N-羟甲基-2,3-二丁硫基四硫富瓦烯并[6,7-c]吡咯的合成

从4,5-二丁硫基-1,3-二硫杂环戊二烯-2-酮和N-对苯磺酰基-2-硫代-1,3-二硫杂环戊二烯并[4,5-c]吡咯出发,经交叉偶联、去保护得2,3-二丁硫基四硫富瓦烯并[6,7-c]吡咯(4)。化合物4在碱存在下与甲醛水溶液(37%)反应生成N-羟甲基化的产物。用核磁共振氢谱研究了标题化合物在不同极性溶剂中的偶合行为。     

四硫富瓦烯类衍生物的合成及表征

以金属钠和二硫化碳为起始原料,合成四硫富瓦烯(TTF)锌的配合物(TTF)Zn(NBu_4)_2。其与卤代烷烃或取代类酰氯反应得到16个对称的四硫富瓦烯硫酮类衍生物,再经醋酸汞氧化分别得到16个四硫富瓦烯氧酮类衍生物,其中13个未见文献报道。操作简单且收率达80%以上,其结构经~1H NMR、~(13)C NMR表征确证。     

氧化还原荧光开关构建的新型高选择性多信号化学传感器的研究

2,3,6,7-四(2′-氰乙硫基)四硫富瓦烯在醇钠的作用下消除氰乙基生成四硫富瓦烯四硫盐,再与9-溴甲基蒽反应生成四(9-亚甲基蒽硫基)四硫富瓦烯,通过氧化还原法发现其荧光能够可逆地增强或减弱,因此它是一个新的氧化还原荧光开关。在多种金属离子中,该新型氧化还原开关只对Fe3+有识别性能,其荧光强度随Fe3+的量增大而增强,其他金属离子没有干扰。所以,它又是一种对Fe3+具有高选择性识别的荧光传感器。该文报告工作的新颖性已为安徽大学图书馆2009年4月30日出具的第2009006号《科技查新报告》所证实。     

双稠合四硫富瓦烯衍生物的合成及电化学性质

以二硫化碳、二甲基甲酰胺等为起始原料,合成了3种新的非对称双稠合四硫富瓦烯(TTF)衍生物:2-(4′,5′-二烷硫基-1′,3′-二硫代环戊烯-2′-叉)-5-(4′,5′-二腈乙硫基-1′,3′-二硫代环戊烯-2′-叉)-1,3,4,6-四硫并环戊烯。通过元素分析、IR1、HNMR对产物结构进行了鉴定。系统地研究了这类非对称双稠合四硫富瓦烯衍生物的导电性能和电化学性质,结果表明除乙基和丙基取代的衍生物呈现半导体性质外,其他取代基的衍生物均为绝缘体。循环伏安研究显示所有化合物的电荷迁移分两步进行,但不是严格的电化学可逆。     

四硫富瓦烯作为催化剂的研究进展

介绍了四硫富瓦烯作为自由基-极性交叉反应的催化剂的反应机理,以及四硫富瓦烯催化的自由基-极性交叉反应在四环生物碱等天然产物合成方面的研究进展,展望了其发展趋势。     

双稠合四硫富瓦烯衍生物的制备及取代基对合成的影响

扩展TTF衍生物的π共轭体系,可以增进分子导体中分子间的S…S相互作用,改善分子导电性。基于这个目的,以二硫化碳、二甲基甲酰胺为起始原料,合成了二种双稠合的四硫富瓦烯衍生物2．(4′,5′-二甲硫基-1′,3′,二硫代环戊烯-2′叉)-5-(4′,5′-二腈乙硫基．1′,3′-二硫代环戊烯-2′叉)-1,3,4,6-四硫并环戊烯和2,5-二(4′,5′-二甲硫基-1′,3′-二硫：、己环戊烯-2′-叉)-1,3,4,6-四硫并环戊烯。这两种化合物具有更为伸展的π共轭体系,因此有可能成为优良的电子给体。中间物及锄物经IR和元素分析进行了结构鉴定。同时讨论了取代基性质对双稠合四硫富瓦烯衍生物的合成收率的影响。     

“A-C≡C-TTF-C≡C-A”型四硫富瓦烯衍生物的合成与性质研究

四硫富瓦烯及其衍生物是性能优良的电子给体.本文利用Sonogashira反应将吡啶基团连接在四硫富瓦烯单元上,合成了"A-C≡C-TTF-C≡C-A"型四硫富瓦烯共轭体系衍生物4,4′(5′)-二-(4-吡啶乙炔基)-四硫富瓦烯(TTF4N).吸收光谱、电化学和Pb2+配位键合研究表明,三键作为桥基能够有效实现分子内的电荷转移.金属Pb2+离子与吡啶基团的配位能够引起TTF4N的吸收光谱、核磁氢谱和电化学性质的显著变化.     

