用均根拓扑指数与路径数预测链烷烃的沸点和热力学性质

以距离矩阵为基础，建构调和均根拓扑指数（K），以表征链烷烃分子的大小 和分支情况，85种链烷烃的沸点(T_b)、标准生成焓(Δ_rH_m~θ)、标准熵(S_m~θ )、标准生成自由能(Δ_fG_m~θ)与K及路径数(P_2, P_3)的回归方程为: ln(793- T_b) = 6.48346-0.10092K + 0.00131P_2-0.01110P_3, R = 0.9996; -Δ_fH_m~θ = 62.664 + 25.331 K + 6.597 P_2 - 0.678 P_3, R = 0.9984; S_m~θ = 170. 691 + 67.425 K - 4.712P_2 + 5.251 P_3, R = 0.9989; Δ_fG_m~θ = -45.677 + 10.060 K + 0.555 P_2 + 2.342P_3, R = 0.9935。它们的计算值与相应实验值 都非常吻合。结果表明，K对链烷烃具有良好的结构选择性和性质相关性。     

烷烃同系物气相色谱保留指数的分子拓扑研究

定义了分子中原子的平衡电负性,并用原子的平衡电负性对分子图进行着色,在距离矩阵的基础上结合分子中各原子的支化度构建了一种新的拓扑指数N1,N2和N3。该拓扑指数对分子结构实现惟一性表征,具有优良的结构选择性。将拓扑指数N1,N2和N3与烷烃在固定相角鲨烷(柱温50　℃)及SE-30(柱温80　℃)上的气相色谱保留指数进行多元线性回归,结果表明烷烃的气相色谱保留指数可分别定量描述为I(Squalane)=23.97842N1-3.86562N2+0.787379N3+42.33061,I(SE-30)=23.83937N1-3.5687N2+0.939876N3+22.11952。用上述回归方程对烷烃的气相色谱保留指数进行预测,结果表明预测值与实验值的平均相对误差均为1.31%,预测结果误差在实验误差范围内。     

高氮含能配合物M(ATZ)(bpy)m·nH2O液相生成反应的热动力学

合成了6种固态高氮含能配合物M(ATZ)(bpy)m·nH2O((1)M=Mn,m=2,n=3;(2)M=Co,m=2,n=7;(3)M=Ni,m=2,n=0;(4)M=Cu,m:1,n=0;(5)M=Pb,m=1,/7,=3;(6)M=Zn,m=1,n=1;ATZ=5,5'-偶氮四唑,bpy=2,2'-联吡啶).对它们的结构和性能进行了表征.用RD496-CK2000微热量计测定了298.15 K下各配合物的液相生成反应焓变分别为:△rHc(1)=241.245 4-0.060 kJ/mol,△rHθ≠(2)=-256.875±0.050 kJ/tool,△rHθm.(3)=-265.172±0.038 kJ/mol,△rHθm:(4)=-236.538±0.038 kJ/tool,△rθm(5)=-249.698±0.038 kJ/mol,△rθm(6)=-185.072±0.048 kJ/tool.通过试验测定得到的所有液相反应的△rθm均为负值,有利于目标物生成;并改变反应温度,研究了它们的液相生成反应的热动力学.改变温度研究了液相生成反应的热动力学,利用反应热化学数据和动力学方程结合热动力学实验数据计算了活化焓(△Hθ≠)、活化熵(△Sθ≠)、活化自由能(△Gθ≠)、表观反应速率常数(k)、表观活化能(E)、指前常数(A)和反应级数(N).     

1273K下LaCrO_3的标准生成自由能测定

用固体电解质电动势法测定了复合氧化物LaCrO_(3(s))在1273K下的标准生成自由能。1/2La_2O_(3(s))+1/2Cr_2O_(3(s))=LaCrO_(3(s))反应的标准自由能变化为:ΔG_(1273K)~0=-30.1±1.5kJ/mol。用氧位递增原理和经验规则对实验测得的LaCrO_(3(s))标准生成自由能进行了检验。经验公式为:ΔG_(f(LaMO_3)1273K)~0=-3177+83.3Z kJ/mol,其中M=Cr、Mn、Co、Ni;Z为M的原子序数。     

分子诱导效应指数与链烷烃的沸点

利用基团的诱导效应指数，首次提出了分子的诱导效应指数的概念，并定义了 链烷烃的有效碳链长度NC＝（MIs,N/MIb,N)·N，式中MIs,N,MIb,N分别为直链和支 链异构体的分子诱导效应指数。研究结果表明，链烷烃的沸点Tb(℃）与NC关系是 ：1n(806.5-Tb)=6.9824-0.11431NC^2/3     

用原子特征自相关拓扑指数预测链烷烃的热力学性质

原子特征值(Si)被定义为:.由Si（ ）建构原子特征自相关拓扑指数(F)及原子特征连接性指数(Y)的公式为:F＝∑(Si.Sj)0.5、Y＝∑(Si.Sj)-0.5.它们与85种链烷烃热力学性质(P) 的二元线性回归方程为:P＝a+bF+cY(或P3).P为标准生成焓、标准熵、标准生成自由能的二元相关指数依次为0.9953、0.9992、0.9941,优于文献方法.     

