp...The title compound (1) was treated with NaH at room temperature in anhydrous DMF to give a sodium salt (containing nitrogen anion) which could shift the methyl group from oxygen to nitrogen atom to form N-methyl phosphinic acid as the reaction temperature was increased to 120 ℃. Three nitro derivatives containing 5,10-dihydrophenophosphazine ring system were prepared for the investigation on the above reaction mechanism which would be possibly regarded as a special inter-molecular substitution, viz., the nucleophilic nitrogen anion from one molecule of 1 attacked the carbon atom of the O-methyl of another 1. In addition, the chemical structures of seven compounds containing 5,10-dihydrophenophos-phazine ring system involved in the experiment were confirmed by IR, 1H NMR, 31P NMR and mass spectroscopy.展开更多
This paper presents a mechanism theory principle for equivalent substitution in kinematic chain of a higher pair for lower pairs. This is the opposite of the principle of the equivalent substitution of lower pairs for...This paper presents a mechanism theory principle for equivalent substitution in kinematic chain of a higher pair for lower pairs. This is the opposite of the principle of the equivalent substitution of lower pairs for a higher pair. Also presented here is a new approach for isomorphism identification in kinematic chains containing higher pairs(KCCHs). Based on this approach, an algorithm for generating nonisomorphic KCCHs has been developed. This algorithm is not restricted by the number of links, the degree of freedom or the number of higher pairs. Using this algorithm, nonisomorphic KCCHs can be generated automatically from the kinematic chains that contain only lower pairs. As an application of this algorithm, all the nonisomorphic KCCHs with N<10(N, the number of links), F≤3 (F, the degree of KCCHs), and H≤2(H, the number of higher pairs) are computer generated.展开更多
室温下,用醋酸硝酰(浓硝酸与冰醋酸混合物)将10-羟基-5,10-二氢磷杂吖嗪-10-氧化物硝化5 h,得10-羟基-2-硝基-5,10-二氢磷杂吖嗪-10-氧化物(74%)。后者在中性介质中,用5%Pd/C作催化剂,氢化还原得到2-氨基-10-羟基-5,10-二氢磷杂吖嗪-10...室温下,用醋酸硝酰(浓硝酸与冰醋酸混合物)将10-羟基-5,10-二氢磷杂吖嗪-10-氧化物硝化5 h,得10-羟基-2-硝基-5,10-二氢磷杂吖嗪-10-氧化物(74%)。后者在中性介质中,用5%Pd/C作催化剂,氢化还原得到2-氨基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物(70%)。经过Salmonella/m amm alian m icrosom e assay测试,该氨基物表现为非诱变性,用它作为重氮组分,分别与3种吡唑啉酮系衍生物偶合得到3种红色酸性偶氮染料。研究了这些染料的光谱性质及其应用性能。结果表明,所合成的新染料比由一般芳香胺与吡唑啉酮形成的偶氮化合物具有深色效应。用波谱分析确定了中间体及其染料的结构。展开更多
The modeling method and identified method adapted to multi-degree-of-freedom structures with strucrural nonlinearities are established.The component mode synthesis method is used to establish the nonlinear governing e...The modeling method and identified method adapted to multi-degree-of-freedom structures with strucrural nonlinearities are established.The component mode synthesis method is used to establish the nonlinear governing equations by extending the connected relationships.Based on the modeling method,the Hilbert transform method is applied to identify the nonlinear stiffness of multi-degree-of-freedom structures.Nonlinear analysis and identification of a typical folding wing configuration with three freeplay hinges are investigated.The nonlinear governing equation is established based on present methods and the computing results of different stiffness are checked by finite element programming.In order to illustrate the influence of the nonlinearities,the frequency response characteristics of the structure are analyzed and Hilbert transform is performed.The Hilbert transform identification method is utilized to identify the nonlinear stiffness of nonlinear hinges in the time domain and several parametric studies are performed.In addition,the comparison of response is made to illustrate the feasibility of the methods.The results show that the extending component mode synthesis method in the present work can be used to establish the governing equation with structural nonlinearities.Based on the modeling method,the Hilbert transform identified method can be extended to multi-degree-of-freedom structures accurately.展开更多
基金Supported by National Natural Science Foundation of China(No.2 9972 0 0 6 ) .
文摘Ph 2NH and PCl 3 interacted at a molar ratio of 1∶1 05 and slow elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H 2O to produce a very hard brown solid believed to be a mixture of 5,10 dihydrophenophosphazine 10 oxide(1a) and 10,10(5H,5H) spirobipenophosphazinium chloride(1b). This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10 hydroxy 5,10 dihydropheno phosphazine 10 oxide(2) with a higher yield(45%) than that of the literature(27%). When treated with excess SOCl 2, compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in 70% as treated with NaOMe in methanol. Compound 2 could also be converted to a bisanion when treated with NaH in DMF. The resulted bisanion reacted with MeI to give 5 methyl 10 hydroxy 5,10 dihydrophenophosphazine 10 oxide in a 73% yield which would be converted to 5 methyl 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in a 56% yield by the same way of synthesizing 10 methoxy 5,10 dihydrophenophosphazine 10 oxide. All these compounds obtained were identified by surveying their melting points, and spectra and elemental analysis.