新品研发辑要

新型四硫富瓦烯硫杂冠醚衍生物的合成简介:由于四硫富瓦烯(以下简称TTF)是一种稳定的、可逆的两电子给体,故可以利用于具有电、光、磁等性质的超分子化合物的构筑上。1985年,Otsubo等首次把TTF结构单元和冠醚结构单元连接在一起合成出了有离子传感性质的TTF冠醚衍生物。     

四硫富瓦烯基四硫纶及其配合物的合成

以二硫化碳、N，N-二甲基甲酰胺（DMF）为起始原料，亚磷酸三丁酯为偶联剂，合成了2，3，6，7-四（2’-氰乙硫基）网硫富瓦烯四硫纶（TTFTT），并以TTFTT为桥配体、邻菲啰啉为封端配体，制得了中心金属离子为Zn^2＋、Ni^2＋的四硫富瓦烯基四硫纶双金属配合物。中间物及产物经IR和元素分析进行了结构表征，其中目标产物元素分析的实测值与计算值比较吻合，说明合成路线合理可行。     

氧化作用控制“四硫富瓦烯-蒽”二元体系的荧光开关行为

利用Wittig反应将高荧光量子产率的蒽基团通过双键连接在四硫富瓦烯单元上,合成了二元共轭体系化合物TTFan.在氧化作用的控制下,四硫富瓦烯单元的给电子能力降低,TTFan的荧光发射强度增大至原来的十几倍,实现了荧光的“off-on”过程.     

Iron compounds electrodeposited onto a transparent semiconductor: Synthesis and characterisation by UV-vis spectroscopy

Homogeneous thin layers of lepidocrocite, green rust incorporating chloride anions (GRCl-GR1) and green rust incorporating sulphate anions (GRSO₄-GR2) were successfully electrodeposited onto tin dioxide substrate (SnO₂). The UV-vis spectroscopy absorbance, measured just after synthesis, increases linearly with the amount of iron compounds confirming that the electrodeposition is a homogeneous process. From the spectra, the absorption coefficients were determined for the three compounds. The monitoring by UV-vis spectroscopy measurements in real time of the oxidation in the air of the two unstable compounds, GRCl and GRSO₄, shows that the two green rusts have a different behaviour due to their own structure. The presence of an isobestic point in the case of GRSO₄ translates one equilibrium with its oxidised compound. This phenomenon is not observed for GRCl, however, the characteristic variation of the absorbance in the high wavelengths gives information on its oxidation reaction. From simple measurements, fruitful information on green rusts is obtained and this experimental system may be applied to other unstable solid compounds.     

Optimum reaction conditions for polypyrrole film deposition with some iron(III) compounds

The optimum reaction conditions for the deposition of smooth conductive polypyrrole (PP) films were monitored using a quartz crystal microbalance technique. This is for oxidative polymerization of pyrrole with some iron(III) compounds. The FeCl₃ · 6H₂O/pyrrole system in aqueous solution at 20 ± 0.5°C was examined in some detail. The effect of the initial molar ratio of the reactants on the yield and the growth rate of the PP film deposition was studied. The optimum molar ratio was found to be approximately 2.4 ± 0.1. A comparison between the growth rate of the PP films was made when different iron(III) compounds were used. The rate is shown to be affected by the nature of the anions in these compunds.     

Herbicide-intercalated zinc layered hydroxide nanohybrid for a dual-guest controlled release formulation

Herbicides, namely 4-(2,4-dichlorophenoxy) butyrate (DPBA) and 2-(3-chlorophenoxy) propionate (CPPA), were intercalated simultaneously into the interlayers of zinc layered hydroxide (ZLH) by direct reaction of zinc oxide with both anions under aqueous environment to form a new nanohybrid containing both herbicides labeled as ZCDX. Successful intercalation of both anions simultaneously into the interlayer gallery space of ZLH was studied by PXRD, with basal spacing of 28.7 Å and supported by FTIR, TGA/DTG and UV-visible studies. Simultaneous release of both CPPA and DPBA anions into the release media was found to be governed by a pseudo second-order equation. The loading and percentage release of the DPBA is higher than the CPPA anion, which indicates that the DPBA anion was preferentially intercalated into and released from the ZLH interlayer galleries. This work shows that layered single metal hydroxide, particularly ZLH, is a suitable host for the controlled release formulation of two herbicides simultaneously.     

