Oligothienylenevinylenes incorporating 3,4-ethylenedioxythiophene (EDOT) units

A new series of π-conjugated oligomers based on various combinations of thiophene and EDOT units and double bonds has been synthesized by Wittig-Horner reactions from phosphonate anions carrying EDOT or bis-EDOT units. Optical and electrochemical results evidence the crucial role of the EDOT moiety for modulating the electronic properties of the oligomers. The insertion of bis-EDOT unit in the middle of the molecule leads to a self-rigidification of the conjugated system due to non covalent S?O intramolecular interactions. The strong electron donor effect of the EDOT units explains the determining role of the relative position of the EDOT units on the localization and stabilization of the positive charges in the radical cation or dication states.     

Synthesis of fluorinated imines and carbodiimides from azides via aza-Wittig reaction

The Staudinger reaction of fluoroalkylazides were studied. A series of N-fluoroalkylimines were synthesized via aza-Wittig reaction of N-fluoroalkyliminophosphoranes. The N,N′-difluoroalkylated carbodiimide was also synthesized via the reaction of N-fluoroalkyliminophosphoranes with carbon dioxide or carbon disulfide.     

Regio- and stereoselective reactions of a rhodanine derivative with optically active 2-methyl- and 2-phenyloxirane

The reaction of a rhodanine derivative (=(Z)-5-benzylidene-3-phenyl-2-thioxo-1,3-thiazolidin-4-one; 1) with (S)-2-methyloxirane (2) in the presence of SiO₂ in dry CH₂Cl₂ for 10 days led to two diastereoisomeric spirocyclic 1,3-oxathiolanes 3 and 4 with the Me group at C(2) (Scheme 2). The analogous reaction of 1 with (R)-2-phenyloxirane (5) afforded also two diastereoisomeric spirocyclic 1,3-oxathiolanes 6 and 7 bearing the Ph group at C(3) (Scheme 3). The structures of 3, 4, 6, and 7 were confirmed by X-ray crystallography (Figs. 1 and 2). These results show that oxiranes react selectively with the thiocarbonyl group (CS) in 1. Furthermore, the nucleophilic attack of the thiocarbonyl S-atom at the SiO₂-activated oxirane ring proceeds with high regio- and stereoselectivity via an S_N2-type mechanism.     

用环加成反应合成含氟杂环化合物的研究

综述了近年来利用一些新型的含氟砌块，通过它们的环加成反应来高效地合成 含氟杂环化合物的研究，其中包括以下两个部分：(1)用1，3—偶极环加成反应合 成五元含氟杂环化合物；(2)用杂原于Diels-Alder反应合成六元含氟杂环化合物．     

原子荧光光谱法测定砷过程中还原反应条件的优化

自然界中砷和砷的化合物一般可通过水、大气和食物等途径进入人体,危害人体健康,原子荧光光谱法测定砷含量被广泛应用。为准确测定样品中砷的含量,以原子荧光光谱法(AFS)测定土壤中总砷含量为例,重点研究高价态砷(Ⅴ)还原为低价态砷(Ⅲ)的实验条件,采用正交实验进行条件优化,建立适合的实验方法。通过设计L9(34)正交实验,高价态砷的还原反应与四个因素有关,即与反应温度、反应时间、盐酸加入量和硫脲的用量呈一定的正相关,结果表明,四个因素中硫脲用量的影响最为显著,其次是盐酸加入量、反应时间和反应温度。通过对四个因素的多水平检验,优化后的实验条件为：硫脲用量2.0 mL、盐酸加入量10%、反应时间20 min、温度20～35 ℃(即普通室温)。采用土壤标准物质验证优化后条件的可行性,得出砷的测定值在标准值范围内,RSD在2.2%～4.2%,精密度和准确性均满足质控要求。优化后的实验条件使得操作简便易行,提高了工作效率。     

Synthesis and Structure Elucidation of Novel Spirooxindole Linked to Ferrocene and Triazole Systems via [3 + 2] Cycloaddition Reaction

