氟烷基取代的双酚A类衍生物的合成

利用相转移催化剂十六烷基三甲基溴化铵(CTMAB)催化的连二亚硫酸钠引发的苯酚衍生物与含氟碘代烷的氟烷基化反应, 合成了含氟烷基取代的酚类化合物. 研究了双酚A与含氟碘代烷的氟烷基化反应, 得到了一类重要的含氟单体, 即含氟烷基取代的双酚A衍生物. 通过改变含氟碘代烷与双酚A的摩尔比, 可以得到单取代、二取代和四取代的含氟烷基双酚A衍生物.     

Design and synthesis of two triazonine-carbaldehyde derivatives using several chemical tools

Several triazonine-carbaldehyde derivatives have been prepared using different protocols; however, some require special reagents and conditions. The aim of study involved the synthesis of two triazonine-carbaldehyde derivative using testosterone or OTBS-testosterone as chemical tool. Triazonine-carbaldehyde derivatives were prepared by a series of reactions that involve the following: (1) synthesis of two nitrobenzamide derivatives by reaction of testosterone or OTBS-testosterone with p-nitrobenzoyl azide using Copper(II) as catalyst; (2) reaction of the nitrobenzamides with ethylenediamine to form two triazonine derivatives using boric acid as catalyst; (3) preparation of hexynyl-triazonine derivatives by the reaction of two triazonines 6-chlorohex-1-yne in basic medium; (4) reaction of hexynyl-triazonine derivatives with benzaldehyde to form two triazoninol analogs; (5) preparation of triazoninynal derivatives through oxidation of triazoninol analogs with dimethyl sulfoxide; and (6) synthesis of triazonine-carbaldehyde derivatives by the reaction of triazoninynal derivatives with hexyne-1 using Copper(II) as catalyst. The chemical structure of compounds was determined by spectroscopic and spectrometric methods. In conclusion, in this work were prepared two triazoninone derivatives using several chemical techniques, which are simple procedures and easy to handle.     

Scope and limitations of a new highly selective synthesis of unsymmetrical monomers for the synthesis of precursors toward poly(arylenevinylene)s

In our laboratory a precursor route to poly(p-phenylenevinylene) derivatives is developed in which unsymmetrically substituted p-xylene derivatives, possessing a benzylic sulfinylalkyl group, are used as monomers. Because of this unsymmetry, we were forced to investigate thoroughly the synthesis of these sulfoxides, as we start from symmetric and readily accessible molecules, namely, bis(halomethyl)-p-xylene derivatives. In a former publication, a new extremely effective route for the production of these unsymmetrically substituted sulfinyl monomers was presented. This paper expands upon these previously reported results. To examine the scope and limitations of this elegant route, this new method was applied to the synthesis of various derivatives not included in the initial work.     

Evaluation of Substituted Pyrazole-Based Kinase Inhibitors in One Decade (2011–2020): Current Status and Future Prospects

Pyrazole has been recognized as a pharmacologically important privileged scaffold whose derivatives produce almost all types of pharmacological activities and have attracted much attention in the last decades. Of the various pyrazole derivatives reported as potential therapeutic agents, this article focuses on pyrazole-based kinase inhibitors. Pyrazole-possessing kinase inhibitors play a crucial role in various disease areas, especially in many cancer types such as lymphoma, breast cancer, melanoma, cervical cancer, and others in addition to inflammation and neurodegenerative disorders. In this article, we reviewed the structural and biological characteristics of the pyrazole derivatives recently reported as kinase inhibitors and classified them according to their target kinases in a chronological order. We reviewed the reports including pyrazole derivatives as kinase inhibitors published during the past decade (2011–2020).     

Recent advances on the pesticidal activity evaluations of sulfone derivatives: A 2010 to 2020 decade in mini-review

Sulfone derivatives, an important synthetic strategy in drug discovery, are acquiring more importance in plant protection field in recent years because of their pesticide activities, such as antifungal, antibacterial, acaricidal, insecticidal, herbicidal, and antiviral activity. Introduction of different pharmacophores into sulfone framework can afford a series of sulfone derivatives to build some sulfone derivatives as novel active molecules. The purpose of this review was to collate literature work reported by researchers on sulfone derivatives for their various pesticidal activities from year 2010 to 2020.     

