新型有机硒化合物的合成及其离子识别研究

设计合成了四个含有氢蒽基团的新型有机硒化合物1,8-二-(2-苄硒基)丙氧基-9,10-二氢蒽(L_1)、1,8-氧双(亚乙硒基丙氧基)-9,10-二氢蒽(L_2)、1,8-二-(2-苄硒基)乙氧基-9,10-二氢蒽(L_3)、1,8-氧双(亚乙硒基亚乙氧基)-9,10-二氢蒽(L_4),利用~1H NMR、~(13)C NMR对化合物进行了结构表征,采用荧光光谱法测定了主体对客体阳离子的识别性能。研究结果发现只有化合物L_1对Ag~+具有选择识别能力,且对Ag~+表现出"off-on"开关性能。化合物L_2与Ag~+和K~+络合后荧光略有增强。     

Reaction of 2,3-Dimethylmercaptopropionic Acid with Methylene Blue as an Indicator Reaction for the Kinetic Determination of Selenium

A new indicator reaction between 2,3-dimethylmercaptopropionic acid and Methyl Blue was proposed for the kinetic determination of selenium. The optimal reaction conditions were found. A linear relationship was observed between the induction period and the Se(IV) concentration in the range between 0.9 and 9.6 ng/mL Se. Masking with EDTA and solvent extraction with diethyldithiophosphoric acid can be used for the separation of interfering elements forming complexes with the reagent.     

Palladium-Catalyzed Organic Reactions Involving Hypervalent Iodine Reagents

The chemistry of polyvalent iodine compounds has piqued the interest of researchers due to their role as important and flexible reagents in synthetic organic chemistry, resulting in a broad variety of useful organic molecules. These chemicals have potential uses in various functionalization procedures due to their non-toxic and environmentally friendly properties. As they are also strong electrophiles and potent oxidizing agents, the use of hypervalent iodine reagents in palladium-catalyzed transformations has received a lot of attention in recent years. Extensive research has been conducted on the subject of C—H bond functionalization by Pd catalysis with hypervalent iodine reagents as oxidants. Furthermore, the iodine(III) reagent is now often used as an arylating agent in Pd-catalyzed C—H arylation or Heck-type cross-coupling processes. In this article, the recent advances in palladium-catalyzed oxidative cross-coupling reactions employing hypervalent iodine reagents are reviewed in detail.     

Electrode Reactions Involving Arsenic and Its Inorganic Compounds

The available information on the electrochemical properties of arsenic and its inorganic compounds is generalized. Processes of practical value are considered. These include the formation of free arsenic from solutions as a solid phase in the form of powder or galvanic coatings; the synthesis of arsine, arsenic acid, and arsenates; and use of electrochemical techniques for the waste water purification.     

有机固体化合物无溶剂反应

介绍近年来化学家发现的有机固体化合物无溶剂反应的种类及其特点,列举几类无溶剂有机合成反应。     

钴—H2O2—水杨基荧光酮反应体系的新催化动力学分析方法研究

在碱性介质中，痕量钴（Ⅱ）能显著催化Ｈ２Ｏ２氧化水杨基荧光酮的指示反应，本文据此建立了测定痕量钴的新催化动力学分析法，方法线性范围为０．１～２．８μｇ／Ｌ，检测限为０．０２μｇ／Ｌ。测得反应表现活化能为５９．０３ｋＪ／ｍｏｌ。测定了人发，茶叶，土壤和水等样品中钴的含量，结果满意。     

Radiation Chemical Studies of Protein Reactions: Effect of Sulfur-Containing Compounds on Optical Rotation

Thiourea, thioglycol, and β, β′-thiodiglycolic acid were found to protect against changes in the internal relationships of the atoms in the protein molecule from radiation damage. The optical rotation behavior closely resembles that of amino acid which shows a similar dependence on concentration.     

Constructing Homodesmic Reactions for Calculating the Enthalpies of Formation of Organic Compounds

The mathematics and software of the homodesmic approach to calculating enthalpies of formation Δ_fH° of organic compounds are described. The program generates a set of independent homodesmic reactions for a studied compound, increasing the reliability of theoretical determinations of the standard enthalpy of formation. The basic steps of program construction, using the algorithm to determine the basis of homodesmic reactions for organic compounds, and calculations for the enthalpies of formation for a random test set comprising 53 CHNO-containing organic compounds of different classes are described. It is shown that the homodesmic approach provides highly reliable theoretical values of Δ_fH° virtually regardless of the quantumchemical approach that is used. The average absolute error of MAD calculations for Δ_fH° of a test set is 2.2 kJ/mol for the simple B3LYP/6-31G(d) approach and 2.1 kJ/mol for the moderately complicated M06-2X/cc-pVTZ approach, while using the complicated method of G3 calculations reduces the MAD value to 1.7 kJ/mol.     

