4-甲基-4-氮杂-21E-苯亚甲基-5-孕烯-3,20-二酮类化合物的合成

报道了一种以KF/Al_2O_3催化合成4-甲基-4-氮杂-21E-苯亚甲基-5-孕烯-3,20-二酮类化合物的方法。以黄体酮为原料,经NaIO_4/KMnO_4氧化裂解、胺解关环得到重要中间体4-甲基-4-氮杂-5-孕烯-3,20-二酮,后者在KF/Al_2O_3催化下经克莱森缩合得到目标产物。考察了不同的催化剂、反应温度、催化剂用量对目标产物的影响。条件优化的结果为:n(3)∶n(KF/Al_2O_3)=1∶1,回流状态下反应4 h,产率为56%~68%。此方法适用性好,为4-氮杂甾体苯亚甲基衍生物的合成提供了一种方便而有效的方法。     

Synthesis,characterization and heterogeneous catalytic application of a nickel(II) Schiff base complex immobilized on MWCNTs for the Hantzsch four-component condensation

A nickel(II) Schiff base complex immobilized on multi-wall carbon nanotubes (MWCNTs) surface as a highly efficient heterogeneous catalyst was synthesized and characterized by IR, X-ray diffraction patterns, scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, elemental analysis, and thermal gravimetric analysis. Then a facile and environmentally benign procedure was developed for synthesis of polyhydroquinoline derivatives via Hantzsch one-pot condensation reaction of aromatic aldehydes, 1,3-diones, ethyl acetoacetate, and ammonium acetate in the presence of above synthesized catalyst under solvent-free conditions. This protocol has the advantages of stability, easy availability, recyclability and eco-friendly nature of catalyst, simple experimental and work-up procedure, and also high to excellent yields. Considering the solvent-free condition and also temperature, time, and yield of the model reaction, the nanocatalyst reported here is among the best catalysts reported so far for synthesis of polyhydroquinolines.     

假性紫罗酮的合成

假紫罗酮,6,10-二甲基-3,5,9-十一碳三烯2-酮,是合成重要香料紫罗酮、维生素A、E的重要中间体。工业上多用改进的Tjemann法,即丙酮与柠檬醛缩合的方法,及用芳樟醇的中间体脱氢芳樟醇制备。我国柠檬醛的来源——野生植物山苍子的资源丰富,所以     

大环二萜类化合物的研究(Ⅳ)——Isosarcophytol—A前体化合物的合成

Isosarcophytol-A(1)是1982年首次从澳大利亚软珊瑚(Nephthea brassica)中分离鉴定的西松烷型(Cembrane)大环二萜类化合物,其结构为6,10,14-三甲基-3-异丙基-3E,5E,9E,13E-环十四碳四烯-1-醇,是Sarcophytol—A(2)的异构体,但有关1的生物活性试验和全合成研究尚未见报道.我们在前文报道了以低价钛诱导的分子内二羰基偶联为环化方法,完成了天然大环二萜类化合物Cembrene—C的全合成和Sarcophytol—A(2)苄醚衍生物(3)的合成.本文报道以天然法呢醇4为起始原料,经区域选择性氧化、羟醛缩合等六步反应,合成了1的前体化合物11.合成路线如下:     

有机锡聚醚的合成及性质的研究

利用界面缩聚技术,将二烷基二氯化锡、二(β-烷氧羰乙基)二氯化锡与有机二元醇、酚、硫醇反应,制成了一系列新的有机锡大分子化合物.对这些新化合物进行了分子量、红外光谱、TG/DTG测试.对有机锡大分子化合物阻止聚氯乙烯(PVC)热分解性能进行了测定.结果表明,新合成的有机锡聚醚化合物可作为PVC热稳定剂使用.     

Derivation of mean-field equations for stochastic particle systems

We study stochastic particle systems on a complete graph and derive effective mean-field rate equations in the limit of diverging system size, which are also known from cluster aggregation models. We establish the propagation of chaos under generic growth conditions on particle jump rates, and the limit provides a master equation for the single site dynamics of the particle system, which is a non-linear birth death chain. Conservation of mass in the particle system leads to conservation of the first moment for the limit dynamics, and to non-uniqueness of stationary distributions. Our findings are consistent with recent results on exchange driven growth, and provide a connection between the well studied phenomena of gelation and condensation.     

Form of the Spectra of Nucleus Dimensions in First-Order Phase Transitions

We study a generalization of the analytic theory of first-order phase transitions to the cases of arbitrary droplet growth, of nonisothermal processes, and of heterogeneous centers in the system. We show that in all these cases, the spectra of droplet dimensions are similar. The same forms of the spectra are also obtained for the stationary condensation process in a spatially inhomogeneous system.     

Pore-Level Modeling of Gas and Condensate Flow in Two- and Three-Dimensional Pore Networks: Pore Size Distribution Effects on the Relative Permeability of Gas and Condensate

We present a mechanistic model of retrograde condensation processes in two- and three-dimensional capillary tube networks under gravitational forces. Condensate filling-emptying cycles in pore segments and gas connection–isolation cycles are included. With the pore-level distribution of gas and condensate in hand, we determine their corresponding relative permeabilities. Details of pore space and displacement are subsumed in pore conductances. Solving for the pressure field in each phase, we find a single effective conductance for each phase as a function of condensate saturation. Along with the effective conductance for the saturated network, the relative permeability for each phase is calculated. Our model porous media are two- and three-dimensional regular networks of pore segments with distributed size and square cross-section. With a Monte Carlo sampling we find the optimum network size to avoid size effects and then we investigate the effect of network dimensionality and pore size distribution on the relative permeabilities of gas and condensate.     

Nonideal Bose Gases: Correlation Inequalities and Bose Condensation

We consider two simple model systems describing effective repulsion in a nonideal Bose gas. The interaction Hamiltonians in these systems can be analytically represented as functions of the occupation number operators for modes with nonzero momenta (p0). One of these models contains an interaction term corresponding to repulsion of bosons with the mode p=0 and ensuring the thermodynamic superstability of the system; the other model does not contain such a term. We use the Bogoliubov–Dirac–Ginibre approximation and the method of correlation inequalities to prove that a Bose condensate can exist in these model systems. Because of the character of interaction, the condensate can be formed in the superstable case for any values of the spatial dimensions, temperature, and positive chemical potentials.