含螺环结构农药研究进展

综述了近年来含螺环结构化合物在农药方面的研究进展, 详细介绍了部分螺环化合物的合成方法, 总结了螺环农药的结构特征. 对该类化合物的应用前景进行了展望.     

Photochromic DNA having fluorescent protein-inspired nucleosides

Molecular switches controlled by light stimuli can be applicable to the variety of the biological application. In this study, skeletal structures of a chromophore of fluorescent protein were applied as aglycones of newly designed photochromic nucleosides, “Fluorescent protein-inspired nuceloside: FIN”. Phosphoramidite units of the photochromic nucleosides having imidazolinone derivatives with benzylidene or 3-pyridilidene groups were successfully synthesized for FIN-containing ODNs. Thermodynamic studies of the FIN-containing ODNs revealed that photo-irradiation with specific wavelength induced stability change of the duplexes.     

Synthesis, Structure and Properties of Two Photochromic Compounds Containing A Pyrazolone-ring

IntroductionThe investigation of organic photochromic materials has increased considerably in recentyears because of their potential commercial application in several areas,such as high-densityoptical storage media,optical switching,etc.[1 ,2 ] .Though numerous organic photochromicmolecular systems or photoactive devices have been explored so far,those systems classifiedaccording to the photochromic structural units mainly belong to a small number of families:fulgides,spiropyrans and spiroxazi…     

Synthesis and Structure Elucidation of New Spiro Compounds with Polyfluoroalkyl and Phosphonate Ester Groups

A series of spiro compounds with polyfluoroalkyl and phosphonate ester groups has been synthesized via several steps. The structures of these compounds were confirmed by ¹H NMR,¹³C NMR, infrared (IR), and mass spectrometry (MS) as well. The possible reaction mechanism for the formation of these products was also proposed.     

含氧、氮、硫杂原子的螺环大分子化合物的研究进展

近20年来, 螺环大分子化合物由于其特殊的结构而引起了科学家们的广泛关注, 作为一类新型的高负载量载体应用于有机合成和催化是螺环大分子化合物重要的应用领域之一. 介绍了含氧、氮、硫等杂原子的线形及树形大分子螺环化合物的合成方法和结构特征, 展望了该类化合物的应用前景, 并提出了一些新的设想.     

一类含多氟烷基侧链的螺环化合物的合成及结构表征

A series of spiro compounds have been synthesized via several steps.The structure of these compounds wereconfirmed by ~1H NMR,~(13)C NMR,IR,MS spectra and X-ray diffraction analysis.The possible mechanism to formthese products was also proposed.     

新型有机光致变色材料螺嗪的结构确证

采用^1H NMR谱、^13C NMR谱、DEPT（θ=3π/4）谱、红外吸收光谱、质谱等仪器分析手段确证了4种新合成的有机光致变色材料螺E嗪化合物的结构,并对化合物的^13C NMR谱化学位移和质谱碎片进行了归属和确认。     

Green Synthesis of Spiro Compounds with Potential Anticancer Activity through Knoevenagel/Michael/Cyclization Multicomponent Domino Reactions Organocatalyzed by Ionic Liquid and Microwave-Assisted

In this work a microwave-assisted Knoevenagel/Michael/cyclization multicomponent domino methodology, using ethanol as solvent and the ionic liquid 1-methylimidazolium chloride as catalyst was developed for the synthesis of spiro compounds. The reaction conditions considered ideal were determined from a methodological study varying solvent, catalyst, amount of catalyst, temperature, and heating mode. Finally, the generality of the methodology was evaluated by exploring the scope of the reaction, varying the starting materials (isatin, malononitrile, and barbituric acid). Overall, the twelve spiro compounds were synthesized in good yields (43–98%) and the X-ray structure of compound 1b was obtained. In addition, the in vitro antiproliferative activities of the spirocycles against four types of human cancer cell lines including HCT116 (human colon carcinoma), PC3 (prostate carcinoma), HL60 (promyelocytic leukemia), and SNB19 (astrocytoma) were screened by MTT-based assay. It is noteworthy that spiro compound 1c inhibited the four cell lines tested with the lowest IC₅₀ values: 52.81 µM for HCT116, 74.40 µM for PC3, 101 µM for SNB19, and 49.72 µM for HL60.     