In the present work, a novel heterocyclic hybrid of a spirooxindole system was synthesized via the attachment of ferrocene and triazole motifs into an azomethine ylide by [3 + 2] cycloaddition reaction protocol. The X-ray structure of the heterocyclic hybrid (1″R,2″S,3R)-2″-(1-(3-chloro-4-fluorophenyl)-5-methyl-1H-1,2,3-triazole-4-carbonyl)-5-methyl-1″-(ferrocin-2-yl)-1″,2″,5″,6″,7″,7a″-hexahydrospiro[indoline-3,3″-pyrrolizin]-2-one revealed very well the expected structure, by using different analytical tools (FTIR and NMR spectroscopy). It crystallized in the triclinic-crystal system and the P-1-space group. The unit cell parameters are a = 9.1442(2) Å, b = 12.0872(3) Å, c = 14.1223(4) Å, α = 102.1700(10)°, β = 97.4190(10)°, γ = 99.1600(10)°, and V = 1484.81(7) ų. There are two molecules per unit cell and one formula unit per asymmetric unit. Hirshfeld analysis was used to study the molecular packing of the heterocyclic hybrid. H···H (50.8%), H···C (14.2%), Cl···H (8.9%), O···H (7.3%), and N···H (5.1%) are the most dominant intermolecular contacts in the crystal structure. O···H, N···H, H···C, F···H, F···C, and O···O are the only contacts that have the characteristic features of short and significant interactions. AIM study indicated predominant covalent characters for the Fe–C interactions. Also, the electron density (ρ(r)) at the bond critical point correlated inversely with the Fe–C distances.     

Azides in the Synthesis of Various Heterocycles

In this review, we focus on some interesting and recent examples of various applications of organic azides such as their intermolecular or intramolecular, under thermal, catalyzed, or noncatalyzed reaction conditions. The aforementioned reactions in the aim to prepare basic five-, six-, organometallic heterocyclic-membered systems and/or their fused analogs. This review article also provides a report on the developed methods describing the synthesis of various heterocycles from organic azides, especially those reported in recent papers (till 2020). At the outset, this review groups the synthetic methods of organic azides into different categories. Secondly, the review deals with the functionality of the azido group in chemical reactions. This is followed by a major section on the following: (1) the synthetic tools of various heterocycles from the corresponding organic azides by one-pot domino reaction; (2) the utility of the chosen catalysts in the chemoselectivity favoring C−H and C-N bonds; (3) one-pot procedures (i.e., Ugi four-component reaction); (4) nucleophilic addition, such as Aza-Michael addition; (5) cycloaddition reactions, such as [3+2] cycloaddition; (6) mixed addition/cyclization/oxygen; and (7) insertion reaction of C-H amination. The review also includes the synthetic procedures of fused heterocycles, such as quinazoline derivatives and organometal heterocycles (i.e., phosphorus-, boron- and aluminum-containing heterocycles). Due to many references that have dealt with the reactions of azides in heterocyclic synthesis (currently more than 32,000), we selected according to generality and timeliness. This is considered a recent review that focuses on selected interesting examples of various heterocycles from the mechanistic aspects of organic azides.     

Conjugates of Iron-Transporting N-Hydroxylactams with Ciprofloxacin

Screening of a library of novel N-hydroxylactams amenable by the Castagnoli-Cushman reaction identified four lead compounds that facilitated ⁵⁵Fe transport into P. aeruginosa cells (one of these synthetic siderophores was found to be as efficient at promoting iron uptake as the natural siderophores pyoverdine, pyochelin or enterobactin). Conjugates of the four lead siderophores with ciprofloxacin were tested for antibacterial activity against P. aeruginosa POA1 (wild type) and the ∆pvdF∆pchA mutant strain. The antibacterial activity was found to be pronounced against the ∆pvdF∆pchA mutant strain grown in CAA medium but not for the POA1 strain. This may be indicative of these compounds being ‘Trojan horse’ antibiotics. Further scrutiny of the mechanism of the antibacterial action of the newly developed conjugates is warranted.     

Synthesis and Luminescent Properties of s-Tetrazine Derivatives Conjugated with the 4H-1,2,4-Triazole Ring

New derivatives obtained by the combination of unique 1,2,4,5-tetrazine and 4H-1,2,4-triazole rings have great application potential in many fields. Therefore, two synthetic few-step methodologies, which make use of commercially available 4-cyanobenzoic acid (method A) and ethyl diazoacetate (method B), were applied to produce two groups of the aforementioned heterocyclic conjugates. In both cases, the target compounds were obtained in various combinations, by introducing electron-donating or electron-withdrawing substituents into the terminal rings, together with aromatic or aliphatic substituents on the triazole nitrogen atom. Synthesis of such designed systems made it possible to analyze the influence of individual elements of the structure on the reaction course, as well as the absorption and emission properties. The structure of all products was confirmed by conventional spectroscopic methods, and their luminescent properties were also determined.     

Decomposition Reaction of Zn-MPA（3-Mercaptopropionic Acid） Complex Under Microwave Irradiation

The thermal decomposition of Zn-MPA complex was investigated under microwave irradiation. ZnO and ZnS nanocrystals could be obtained by decomposing Zn-MPA（3-mercaptopropionic acid） complex under different reaction conditions. It was found that both the pH value of the solution and the molar ratio of Zn2＋ and MPA can play an important role in the formation of ZnO and ZnS nanocrystals. MPA mainly acts as an S source or as a complexing agent. This study provides a new route for the controllable preparation of semiconductor nanocrystals.