有机噻吩类衍生物作为电致变色材料*

噻吩类衍生物包括聚噻吩衍生物和齐聚噻吩衍生物。本文从有目的地设计、合成噻吩类衍生物的角度出发,探索了其作为电致变色材料的应用,综述了噻吩类衍生物作为电致变色材料的最新研究进展。     

6-取代喹唑啉衍生物的合成及抗肿瘤活性研究进展

喹唑啉及其衍生物作为重要的药效团,具有广谱的抗肿瘤生物活性,一直是药物化学研究的热点。本文围绕近年来6-酰胺类、卤代类、醚类、与7-位成环类、杂环类等喹唑啉衍生物的合成及其抗肿瘤活性作用机制研究进行概述,以期为活性更高、毒性更小的新型抗肿瘤化合物的设计合成提供参考。     

Synthesis of Carbazole Alkaloids by Ring‐Closing Metathesis and Ring Rearrangement–Aromatization

Aprocess for the assembly of carbazole alkaloids has been developed on the basis of ring‐closing metathesis (RCM) and ringrearrangement–aromatization (RRA) as the key steps. This method is based on allyl Grignard addition to isatin derivatives to provide smooth access to 2,2‐diallyl 3‐oxindole derivatives through a 1,2‐allyl shift. The diallyl derivatives were used as RCM precursors to afford a novel class of spirocyclopentene‐3‐oxindole derivatives, which underwent a novel RRA reaction to afford carbazole derivatives. The synthetic sequence to carbazoles was shortened by combining the RCM and RRA steps in an orthogonal tandem catalytic process. The utility of this methodology was further demonstrated by the straightforward synthesis of carbazole alkaloids, including amukonal derivative, girinimbilol, heptaphylline, and bis(2‐hydroxy‐3‐methylcarbazole).     

Enantioselective α-heterofunctionalisation of carbonyl compounds: organocatalysis is the simplest approach

Enantioselective organocatalytic processes have reached maturity in recent years with an impressive number of applications now available. The application of these advantageous methodologies to the construction of chiral α-hetereofunctionalised carbonyl compounds allows us to obtain important chiral building blocks, such as α-amino acids, α-amino alcohols, aziridines, epoxides, 1,2-diols and α-sulfenylated, selenenylated and halogenated carbonyl derivatives. Proline, imidazolidinone derivatives, cinchona alkaloids and their ammonium salts, as well as Brønsted acid derivatives, have been used as chiral catalysts for these purposes. A survey of contributions in this field will be discussed throughout this review.     

TEMPO and its derivatives mediated reactions under transition-metal-free conditions

2,2,6,6-Tetramethyl-l-piperidinyl-N-oxyl(TEMPO)and its derivatives as stable radicals can participate in many reactions.During the process,TEMPO and its derivatives could act not only as the substrates to capture or initiate new radical intermediates to provide new compounds but also as organic catalysts or oxidants for transformations of alkenes,alcohols,aldehydes and so on to synthesize various high valueadded compounds.In this review,we would introduce recent advances of the transformations of different substrates mediated by TEMPO and its derivatives under transition-metal-free conditions.     

Use of fluorinated diphenylolmethane derivatives for preparing heat-resistant elastic polyurethanes

Fluorinated diphenylolmethane derivatives were used for the first time as chain extenders in urethane formation reactions in preparation of elastic materials. Fluorinated diphenylolmethane derivatives exhibit positive surface activity. Owing to this fact and to the presence of reactive hydroxy groups, these derivatives allow preparation of fluorinated polyurethane materials with enhanced resistance to heat and aggressive media.     

固定化脯氨酸及其衍生物用于催化不对称有机合成

脯氨酸及其衍生物作为有机手性催化剂,在不对称有机合成中得到广泛应用。该类催化剂具有结构简单、来源丰富和选择性高等优点,但仍存在催化剂用量大、难以回收以及无法重复利用等不足。近年来,随着固定化技术的发展,固定化脯氨酸及其衍生物受到广泛关注。固定化脯氨酸及其衍生物催化剂可以简化不对称催化中产物的分离过程,实现催化剂的便利回收与循环使用。本文综述了固定化脯氨酸及其衍生物的制备及在催化不对称有机合成(如Aldol反应、Michael加成反应、Mannich反应等)中的研究进展。     

