基于数据挖掘方法的开放骨架磷酸铝定向合成参数分析

开放骨架磷酸铝化合物是多孔晶体材料的一个重要家族。然而,这类材料的合成受到反应原料、凝胶组成、溶剂、模板剂、结晶温度和结晶时间等多个因素的影响。本文以吉林大学"无机制备与合成化学国家重点实验室"建立的开放骨架磷酸铝合成反应数据库为研究对象,采用最大权重最小冗余特征选择算法(Maximum weight and minimum redundancy,MWMR),在充分考虑合成参数自身的重要程度和合成参数之间的相关关系的前提下,分析了溶剂、模板剂等合成参数对于合成含有(8,6)元环结构开放骨架磷酸铝的影响。通过大量实验验证了该方法在开放骨架磷酸铝合成参数分析中的有效性,分析了合成参数对产物生成的影响。实验结果表明模板剂的几何参数、模板剂中C原子和N原子的个数比,溶剂的偶极距等参数可能对于该类结构的合成具有较为重要的影响。     

基于数据挖掘方法的开放骨架磷酸铝定向合成参数分析

开放骨架磷酸铝化合物是多孔晶体材料的一个重要家族。然而,这类材料的合成受到反应原料、凝胶组成、溶剂、模板剂、结晶温度和结晶时间等多个因素的影响。本文以吉林大学“无机制备与合成化学国家重点实验室”建立的开放骨架磷酸铝合成反应数据库为研究对象,采用最大权重最小冗余特征选择算法(Maximum weight and minimum redundancy,MWMR),在充分考虑合成参数自身的重要程度和合成参数之间的相关关系的前提下,分析了溶剂、模板剂等合成参数对于合成含有(8,6)元环结构开放骨架磷酸铝的影响。通过大量实验验证了该方法在开放骨架磷酸铝合成参数分析中的有效性,分析了合成参数对产物生成的影响。实验结果表明模板剂的几何参数、模板剂中C原子和N原子的个数比,溶剂的偶极距等参数可能对于该类结构的合成具有较为重要的影响。     

数据挖掘辅助定向合成(Ⅰ)具有特定孔道结构的微孔磷酸铝

采用决策树方法对微孔磷酸铝的合成反应数据库进行了数据挖掘研究, 结果表明, 有机胺模板剂的属性对特定孔道的生成起着至关重要的作用. 进一步分析得到合成十二元环AlPO4-5微孔磷酸铝的约束条件, 并从理论上预测出用于合成十二元环AlPO4-5微孔磷酸铝的一系列新的有机胺模板剂. 部分理论分析结果得到了分子力学计算的有力支持, 并被合成实验所验证.     

数据挖掘辅助定向合成（I）——具有特定孔道结构的微孔磷酸铝

采用决策树方法对微孔磷酸铝的合成反应数据库进行了数据挖掘研究．结果表明，有机胺模板剂的属性对特定孔道的生成起着至关重要的作用．进一步分析得到合成十二元环AlPO4-5微孔磷酸铝的约束条件，并从理论上预测出用于合成十二元环AlPO4-5微孔磷酸铝的一系列新的有机胺模板剂．部分理论分析结果得到了分子力学计算的有力支持，并被合成实验所验证．     

用分子动力学模拟方法研究层孔与微孔磷酸铝化合 物中有机胺的模板作用: 指 导定向合成的有效途径

用分子动力学方法,研究了有机胺模板剂对二维层孔与三维微孔磷酸铝化合物的模板作用。依据主-客体间的非键相互作用能量,可以有效地预测出适于某一特定结构的有机胺模板剂。通过选择理论预测的有机胺分子作模板剂,在溶剂热体系中可以定向地合成出具有特定结构的化合物。这一工作对于微孔功能体系的分子工程学研究具有一定的指导意义。     

用分子动力学模拟方法研究层孔与微孔磷酸铝化合 物中有机胺的模板作用: 指 导定向合成的有效途径

用分子动力学方法,研究了有机胺模板剂对二维层孔与三维微孔磷酸铝化合物的模板作用。依据主-客体间的非键相互作用能量,可以有效地预测出适于某一特定结构的有机胺模板剂。通过选择理论预测的有机胺分子作模板剂,在溶剂热体系中可以定向地合成出具有特定结构的化合物。这一工作对于微孔功能体系的分子工程学研究具有一定的指导意义。     

新型层状氟化磷酸铝[C4H12N2][Al2(PO4)2(H2O)2F2]的水热合成与表征

自从1982年Wilson等发现一类新型微孔材料磷酸铝分子筛(AlPO4-n)以来,大量具有新颖结构的磷酸铝化合物被合成出来,它们在催化、离子交换、吸附和主-客体组装等方面均具有潜在的应用前景,这类化合物大多是在水热或溶剂热体系中和有机模板剂存在条件下合成的,1978年,Flanigen等首先在反应体系中加入氟离子作矿化剂合成了硅晶体,后来,氟离子方法在硅铝体系和金属磷酸盐体系中也得到了广泛的应用,氟离子在反应过程中起到矿化剂或结构导向剂的作用,     

开放骨架磷酸铝合成反应数据库的建立与应用（I）

本文介绍了开放骨架磷酸铝合成反应数据库的建立、收录的数据资料信息和数据库的检索查询方法,并对该数据库就骨架元素组成、反应产物的结构维数、孔道环数、合成所用的有机模板剂等方面做了统计分析．磷酸铝合成反应数据库的建立对于微孔功能体系的分子工程学研究提供了重要的基础数据．     

模板固相合成磷酸铝及其表征

Ｔ－磷酸铝的合成用水热方法,需９５０℃,２０天才能得到［１］。研究结果表明用固相方法,１５０℃,２小时合成了Ｔ－磷酸铝,同样条件下有模板存在可以得到磷酸铝微晶和Ｔ－磷酸铝,用ＸＲＤ、ＩＲ、ＩＣＰ和化学分析方法对产物进行了表征。 磷酸铝是一类具有广而重要应用的材料,过去十多年里,应用模板在胶态介质中水热方法合成了具有微孔、小孔、中孔的一系列磷酸铝类材料。由于其具有多种结构和组成,对热和水热的稳定性,使得它们在吸附分离、催化剂及催化剂载体、土壤科学、污水处理、医药上调节胃酸等中起着重要作用。特别是在…     

基于特征选择的决策树方法在磷酸铝AlPO4-5定向合成中的应用

分子筛类开放骨架材料的合成与结构关系研究对实现这类材料的定向合成起着至关重要的作用. 本文在建立开放骨架磷酸铝合成反应数据库的基础上, 提出了利用基于特征选择的决策树(C5.0)方法, 考察了不同反应条件(即各反应特征参数)对磷酸铝分子筛AlPO4-5生成的影响. 基于决策树模型, 利用8个反应特征参数,可以有效预测磷酸铝分子筛AlPO4-5的生成, 准确率达到88.18%, 接收者操作特性(ROC)曲线下面积(AUC)达到90%. 研究结果表明, 在众多的反应特征参数中, 有机模板剂的几何尺寸参数, 特别是模板剂的次长距离, 是影响AlPO4-5分子筛合成的重要因素.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.