用原子特性自相关拓扑指数预测链烷烃的热力学性质

原子特征值 ( Si)被定义为 :Si=ni- 1ki mi( ∑Eij+ hi Ei)。由 Si建构原子特征自相关拓扑指数 ( F )及原子特征连接性指数 ( Y)的公式为 :F =∑( Si· Sj) 0 .5、Y=∑ ( Si·Sj) - 0 .5。它们与 85种链烷烃热力学性质 ( P)的二元线性回归方程为 :P =a + b F +c Y(或 P3) 。 P为标准生成焓、标准熵、标准生成自由能的二元相关指数依次为 0 .9953、0 .9992、0 .9941 ,优于文献方法     

实验与理论研究G-四链体中鸟嘌呤自由基阳离子脱质子反应

G-四链体传输空穴的特殊性质使其有望应用于发展分子电子器件.由于鸟嘌呤自由基阳离子（G^·+）脱质子反应会中断空穴传递,影响传递效率,我们对G-四链体AG₃（T₂AG₃）₃中G^·+脱质子过程展开了理论与实验的研究.根据瞬态紫外可见吸收光谱,确定了脱质子产物是G（N（2）-H）^·;通过测量不同温度下G^·+脱N（2）-H质子的速率常数,得到脱质子活化能为20.0±1.0 kJ/mol.进而,采用显性水和连续溶剂化模型相结合的方法模拟G-四链体中G^·+脱质子环境,在M062X/6-31G（d）水平上得到了脱质子势垒（26.4 kJ/mol）.结合实验值,理论计算的势能面描述了G-四链体中G^·+脱N2-H的过程.这些结果为G-四链体在电子器件方面的应用提供了重要依据和指导.     

异戊烯与甲醇成醚反应机理的量子化学研究

对2-甲基-1-丁烯、2-甲基-2-丁烯与甲醇反应生成甲基叔戊基醚的反应历程进行了量子化学研究, 结果表明, 反应过程包括两个基元步骤: 2-甲基-1-丁烯和2-甲基-2-丁烯与氢离子作用生成碳正离子, 活化能分别为E1=2.26 kJ/mol, E2=7.72 kJ/mol; 甲醇与叔碳正离子反应成醚, 活化能为E3=1.29 kJ/mol, 碳正离子的生成是反应的速控步骤. 2-甲基-1-丁烯与2-甲基-2-丁烯相互转化的异构化活化能分别为E'1=4.40 kJ/mol, E'2=63.11 kJ/mol, 高于成醚的活化能, 反应体系不发生烯烃相互转化的异构化反应.     

高氮含能配合物M（ATZ）（bpy）m·nH2O液相生成反应的热动力学

合成了6种固态高氮含能配合物M（ATZ）（bpy）m·nH2O（（1）M=Mn,m=2,n=3;（2）M=Co,m=2,n=7;（3）M=Ni,m=2,n=0;（4）M=Cu,m=1,n=0;（5）M=Pb,m=1,n=3;（6）M=Zn,m=1,n=1;ATZ=5,5′-偶氮四唑,bpy=2,2′-联吡啶）。对它们的结构和性能进行了表征。用RD496-CK2000微热量计测定了298.15 K下各配合物的液相生成反应焓变分别为：ΔrHm^θ（1）=241.245±0.060 kJ/mol,ΔrHm^θ（2）=-256.875±0.050 kJ/mol,ΔrHm^θ（3）=-265.172±0.038 kJ/mol,ΔrHm^θ（4）=-236.538±0.038 kJ/mol,ΔrH^θm（5）=-249.698±0.038 kJ/mol,ΔrHm^θ（6）=-185.072±0.048 kJ/mol。通过试验测定得到的所有液相反应的ΔrHm^θ均为负值,有利于目标物生成;并改变反应温度,研究了它们的液相生成反应的热动力学。改变温度研究了液相生成反应的热动力学,利用反应热化学数据和动力学方程结合热动力学实验数据计算了活化焓（ΔH≠^θ）、活化熵（ΔS≠^θ）、活化自由能（ΔG≠^θ）、表观反应速率常数（k）、表观活化能（E）、指前常数（A）和反应级数（n）。     

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.     

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.     

关于"对‘燃料电池物理及化学性能的有限时间热力学分析方法'的讨论”答复

把有限时间热力学理论用于化学过程的研究,将会得到一系列新的结论,开展这方面的研究是很有意义的.文献[1]以燃料电池为例,在同时考虑化学反应及传热不可逆性的情况下,研究了燃料电池的性能界限,文献[2]指出了文献[1]计算化学反应及传热不可逆性而引起系统与有关环境的总熵产生率的错误以及由此而导致的结论所存在的问题,并进行了富有启发性的分析与讨论.但文献[2]对于系统与有关环境的总熵产生率的计算也是不正确的,由此得到的其它结论自然不能成立.本文将就此情况下系统与有关环境的总熵产生率的计算再次进行讨论,并给出电池功率和效率的有限时间热力学性能界限.     