喹嗪并[3,4,5,6-ija]喹啉衍生物的合成及其光解水制氢性能

设计、合成了一系列4,5,9,10-四芳基喹嗪并喹啉衍生物,并在均相光解水制氢体系中研究其光敏活性。研究结果表明,二氯化钯是其有效制氢的催化剂,还原淬灭是光敏剂的主要淬灭途径。通过光电物理化学性能研究表明,这类喹嗪并喹啉衍生物的取代基效应明显,而甲氧基有利于提高其荧光量子效率,最高可达0.48;同时供电子甲氧基取代基能明显提高光敏剂制氢性能,光敏剂3e的制氢总转换数(TON)可达341。     

Study on various fluorescein derivatives as pH sensors

Various fluorescein derivatives were examined as fluorescent pH sensors. Fluorescein derivatives bearing benzylic amine moieties displayed opposite fluorescent changes compared to those of simple fluorescein derivatives upon pH changes. Photo-induced electron transfer (PET) mechanism controls the fluorescent changes of these derivatives. In this Letter, modulations of pK_a values were successfully demonstrated through variations of substituent groups.     

The reaction of vinyl ethers with acridine

The reaction of vinyl ethers with acridine gives new acridine derivatives in the presence of an organic ammonium salt and alcohol. An organic ammonium salt such as acridinium chloride affect this reaction. All of the addition products were obtained as dihydroacridinyl derivatives. Moreover, in the reaction of ketene silyl acetal with acridine, the addition products were also obtained as the dihydroacridine derivatives.     

Intercalation of organic dye molecules into double-stranded DNA. Part 2: the annelated quinolizinium ion as a structural motif in DNA intercalators

DNA intercalators represent an important class of compounds with a high potential as DNA-targeting drugs. In this review it is demonstrated that annelated quinolizinium derivatives such as coralyne and derivatives thereof intercalate into DNA and that this structural motif allows several variations of the substitution pattern without loss of intercalating properties. The commonly applied methods for the evaluation of the DNA association, mainly spectroscopic studies, are pointed out. In addition, studies on the biological activities of annelated quinolizinium derivatives, such as topoisomerase poisoning or cell toxicity, are highlighted.     

Anhydrous proton conductivities of squaric acid derivatives

In this communication, we introduce squaric acid derivatives as anhydrous proton conductors. We report the synthesis, characterization and proton conductivities of four squaric acid derivatives. The anhydrous proton conductivity of one of the derivatives was 2.3 × 10(-3) S cm(-1) at 110 °C, comparable to the conductivity of molten 1H-1,2,3-triazole or 1H-imidazole.     

Alpha-substituted organic peroxides: synthetic strategies for a biologically important class of gem-dihydroperoxide and perketal derivatives

In this paper we review the recent developments in the synthesis of alpha-substituted hydroperoxides. Alpha-substituted hydroperoxides are interesting compounds due to their chemistry and bioactivity and as intermediates for the synthesis of other peroxides, of which cyclic peroxides are of major importance. Although the emphasis of this report will be on the derivatives of gem-dihydroperoxides, perketals, as well as the less studied nitrogen and sulfur derivatives, will also be covered.     

碳十硼烷及其衍生物的反应性及应用

碳十硼烷(C₂B₁₀H₁₂)是由2个C原子和10个B原子组成的二十面体笼状结构大分子,有邻位、间位和对位三种异构体。碳十硼烷庞大的体积以及类芳香族三维刚性结构使它具有优异的高温稳定性和化学稳定性,良好的溶解性使其具有广泛而灵活的应用。本文总结了近年来碳十硼烷和碳十硼烷衍生物在C原子、B原子上的化学反应性以及在环加成和金属络合方面的研究。另外,由于碳十硼烷衍生物特殊的立体结构,优异的耐高温性、热氧化性及高硼含量,本文综述了碳十硼烷衍生物近年来在功能材料、催化剂及生物医药等多个领域的应用进展。     

多巴及其衍生物黏附性的研究与应用进展

多巴(DOPA)是海洋贻贝等生物分泌黏液的重要组成部分,它具有很强的黏附性,不仅可以黏附在无机材料表面,也可以黏附在有机材料表面。进一步的研究表明,含邻苯二酚基团的多巴类衍生物同样具有与多巴相类似的强黏附性,由此发展起来的聚多巴胺涂层在诸多领域已得到应用。基于上述研究成果,科学家们将多巴及其衍生物引入高分子中,得到了一系列黏附性能强的仿生高分子,在各领域也已得到应用。本文综述了多巴及其衍生物黏附机理的研究和它们在各领域的应用现状。