基金supported by National Natural Science Foundation of China (Grant No. 51075079)National Hi-tech Research and Development Program of China(863 Program,Grant No. 2008AA04Z202)
文摘For at least the past five decades,structural synthesis has been used as a main means of finding better mechanisms with some predefined function.In structural synthesis,isomorphism identification is still a problem unsolved well,and to solve this problem is very significant to the design of new mechanisms.According to the given degree of freedom（DOF） and link connection property of planar closed chain mechanisms,vertex assortment is obtained.For solving the isomorphism problem,a method of the adding sub-chains is proposed with the detailed steps and algorithms in the synthesizing process.Employing this method,the identification code and formation code of every topological structure are achieved,therefore many isomorphic structures could be eliminated in time during structural synthesis by comparing those codes among different topological graphs,resulting in the improvement of synthesizing efficiency and accuracy,and the approach for eliminating rigid sub-chains in and after the synthesizing process is also presented.Some examples are given,including how to add sub-chains,how to detect simple rigid sub-chains and how to obtain identification codes and formulation codes et al.Using the adding sub-chain method,the relative information of some common topological graphs is given in the form of table.The comparison result is coincident with many literatures,so the correctness of the adding sub-chain method is convinced.This method will greatly improve the synthesizing efficiency and accuracy,and has a good potential for application.
基金The authors would like to acknowledge support from the National Natural Science Foundation of China(29972006) especially to express the deep appreciation to Professor Q. J. Peng and Miss K. Jin from our laboratory for their assistance in performing str
文摘Hydroxy-5-methyl-5, 10- dihydrophenophosphazine 10-oxide (1) was prepared by a new technique of treating 10-methoxy-5,10-dihydrophenophosphazine 10-oxide (2) with an equivalent of NaH in anhydrous DMF, and then at 120C for 3~4 h, which not only avoided poisonous and expensive methyl iodide used in literature, but made the consumption of NaH greatly decrease as well. The possible reaction mechanism was also described. The chemical structure of 1 was confirmed by IR, NMR, and mass spectroscopy.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 9972 0 0 6)
文摘The title compound (1) was treated with NaH at room temperature in anhydrous DMF to give a sodium salt (containing nitrogen anion) which could shift the methyl group from oxygen to nitrogen atom to form N-methyl phosphinic acid as the reaction temperature was increased to 120 ℃. Three nitro derivatives containing 5,10-dihydrophenophosphazine ring system were prepared for the investigation on the above reaction mechanism which would be possibly regarded as a special inter-molecular substitution, viz., the nucleophilic nitrogen anion from one molecule of 1 attacked the carbon atom of the O-methyl of another 1. In addition, the chemical structures of seven compounds containing 5,10-dihydrophenophos-phazine ring system involved in the experiment were confirmed by IR, 1H NMR, 31P NMR and mass spectroscopy.
文摘This paper presents a mechanism theory principle for equivalent substitution in kinematic chain of a higher pair for lower pairs. This is the opposite of the principle of the equivalent substitution of lower pairs for a higher pair. Also presented here is a new approach for isomorphism identification in kinematic chains containing higher pairs(KCCHs). Based on this approach, an algorithm for generating nonisomorphic KCCHs has been developed. This algorithm is not restricted by the number of links, the degree of freedom or the number of higher pairs. Using this algorithm, nonisomorphic KCCHs can be generated automatically from the kinematic chains that contain only lower pairs. As an application of this algorithm, all the nonisomorphic KCCHs with N<10(N, the number of links), F≤3 (F, the degree of KCCHs), and H≤2(H, the number of higher pairs) are computer generated.
文摘室温下,用醋酸硝酰(浓硝酸与冰醋酸混合物)将10-羟基-5,10-二氢磷杂吖嗪-10-氧化物硝化5 h,得10-羟基-2-硝基-5,10-二氢磷杂吖嗪-10-氧化物(74%)。后者在中性介质中,用5%Pd/C作催化剂,氢化还原得到2-氨基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物(70%)。经过Salmonella/m amm alian m icrosom e assay测试,该氨基物表现为非诱变性,用它作为重氮组分,分别与3种吡唑啉酮系衍生物偶合得到3种红色酸性偶氮染料。研究了这些染料的光谱性质及其应用性能。结果表明,所合成的新染料比由一般芳香胺与吡唑啉酮形成的偶氮化合物具有深色效应。用波谱分析确定了中间体及其染料的结构。
基金supported by the National Natural Sciences Foundation of China(Grant Nos.91116005 and 10902006)
文摘The modeling method and identified method adapted to multi-degree-of-freedom structures with strucrural nonlinearities are established.The component mode synthesis method is used to establish the nonlinear governing equations by extending the connected relationships.Based on the modeling method,the Hilbert transform method is applied to identify the nonlinear stiffness of multi-degree-of-freedom structures.Nonlinear analysis and identification of a typical folding wing configuration with three freeplay hinges are investigated.The nonlinear governing equation is established based on present methods and the computing results of different stiffness are checked by finite element programming.In order to illustrate the influence of the nonlinearities,the frequency response characteristics of the structure are analyzed and Hilbert transform is performed.The Hilbert transform identification method is utilized to identify the nonlinear stiffness of nonlinear hinges in the time domain and several parametric studies are performed.In addition,the comparison of response is made to illustrate the feasibility of the methods.The results show that the extending component mode synthesis method in the present work can be used to establish the governing equation with structural nonlinearities.Based on the modeling method,the Hilbert transform identified method can be extended to multi-degree-of-freedom structures accurately.