螺[1—溴—4—l—孟氧其—5—氧杂—6—氧代双环[3.1.0]已烷2,3‘—（4’—甲氧 …

本文报道了利用新手性还源合成的标题化合物Ｃ２９Ｈ４５ＢｒＯ７（Ｍｒ＝５８５．５６）的晶体结构,该晶体属正交晶系,空间群为Ｐ２１２１２１,晶胞参数α＝９．７４８（４）,ｂ＝１２．５３７（５）,ｃ＝２５．８５１（９）Ａ,Ｖ＝３１５９（２）Ａ＾３,Ｚ＝４,Ｄｘ＝１．２３１ｇ／ｃｍ＾２,μ１．３４１ｍｍ＾－１,Ｆ（０００）＝１２４０,偏离因子Ｒ＝０．０４７５,ＲＷ＝０．０６０９,分子中共有５个环,１２个手     

神奇的手性螺环配体

过渡金属参与的不对称催化反应是有机合成化学研究的前沿和热点. 寻找和发现新颖配体骨架并开展新型高效的手性配体及催化剂的设计合成是不对称催化反应研究的核心内容. 从20世纪90年代,特别是进入21世纪以来,螺环骨架手性配体受到了广泛的关注,并逐渐发展成为特色鲜明的手性配体类别. 手性螺环配体的骨架已由多手性的螺[4.4]壬烷骨架发展到只具有单一手性的螺二氢茚和螺[4.4]壬二烯等螺环骨架类型,形成了包括手性螺环单磷配体、双膦配体、膦氮配体、双氮配体等丰富的手性配体库. 这些手性螺环配体及其催化剂不仅在不对称催化氢化、不对称碳―碳键形成、不对称碳―杂原子键形成等多种类型的不对称催化反应中均表现出优异的催化活性和对映选择性,且使得许多原先难以控制对映选择性的不对称催化反应变得可能. 而今,手性螺环结构已成为“优势结构”,相应的手性螺环配体及其催化剂已被国内外同行广泛采用. 手性螺环配体的兴起为手性催化剂研究增加了活力,极大地促进了不对称合成化学的发展. 今后,手性螺环配体的研究除了将向新型、高效、高选择性手性配体及催化剂方向发展外,将其应用于新的不对称催化反应的对映选择性控制、以及应用于手性天然产物和药物的高效不对称合成将成为新的研究热点.     

含氧、氮、硫杂螺环结构的光致变色化合物研究进展

有机螺环光致变色化合物具有较好的化学稳定性、光敏性和抗光疲劳性, 可应用于光过滤器及光学记录存储. 为了获得性能优良的螺环光致变色化合物, 新的设计合成一直是该领域研究的热点. 总结了对含氧、氮、硫杂螺环结构的光致变色化合物的研究进展, 描述了螺环化合物的结构特征和部分化合物的合成过程, 展望了螺环光致变色化合物的发展前景.     

A Nazarov-Ene Tandem Reaction for the Stereoselective Construction of Spiro Compounds

The different reactivity of trienones under Lewis and Brønsted acids catalysis was investigated, resulting in distinct cyclization products and carbon backbones that originated either from a conjugate Prins cyclization or an interrupted Nazarov cyclization. In particular, an unprecedented Nazarov cyclization tandem reaction is presented, terminating the oxyallyl cation by an ene-type reaction, and leading stereoselectively to bicyclic spiro compounds. The terminal olefin of this motif represents a useful handle for further functionalization, making it a strategic intermediate in total syntheses. The tandem Nazarov/ene cyclization was shown to be preferred over a Nazarov/[3+2] tandem reaction for all our substrates, independent of chain length. Deuteration studies further support the mechanistic hypothesis of the terminating ene reaction.     

含芴、蒽螺环结构电致发光材料的研究进展

螺环芳香类化合物具有大的共轭体系和较好的刚性共面性, 而且玻璃化温度高, 热稳定性好(熔点大于300 ℃), 制作电致发光(EL)器件工艺简单, 不需要复杂的设备, 因而有可能降低器件制作成本, 特别是易于制备大面积器件. 对近年来含芴、蒽螺环结构发光材料的研究进展进行了总结, 重点介绍了含有双螺、单螺结构的有机电致发光材料的结构和特性, 给出了部分有机化合物的合成方法. 对含有硅元素的螺环化合物发光材料进行了简单介绍.     