Regiospecific synthesis of quercetin O-β-d-glucosylated and O-β-d-glucuronidated isomers

Quercetin, the polyphenolic compound, which has the highest daily intake, is well known for its protective effects against aging diseases and has received a lot of attention for this reason. Both quercetin 3-O-β-d-glucuronide and quercetin 3′-O-β-d-glucuronide are human metabolites, which, together with their regioisomers, are required for biological as well as physical chemistry studies. We present here a novel synthetic route based on the sequential and selective protections of the hydroxyl functions of quercetin allowing selective glycosylation, followed by TEMPO-mediated oxidation to the glucuronide. This methodology enabled us to synthesize the five O-β-d-glucosides and four O-β-d-glucuronides of quercetin, including the major human metabolite, quercetin 3-O-β-d-glucuronide.     

Cl+F2→ClF+F和F+ClF′→ClF+F′反应机理的密度泛函理论研究

用密度泛函理论(DFT)B3LYP方法, 在6-311G基组下,计算研究了反应Cl+F2→ClF+F和对称反应F+ClF′→ClF+F′的机理。求得前者的过渡态为三角形,活化能为15.57 kJ*mol-1;后者的过渡态为线形和三角形,活化能分别为11.52和196.25 kJ*mol-1。结果均经过振动分析和IRC计算验证。     

丙三醇浓溶液玻璃化转变与结构松弛参数DSC分析

In order to examine the effects of water contents and heating/cooling rates on the glass transition and the structure relaxation parameters of glycerol/water mixtures, five aqueous solutions (60%, 70%, 80%, 90% and 100%) were investigated using the differential scanning calorimetry. Four scanning rates (10, 15, 20, 25 K/min) were used to obtain the glass transition parameters. The fitting results of plasticization constants indicated that Gordon-Taylor relationship could not be used effectively without considering scanning rates and that point on calorimetric step was chosen as the glass transition temperature. The specific heat changes during glass transition processes were relative not only to water content but also to heating rates. With the increasing of water contents in glycerol aqueous solutions, the structure relaxation activation energies and dynamic fragilities were decreased. Since the thermodynamic fragilities were increased with the increasing of water content, so the dynamic fragility and thermodynamic fragility were changed inversely if the water contents were changed in glycerol/water mixtures.     

Deuterodehalogenation—a mild method for synthesising deuterated heterocycles

We report a mild and efficient method for introducing deuterium into a range of heterocycles by reacting readily available halide analogues in a deuterodehalogenation reaction using D₈-IPA or Et₃SiD under palladium-catalysed conditions.     

The conversion of 2-cyano cyanothioformanilides into 3-aminoindole-2-carbonitriles using triphenylphosphine

2-Cyano cyanothioformanilide 3a reacts with triphenylphosphine in the presence of water to give 2-(cyanomethyleneamino)benzonitrile 4a, 2-(cyanomethylamino)benzonitrile 5, 3-aminoindole-2-carbonitrile 2a and (2-cyanoindol-3-yl)iminotriphenylphosphorane 6a. In the presence of p-toluenesulfonic acid in MeOH the reaction between 2-cyano cyanothioformanilide 3a and triphenylphosphine (2 equiv) gives 3-aminoindole-2-carbonitrile 2a in 90% yield. Under the same conditions 2-(cyanomethyleneamino)benzonitrile 4a gives anthranilonitrile 8a, 3-aminoindole-2-carbonitrile 2a and N-(2-cyanophenyl)formamide 9. In addition, substituted 2-cyano cyanothioformanilides 3b-f react with triphenylphosphine and p-toluenesulfonic acid in MeOH to give 3-aminoindole-2-carbonitriles 2b-f in 63-75% yields. Under analogous conditions 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 2g gives only 4,5-dimethoxyanthranilonitrile 8g and 4,6,7-trimethoxyquinazoline-2-carbonitrile 14g, but in refluxing dry PhMe in the absence of p-toluenesulfonic acid 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 3g, (2-cyano-5,6-dimethoxyindol-3-yl)iminotriphenylphosphorane 6g and 2-(cyanomethyleneamino)-4,5-dimethoxybenzonitrile 4g are obtained. The structure of 2-(cyanomethyleneamino)-4,5-dimethoxybenzonitrile 4g is supported unambiguously via independent synthesis and comparison to the isomeric 6,7-dimethoxyquinazoline-2-carbonitrile 15. All new compounds are fully characterised and a tentative mechanism for the transformation of 2-cyano cyanothioformanilides to indoles is proposed.