Reactions of Nucleophiles with Nitroarenes: Multifacial and Versatile Electrophiles

In this overview, it is shown that there are many initial reactions between nitroarenes and nucleophiles: addition to the electron‐deficient ring at positions occupied by halogen and hydrogen atoms, addition to the nitro group, single‐electron transfer (SET), and other types of initial reactions. The resulting intermediates react further in a variety of ways to form products of nucleophilic substitution of a halogen atom (S_NAr), a hydrogen atom (S_NArH), and others. Many variants of these processes are briefly discussed, particularly in relation of rates of the initial reactions and further transformations.     

Computation of generalized real radicals of polynomial ideals

For an ordered field (K,T) and an idealI of the polynomial ring , the construction of the generalized real radical ofI is investigated. When (K,T) satisfies some computational requirements, a method of computing is presented. Project supported by the National Natural Science Foundation of China (Grant No. 19661002) and the Climbing Project.     

Synthesis of thiopheno-quinizarine derivatives

4,11-Dihydroxyanthra[2,3-b]thiophene-5,10-dione (thiophenoquinizarine) and its 3-methyl derivative were obtained by the cyclization of quinizarin-2-yl derivatives of mercaptoacetaldehyde or mercaptoacetone in acid medium. 4,11-Dimethoxy-and 4,11-dibutoxyanthra[2,3-b]thiophene-5,10-dione were synthesized by the alkylation of the hydroxyl group in the synthesized anthrathiophenes with dimethylformamide dimethylacetal or butyl iodide respectively. Radical bromination of 4,11-dimethoxy-3-methylanthra[2,3-b]thiophene-5,10-dione, depending on the amount of N-bromo-succinimide taken, leads to the formation of 3-bromomethyl-or 3-dibromomethyl-4,11-dimethoxy-anthra[2,3-b]thiophene-5,10-diones. The action of sodium acetate on the obtained bromo derivatives with subsequent hydrolysis of the intermediate acetates led to the synthesis of 3-hydroxymethyl-or 3-formyl-4,11-dimethoxy-anthra[2,3-b]thiophene-5,10-diones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1478–1485, October, 2007.     

Unexpected Radical Telomerisation of Vinylidene Fluoride with 2-Mercaptoethanol

The radical telomerisation of vinylidene fluoride (VDF) with 2-mercaptoethanol as chain transfer agent (CTA) was studied to synthesise fluorinated telomers which bear a hydroxy end-group, such as H(VDF)_nS(CH₂)₂OH, under thermal (di-tert-butyl peroxide as the initiator) or photochemical initiations. A careful structural study of a typical H-VDF-S(CH₂)₂OH telomer was performed by ¹H and ¹⁹F NMR spectroscopy. These analytical methods allowed us to explore the selective addition of the thiyl radical onto the hydrogenated side of VDF, and the telomer containing one VDF unit was obtained selectively. Surprisingly, for higher [VDF]_o initial concentrations, a monoadduct telomer was produced as well as PVDF homopolymer. This feature was related to the fast consumption of the CTA. The kinetics of radical telomerisation led to a quite high transfer constant of the CTA (40 at 140 °C) that evidences the formation of a monoadduct as the only telomer formed.     

Charge transfer complexes and cation radical salts of azino-diselenadiazafulvalene

The synthesis and the redox behaviour of electroactive donor molecules incorporating an azino spacer group between a benzoselenazole core and another heterocyclic moiety, either a benzoselenazole one or a thiazole one, are reported. Neutral complexes were obtained with TCNQ and, for the first time with dithiadiazafulvalene or diselenadiazafulvalene derivatives, cation radical salts by electrocrystallization. Crystal structures data of these complexes are presented and their geometries compared with those deduced from theoretical calculations.     

线电荷与接地半无限大导体板所形成的电场

将镜像法和保角变换法相结合,计算由线电荷与接地半无限大导体板所形成的电场,给出其电势分布和场强分布,进一步得出等势线方程和电场线方程,并利用数学软件MATLAB绘制出等势线图和电场线图.     

Pulse radiolysis study on the mechanisms of reactions of CCl3OO. radical with quercetin, rutin and epigallocatechin gallate

The mechanisms of reactions between CC1₃OO^• radical and quercetin, rutin and epigallocatechin gallate (EGCG) have been studied using pulse radiolytic technique. It is suggested that the electron transfer reaction is the main reaction between CC1₃OO^• radical and rutin, EGCG, but there are two main pathways for the reaction of CC1₃OO^• radical with quercetin, one is the electron transfer reaction, the other is addition reaction. The reaction rate constants were determined. It is proved that quercetin and rutin are better CC1₃OO^• radical scavengers than EGCG.     

Atom Transfer Radical Polymerization (ATRP) of Ethyl Acrylate: Its Mechanistic Studies

Atom transfer radical polymerization (ATRP) of ethyl acrylate was carried out in bulk using ethyl 2-bromoisobutyrate as initiator, CuBr as well as CuCl as catalyst in combination with different ligands e.g., 2,2′ bipyridine (bpy)andN,N, N′,N″,N″-pentamethyldiethylenetriamine (PMDETA). In most of the cases very high conversion (72–98%) was achieved. The polymerization was well controlled with a linear increase of molecular weight (M_n^SEC) with conversion and relatively narrow molecular weight distributions (polydispersity index 1.2–1.3). Use of PMDETA as the ligand resulted in faster polymerization rate (98% conversion in 1 h) than those using bipyridine (72% conversion in 5 h). The MALDI-TOF-MS analysis of poly (ethyl acrylate) (PEA) prepared by using bpy as ligand showed the presence of halogen as the end group. On the contrary, when PMDETA was used as the ligand, the mass analysis showed no trace of this end group.     

Tetraacylgermanes: Highly Efficient Photoinitiators for Visible‐Light‐Induced Free‐Radical Polymerization

In this contribution a convenient synthetic method to obtain tetraacylgermanes Ge[C(O)R]₄ (R=mesityl ( 1 a ), phenyl ( 1 b )), a previously unknown class of highly efficient Ge‐based photoinitiators, is described. Tetraacylgermanes are easily accessible via a one‐pot synthetic protocol in >85 % yield, as confirmed by NMR spectroscopy, mass spectrometry, and X‐ray crystallography. The efficiency of 1 a , b as photoinitiators is demonstrated in photobleaching (UV/Vis), time‐resolved EPR (CIDEP), and NMR/CIDNP investigations as well as by photo‐DSC studies. Remarkably, the tetraacylgermanes exceed the performance of currently known long‐wavelength visible‐light photoinitiators for free‐radical polymerization     

线型高聚物分子量分布函数的另一种推导方法

针对自由基聚合歧化终止和偶合终止两类机理生成的线型高聚物,应用统计物理的基本原理,对其分子量分布重新进行了理论推导,其方法简洁清晰,无须任何附加假定,导出FlorySchulz分布.结果有助于从另一方面理解FlorySchulz分布的物理学基础.