Synthesis and Photochromic Properties of the Derivatives of Spiropyrans Containing a Mesogenic Group

The photochromic compounds continue to attract significant attention in view of their general applicability as optical information storage materials or switching devices1-2.In order to develop novel bifunctional and multifunctional materials,special attention has been paid to photochromic liquid crystalline compounds.Many studies have been carried out for all kinds of mixed systems,which are to dope small amounts photochromic compounds into liquid crystal3-4.However,the combination of the prop…     

二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基的合成

以1,4-环己二酮、丙二酸二乙酯及多元醇等为原料, 经过两次“一锅煮”法合成了六种二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基螺环树形化合物, 其中烷氧基为异戊氧基、三羟甲基甲氧基、2,2-二溴甲基-3-羟丙氧基、2,2-二羟甲基丙氧基、二羟甲基膦甲氧基和(N-羟甲基-N-二羟甲基氨基乙基)甲氧基. 利用IR, NMR, MS和元素分析对合成的化合物进行了结构认证, 对影响反应的因素进行了讨论.     

Synthesis,Structure and Photochromic Properties of 1-Phenyl-3-Methyl-4-(4-Bromobenzal)-Pyrazolone-5 Thiosemicarbazone

A new organic photochromic compound containing pyrazolone-ring, 1-phenyl-3-methyl-4-(4-bromobenzal)-pyrazolone-5 thiosemicarbazone (PM4BrBP-TSC), was synthesized and characterized by elemental analyses and single crystal X-ray diffraction. The X-ray determination indicated that PM4BrBP-TSC is of orthorhombic system, space group Pbca with cell dimensions of a = 12.184(2) Å, b = 18.121(3) Å, c = 18.554(4) Å, V = 4096.4(12) ų, Z = 8 and R = 0.0387. The photochromic properties and photocolored kinetics of PM4BrBP-TSC were studied by Time-dependent UV-Vis reflectance spectra and fluorescence spectra under 365 nm light irradiation. The crystal structure analysis showed that the photochromic properties were related to the photoisomerization from enol tautomer to keto one.     

苯氧基萘并萘醌类光致变色材料

首次综述了在成电子和记录器件方面很有应用前景的苯氧基萘并萘醌类光致变色化合物和聚合物在合成，光致变色机理，光化学性质和应用探索方面的进展。     

Photochromic Properties of Pyrryl Fulgides

We evaluated the photochromic properties of pyrryl fulgides by means of comparing their quantum yields of photocoloring, thermal stabilities and fatigue resistances.     

Photochromic Nucleosides and Oligonucleotides

Photochromism is a reversible phenomenon wherein a material undergoes a change in color upon exposure to light. In organic photochromes, this effect often results from light-induced isomerization reactions, leading to alterations in either the spatial orientation or electronic properties of the photochrome. The incorporation of photochromic moieties into biomolecules, such as proteins or nucleic acids, has become a prevalent approach to render these biomolecules responsive to light stimuli. Utilizing light as a trigger for the manipulation of biomolecular structure and function offers numerous advantages compared to other stimuli, such as chemical or electrical treatments, due to its non-invasive nature. Consequently, light proves particularly advantageous in cellular and tissue applications. In this review, we emphasize recent advancements in the field of photochromic nucleosides and oligonucleotides. We provide an overview of the design principles of different classes of photochromes, synthetic strategies, critical analytical challenges, as well as structure–property relationships. The applications of photochromic nucleic acid derivatives encompass diverse domains, ranging from the precise photoregulation of gene expression to the controlled modulation of the three-dimensional structures of oligonucleotides and the development of DNA-based fluorescence modulators. Moreover, we present a future perspective on potential modifications and applications.     

新型螺吡喃化合物的合成及应用研究

设计合成了几种新型螺吡喃化合物(SP), 采用¹H NMR, IR 和MS 对其结构进行表征. 研究了目标产物的光致变色性能及其影响因素, 并对SP1 在高分子材料领域的应用作了初步研究. 结果表明: 苯并吡喃环连有强吸电子基时, 最大吸收峰红移; 1 位N原子上连有柔性长链基团时, 热褪色速率较慢; 采用紫外光照射目标产物不同时间, SP1 表现出较好的抗光疲劳性. 分别以SP1 为接枝组分和共混组分制备两种高分子材料SP-g-hPMMA 和SP-m-PMMA, 通过紫外光辐照动力学研究表明, SP-g-hPMMA 和SP-m-PMMA 均表现出比SP1 优异的光致变色性能, 且不影响PMMA 的机械性能. SP1 有望用于高分子光致变色材料领域.