Bimolecular Reactions of Radical Generation Involving Nitrogen-Containing Compounds with Multiple Bonds

Retrodisproportionation reactions R"C=NR" + HY R" NHR" + , RCN + HY R =NH + , RN=NR + HY R NHR + , RNO + HY R OH + , and RNO₂ + HY RN( )OH + (where HY represents hydrocarbons, alcohols, phenols, amines, thiophenols, etc.) are considered as sources of radical generation. The enthalpies of these reactions are calculated. The parabolic model is used to calculate the rate constants for 254 such reactions. Various HY compounds acting as hydrogen-atom donors are compared with nitrogen-containing compounds acting as hydrogen-atom acceptors. The PhN(O) and PhNO₂ compounds exhibit the highest activity among the studied acceptors.     

硒酵母中有机硒及硒代氨基酸含量的测定方法

报道了人工培养硒酵母中有机硒及硒代胱氨酸（ＳｅＣｙｓ）和硒代蛋氨酸（ＳｅＭｅｔ）含量的测定方法。采用透析处理法使硒酵母中的无机硒和有机硒得以分离,并采用催化分光光度法测定了硒酵母中有机硒的含量;采用氨基酸自动分析仪测定了硒酵母中ＳｅＣｙｓ和ＳｅＭｅｔ的含量。     

荧光法测定水样中的硒(Ⅳ)、硒(Ⅵ)和有机硒

本文提出了水样中硒（Ⅳ）、硒（Ⅵ）和有机硒的荧光测定方法。基于酸性介质中２,３－二氨基萘与硒（Ⅳ）的选择性反应,直接测定硒（Ⅳ）;利用盐酸还原硒（Ⅵ）和ＨＮＯ３－ＨＣｌＯ４消化有机硒后,用差减法分别测出硒（Ⅵ）和有机硒。检出限０．０７μｇ／Ｌ,线性范围０～１０μｇ／Ｌ。硒（Ⅳ）、硒（Ⅵ）和有机硒的相对标准偏差与回收率分别为２．４％和９８．５％～１０１．５％、３．１％和９４．８％～１０３％、４．０％和９４．５％～９８．８％。     

Condensation Reactions of Sulfur-Containing Chalcone Analogs

Three-component condensation of heterocyclic chalcone analogs containing a thiophene ring with 5,5-dimethylcyclohexane-1,3-dione (dimedone) and ammonia at 140–145°C under pressure afforded functionalized 1,4,5,6,7,8-hexahydroquinoline derivatives; the corresponding triketones were formed under milder conditions (100–105°C). The condensation of 1,3-di(thiophen-2-yl)prop-2-en-1-one with dimedone and ammonia under harsh conditions unexpectedly produced functional 1,2,3,4,5,6,7,8,9,10-decahydroacridine derivative. Heterocyclic chalcone analogs reacted with ethyl acetoacetate in the presence of ammonia to give cyclocondensation products, ethyl 2-oxocyclohex-3-ene-1-carboxylates.     

Kinetic and Synthetical Manifestations of Important Reactions of Hydrophosphoryl Compounds

Abstract

Hydrophosphoryl compounds (HPC) is one of the most important and interesting types of organophosphorus substances. That is why a lot of their reactions are the authorized reactions in organic chemistry (Michaelis-Becker, Pudovik, Abramov and Kabachnic-Fields Reactions). In the presented work we have carried out systematic kinetic and synthetical investigation of mechanisms of the Pudovik, Abramov and Kabachnic-Fields reactions and also the reactivity of HPC in these reactions.     

有机化学主要章节内容的图示总结

以图示方式归纳总结有机化学中烯烃、炔烃、单环芳烃、卤代烷、醇、酚、醛、酮、羧酸及其衍生物、β-二羰基化合物、胺及重氮盐的化学性质、重要反应及其相关应用,将有机化学反应的知识系统化,帮助学生形成脉络清晰的知识体系。     

Synthesis and Chemistry of New Central and Planar Chiral Sulfur-Containing Ferrocenyl Compounds

Abstract

Enantiomerically pure 2-hydroxyalkyl, 2-aminoalkyl and 2-iminoalkyl ferrocenyl p-tolylsulfides are easily prepared in good yields and with complete diastereocontrol from (S)-(2-p-tolylthio)ferrocencarboxyaldehyde. 2-Iminoalkyl ferrocenyl derivatives can be used as ligands in asymmetric catalysis and as starting materials for asymmetric Staudinger reaction.     

Effects of Aminophenol Derivatives on Radiation-Induced Reactions Involving Various Organic Radicals

The effects of some aminophenol derivatives, diphenylamine, and ionol on the formation of ethanol and hexane radiolysis products in aerated and deaerated solutions were studied. The results allowed conclusions to be made about the effect of the structure of test compounds on their reactivity to oxygen- and carbon-centered radicals. It was found that 4,6-di-tert-butyl-2-(N-acetylamino)phenol, 4,6-di-tert-butyl-2-(N-benzoylamino)phenol, 2-hydroxydiphenylamine, and 4-hydroxydiphenylamine were highly competitive with commercial antioxidants in the efficiency of inhibition of radiation-induced processes of hexane oxidation. N-(2-Hydroxy-3,5-di-tert-butylphenyl)aniline, 4,6-di-tert-butyl-2-cyclohexylaminophenol, 2-hydroxydiphenylamine, 4-hydroxydiphenylamine, and N-phenyl-1,4-benzoquinonemonoimine were superior to ionol and diphenylamine in the inhibition of reactions of alkyl and -hydroxyalkyl radicals.