直链饱和一元醇物理性质递变规律研究

以直链饱和一元醇同系物结构重复单元数值连续变化为模型假定 ,获得了描述直链饱和一元醇同系物物理性质递变规律的数学表达式 :P =(a0 +a1n) / (1+b1n) ,其中a0 ,a1,b1均为常数 ,n为结构重复单元数值 ,P为直链饱和一元醇同系物的物理性质 .通过非线性回归分析 ,得到回归方程 ,结果表明直链饱和一元醇同系物的物理性质与重复单元数值之间满足上述关系式 ,均显示优良的相关性     

有机同系物性质的递变规律研究

以有机同系物结构重复单元数值连续变化为模型,得到同系物行质递变的两个基本规律：P=a+bn和P=c+kln(n+a/n+b),a,b,c,k均为常数,n为结构重复单元数值,P为同系物的物性。一般地,加和型性能遵守直线变化规律,而结构型和凝聚型性能遵守同系对数线性规律。     

正烷基环己烷同系物凝聚型物理性质递变规律

以H—(CH2)n—环己烷同系物结构重复单元数值n连续变化为模型,获得了描述该同系物凝聚型物理性质P递变规律的数学表达式:P=a+bnc,其中a、b、c均为常数,n为结构重复单元数值,P为同系物的凝聚型物理性质.通过非线性回归分析,得到回归方程 结果表明该同系物的凝聚型物理性质与重复单元数值之间显示优良的相关性.     

直链烷烃物理性质递变规律研究

以直链烷烃同系物结构重复单元数值连续变化为模型假定,获得了描述直链烷烃同系物物理性质递变规律的数学表达式: P＝a+bn(1/c),其中a、 b、 c均为常数, n为结构重复单元数值, P为直链烷烃同系物的物理性质。通过非线性回归分析,得到回归方程,结果表明直链烷烃同系物的物理性质与重复单元数值之间满足上述关系式,均显示优良的相关性。     

直链饱和一元胺物理性质递变规律研究

以直链饱和一元胺同系物结构重复单元数值连续变化为模型假定 ,获得了描述直链饱和一元胺同系物物理性质递变规律的数学表达式 :P =a +bnc,其中a、b、c均为常数 ,n为结构重复单元数值 ,P为直链饱和一元胺同系物的物理性质 .通过非线性回归分析 ,得到回归方程 ,结果表明直链饱和一元胺同系物的物理性质与重复单元数值之间满足上述关系式 ,均显示优良的相关性     

一个新的有机同系物电离能拟合公式

本文提出有机同系物电离能拟合公式: NlogIp=a+bn, 其中N为组成同系物分子的原子总数, n为重复单元的重复度, a, b是和能级有关的常数。以NlogIp对n进行线性回归分析, 结果46个同系列150组光电子能谱数据所得相关系数r全部大于0.997, 其中131组达到1.000,优秀率为100%。     

有机同秩物概念及单取代烷烃同秩物生成焓和电离能变化规律

提出了“有机同秩列”、“有机同秩物”、“有机同秩异构体”等概念体系,并以单取代烷烃同秩物Xi-（CH2）/-H（Xi=F、CI、Br、I、NO2、CN、NC、OH、NH2、SH、COOH、CHO）为例,对其气相标准摩尔生成焓（△rHm）、电离能（IP）的结构-性能关系进行了研究,分别对j=2～8的七组同秩物的生成焓及j=2～4的三组同秩物的电离能建立了数学模型：△rHm（j）=a＋b△iHm（1）＋cPEI（R）和IP（j）：a＋bIP（1）＋bPEI（R）,得到了有意义的结果．研究表明,从有机同秩物的角度可以建立一种新的分子结构．性能相关方法,它与有机同系物方法相互独立又互为补充．本文提出的概念体系不仅增加了新的有机化学理论和概念,还为有机物结构-性能变化规律的研究开辟了新视角．     

Synthesis and Structure of {（Tab-Tab）[Ag2（μ-Cl）41.2MeCN}n （Tab = 4-（Trimethylammonio）benzenethiolate）

In the presence of Et4NCl·H2O, reaction of AgCl with TabHPF6 in MeCN afforded the title complex {（Tab-Tab）[Ag2（μ-Cl）4]-2MeCN}n 1. 1 crystallizes in the orthorhombic space group Pbcn with a = 16.782（3）, b = 6.8358（14）, c = 26.194（5） A, V = 3004.9（10） A3, Z = 8,μ = 1.817 mm^-1, Dc = 1.711 g/cm3, T= 223 K, C1lH16AgCl2N2S, Mr= 387.10, F（000） = 1544, S= 1.160, R = 0.0528 and wR = 0.0896 for 2732 observed reflections with I 〉 2σ（I）. 1 contains a 1D linear [Ag2Cl4]n^2n- chain coupled with the [Tab-Tab]2＋ dications. Intermolecular hydrogen bonding interactions between the protons of methyl groups from the Tab-Tab dications and the chlorides result in the formation of a 2D hydrogen-bonded network.     

层状结构杂合物（CnH2n＋1 NH3）2 NiCl4（n ＝4，8，12）的合成与表征

采用低温固相合成法制备了3种有机／无机杂合物（ Cn H2n ＋1 NH3）2 NiCl4（ n ＝4,8,12）,通过元素分析、X 射线粉末衍射、红外光谱和紫外‐可见吸收光谱对杂合物进行了表征。实验结果表明,利用低温固相合成法可成功制备杂合物（Cn H2n ＋1 NH3）2 NiCl4（ n ＝4,8,12）,3种产物均具有明显的层状结构且分别属于单斜晶系、六方晶系和正交晶系。     

直链饱和一元羧酸凝聚型物理性质递变规律

有机同系物的物理性质大致可分加和型、结构型和凝聚型性质三大类。加和型性质是以组成原子的种类和数目为基础的 ,在同一系列中 ,这类性质是碳原子数的线性函数。结构型性质与分子中电子活动有关 ,蒋明谦先生曾对有机同系物各种结构型性质进行研究 ,提出了有机同系物结构型性质的同系线性规律[1 ] ,但该规律对凝聚型性质却无力有效描述。引起凝聚型性质的主要原因是分子间相互作用 ,由于作用机制的复杂性 ,与结构重复单元数值ｎ呈比较复杂的关系。尽管最近有人用指数函数[2 ] 来描述直链饱和一元羧酸结构型和凝聚型性能递变规律 ,这类函数…     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.