The fullerene complex, η 2 C 60 [Ru(NO)(PPh 3)] 2, has been prepared by the reaction of C 60 with Ru(NO) 2(PPh 3) 2 under a nitrogen atmosphere and refluxing. The new complex was characterized by means of elemental a...The fullerene complex, η 2 C 60 [Ru(NO)(PPh 3)] 2, has been prepared by the reaction of C 60 with Ru(NO) 2(PPh 3) 2 under a nitrogen atmosphere and refluxing. The new complex was characterized by means of elemental analysis, IR, XPS, electronic spectra and 31 P NMR. The results show that the complex of η 2 form can be formed by C 60 bonding to Ru(NO) 2(PPh 3) 2 in the σ π way and there is hyperconjugation effect in the molecule. So electrons will flow easier and photoelectric effect for this new compound is expected. In addition, the structure of the complex has been supposed. The ruthenium is 4 coordinate in the complex, bonding to two carbon atoms, to one PPh 3 and to one NO.展开更多
The catalytic hydrogenation of D-glucose over a 3 wt% Ru/C catalyst was studied varying the operating conditions in mild conditions range to optimize the obtention of D-sorbitol. The stirring speed, temperature, press...The catalytic hydrogenation of D-glucose over a 3 wt% Ru/C catalyst was studied varying the operating conditions in mild conditions range to optimize the obtention of D-sorbitol. The stirring speed, temperature, pressure, and initial glucose concentration were varied between 250 - 700 rpm, 343 - 383 K, 0.5 - 2 MPa, and 0.033 - 0.133 M, respectively. To verify the absence of mass transport limitations, the diffusion of reagents in the gas-liquid interface, the liquid-solid interface, and the internal diffusion in the particles were evaluated. Under the operating conditions studied, the reaction rate showed an order with respect to H<sub>2</sub> of 0.586 and with respect to glucose of 0.406. The kinetic data were adjusted using 3 general models and 19 different sub-models based on Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetics. Model 3a was the best one interpreting the aqueous phase hydrogenation of glucose (both reagents competitively adsorbed on the catalyst). The H<sub>2</sub> adsorption is dissociative and the rate-limiting step is the surface chemical reaction.展开更多
对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2...对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。展开更多
The rods that were shaped from nanocrystalline WC- 10.21 Co-0.42 VC/ Cr3 C2 （ wt% ） composite powders by using powder extrusion molding （PEM） were investigated. The nanocrystalline WC- 10.21 Co- 0. 42 VC/ Cr3 C2 ...The rods that were shaped from nanocrystalline WC- 10.21 Co-0.42 VC/ Cr3 C2 （ wt% ） composite powders by using powder extrusion molding （PEM） were investigated. The nanocrystalline WC- 10.21 Co- 0. 42 VC/ Cr3 C2 （ wt% ） composite powders were prepared by the spray thermal decomposition-continuous reduction and carburization technology. In order to improve the properties of rods shaped by using powder extrusion molding, the cold isostatic pressing （CIP） technology was used before or after debinding. Specimens were siutered by vacuum siutering and hot isostatic pressing （HIP）. The density, Rockwell A hardness, magnetic coercivity , and magnetic saturation induction of siutered specimen were measured. The microstructure of the green bodies and the siutered specimens was studied by scanning electron microscopy （SEM）. Results show that the rod formed by using powder extrusion molding after debinding and followed by cold isostatic pressing can be siutered to 99.5% density of composite cemented carbide rods with an average grain size of about 200- 300 nm, magnetic coercivity of 30.4 KA / m, Rockwell A hardness of 92.6 and magnetic saturation induction of 85% . Superfine WC- 10 Co cemented carbide rods with excellent properties were obtained.展开更多
文摘The fullerene complex, η 2 C 60 [Ru(NO)(PPh 3)] 2, has been prepared by the reaction of C 60 with Ru(NO) 2(PPh 3) 2 under a nitrogen atmosphere and refluxing. The new complex was characterized by means of elemental analysis, IR, XPS, electronic spectra and 31 P NMR. The results show that the complex of η 2 form can be formed by C 60 bonding to Ru(NO) 2(PPh 3) 2 in the σ π way and there is hyperconjugation effect in the molecule. So electrons will flow easier and photoelectric effect for this new compound is expected. In addition, the structure of the complex has been supposed. The ruthenium is 4 coordinate in the complex, bonding to two carbon atoms, to one PPh 3 and to one NO.
文摘The catalytic hydrogenation of D-glucose over a 3 wt% Ru/C catalyst was studied varying the operating conditions in mild conditions range to optimize the obtention of D-sorbitol. The stirring speed, temperature, pressure, and initial glucose concentration were varied between 250 - 700 rpm, 343 - 383 K, 0.5 - 2 MPa, and 0.033 - 0.133 M, respectively. To verify the absence of mass transport limitations, the diffusion of reagents in the gas-liquid interface, the liquid-solid interface, and the internal diffusion in the particles were evaluated. Under the operating conditions studied, the reaction rate showed an order with respect to H<sub>2</sub> of 0.586 and with respect to glucose of 0.406. The kinetic data were adjusted using 3 general models and 19 different sub-models based on Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetics. Model 3a was the best one interpreting the aqueous phase hydrogenation of glucose (both reagents competitively adsorbed on the catalyst). The H<sub>2</sub> adsorption is dissociative and the rate-limiting step is the surface chemical reaction.
文摘对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。
基金Funded by Open Foundation of State Key Laboratory of AdvancedTechnologyfor Materials Synthesis and Processing, Wuhan Universi-ty of Technology, the Post PhD Science Foundation of China(2003034504) andthe Foundation of Wuhan University of Technol-ogy(2003XJJ202)
文摘The rods that were shaped from nanocrystalline WC- 10.21 Co-0.42 VC/ Cr3 C2 （ wt% ） composite powders by using powder extrusion molding （PEM） were investigated. The nanocrystalline WC- 10.21 Co- 0. 42 VC/ Cr3 C2 （ wt% ） composite powders were prepared by the spray thermal decomposition-continuous reduction and carburization technology. In order to improve the properties of rods shaped by using powder extrusion molding, the cold isostatic pressing （CIP） technology was used before or after debinding. Specimens were siutered by vacuum siutering and hot isostatic pressing （HIP）. The density, Rockwell A hardness, magnetic coercivity , and magnetic saturation induction of siutered specimen were measured. The microstructure of the green bodies and the siutered specimens was studied by scanning electron microscopy （SEM）. Results show that the rod formed by using powder extrusion molding after debinding and followed by cold isostatic pressing can be siutered to 99.5% density of composite cemented carbide rods with an average grain size of about 200- 300 nm, magnetic coercivity of 30.4 KA / m, Rockwell A hardness of 92.6 and magnetic saturation induction of 85% . Superfine WC- 10 Co cemented carbide rods with excellent properties were obtained.
