Asymmetric intramolecular Friedel–Crafts reaction catalyzed by a spiropyrrolidine organocatalyst: Enantioselective construction of indolizine and azepine frameworks

The asymmetric intramolecular Friedel–Crafts type Michael reaction of α,β-unsaturated aldehyde with pyrrole, catalyzed by a spiropyrrolidine (SP)-type organocatalyst, has been accomplished, which allows the construction of a series of azepine and indolizine frameworks with high to excellent enantioselectivities (up to 98% ee). Moreover, the substrate scope could be extended to generate a quaternary center in indolizine frameworks (up to 96% ee).     

3-(4-硝基苯基)氨基-1H-吲哚-4(5H)-酮的简便合成及结构表征

以对甲氧基乙二醛一水合物、3-苯氨基-5,5-二甲基-2-环己烯-1-酮和4-硝基苯胺为原料,对甲苯磺酸为催化剂,在乙醇溶剂中,微波辐射下多组分一步法合成标题化合物C29H27N3O4.其结构通过单晶X射线衍射法确定,晶体属三斜晶系,空间群P1,Mr=481.54,晶胞参数:a=0.617 80(5)nm,b=1.291 04(11)nm,c=1.606 78(13)nm,V=1.237 45(18)nm3,Z=2,Dc=1.292 Mg·m-3,μ=0.087mm-1,F(000)=508.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子R=0.059 3,Rw=0.134 8.在晶体结构中新形成的吡咯环为芳构化的共平面结构.     

二氯丙醇环化合成环氧氯丙烷的固体超强碱催化剂研究

对以二氯丙醇环合反应生产环氧氯丙烷过程中所采用的催化剂进行了研究.采用溶胶凝胶法制备了不同种类的固体超强碱催化剂,并考察了这些催化剂的组分配比、焙烧温度等因素对催化剂性能的影响.其中对于组分为BaK/γ-Al2O3的固体超强碱催化剂,在焙烧温度为600℃、Ba∶K∶Al=4∶1∶10,反应温度为125℃时其催化活性最高.采用气相色谱分析法对产品进行表征,测得1,3-DCH转化率和ECH收率可达到80.03%和74.30%.同时采用红外光谱、NH3-TPD谱图、BET比表面和表面碱强度等分析手段对催化剂的性能进行了表征.     

Growth of Solutions of Some Linear Difference Equations with Meromorphic Coefficients

In this paper, we investigate the properties of solutions of some linear difference equations with meromorphic coefficients, and obtain some estimates on growth and value distribution of these meromorphic solutions.     

Effect of the Scanning Step on the Surface Quality of Microdevices in Femtosecond-Laser Micromachining and its Optimization

Direct writing technique is usually used in femtosecond-laser two-photon micromachining. The size of the scanning step has important influence on the surface quality and machining efficiency of microdevices. According to the mechanism of two-photon polymerization combining the distribution function of the light intensity and the free-radical-concentration theory, we establish the mathematical model of coverage of solidification unit and analyze the effect of coverage on the machining quality and efficiency of microdevices. Using the principle of exposure equivalence, we also obtain the analytic expression of the relationship between the surface-quality characteristic parameters of microdevices and the scanning step and carry out the numerical simulation and experiment. The results show that the scanning step has little influence on the surface quality of the line when it is much smaller than the size of the solidification unit. However, when the scanning step is gradually increasing, the smoothness of the line surface is reduced rapidly, and the surface quality becomes worse drastically. For stereo-device processing with different slopes, we propose a kind three-dimensional continuous-variable scanning method and provide the calculation expression of the scanning step. From the experimental example of fabricating a spherical structure, we show that, compared with the fixed-step scanning method, the continuous-variable scanning-step method should be used to improve the surface quality of microdevices.