水滑石类吸附剂的研究进展

水体中阴离子类污染物引起人们广泛注意,近年来,水滑石类化合物作为廉价可循环利用的吸附剂,对阴离子类污染物显示了良好的吸附特性。从水滑石类化合物(HTLcs)的制备、对阴离子的吸附等方面简要介绍了目前国内外对HTLcs的研究进展。     

Adsorption and desorption properties of cationic polyethylene film gels to organic anions and their regeneration

An investigation was undertaken on the adsorption and desorption properties of 2‐(dimethylamino)ethyl methacrylate grafted polyethylene (PE‐g‐PDMAEMA) films to anionic dye anions with one to three sulfonic groups in response to pH and temperature changes. The amounts of dye anions adsorbed on the PE‐g‐PDMAEMA films passed through the maximum values at about pH 3 because of an increase in the protonation of dimethylamino groups caused by a decrease in the pH value. The amounts of adsorbed dye anions decreased below pH 3 because the ionic strength increased with the addition of HCl to adjust the initial pH values of the aqueous dye solutions. The amounts of adsorbed dye anions decreased with an increase in the number of sulfonic groups in the dye molecules at the same pH value because electrostatic repulsion was generated between free sulfonic groups of the dye anions adsorbed onto the PE‐g‐PDMAEMA films and free dye anions in the medium. A large number of dye anions adsorbed were desorbed from the PE‐g‐PDMAEMA film with initial pH values above 11.0. The cyclic processes of adsorption at pH 3.0 and desorption at pH 11.0 were repeated without considerable fatigue. The PE‐g‐PDMAEMA films showed practically regenerative adsorption and desorption behavior in response to the pH changes. In addition, when the dye‐anion‐adsorbed PE‐g‐PDMAEMA films were alternately immersed in water at two different temperatures, dye anions were desorbed in water at higher temperatures without any chemical agents because of the deprotonation of dimethylamino groups and thermosensitive contraction of grafted PDMAEMA chains. These results indicate that PE‐g‐PDMAEMA films can be applied as regenerative ion‐exchange membranes for adsorption and desorption processes of anionic compounds in response to the pH and temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 381–391, 2006     

2,5-二氯-N-[2-(异丙基磺酰基)苯]嘧啶-4-胺的合成优化

以1-（异丙基磺酰基）-2硝基苯为起始原料,经过还原、亲核取代反应生成目标产物2,5-二氯-N-[2-（异丙基磺酰基）苯]-4-胺。并参考文献优化反应条件,如溶剂的选择与配比、反应物的配比、缚酸剂的选择与配比、投料方式、后处理重结晶溶剂的选择,得到纯度高、收率高的目标化合物,其经氢谱和质谱进行结构表征。该工艺具有反应时间短、成本较低、产物收率高的优势,在一定程度上符合工业化生产的要求。     

Adsorption and desorption properties of expanded poly(tetrafluoroethylene) films grafted with DMAEMA and their regeneration

An investigation was undertaken on the adsorption and desorption properties of the expanded poly (tetrafluoroethylene) (ePTFE) films grafted with 2‐(dimethylamino)ethyl methacrylate (DMAEMA) to anionic dye anions with one to three sulfonic groups in response to temperature changes. The amount of adsorbed metanil yellow (MY) anions increased with the grafted amount and most of the dimethylamino groups appended to the grafted PDMAEMA chains worked as an adsorption site to MY anions for the DMAEMA‐grafted ePTFE (ePTFE‐g‐PDMAEMA) films with the grafted amounts of higher than 1.1 mmol/g. When the dye‐anion‐adsorbed ePTFE‐g‐PDMAEMA films were alternately immersed in water at two different temperatures, dye anions were desorbed from the ePTFE‐g‐PDMAEMA films at higher temperatures without any chemical agents. The amount of desorbed dye anions increased with an increase in the temperature of water from 40 to 80°C. Desorption of dye anions is caused by either deprotonation of dimethylamino groups appended to the grafted PDMAEMA chains or thermosensitive contraction of the grafted PDMAEMA chains. These results indicate that the ePTFE‐g‐PDMAEMA films can be applied as a regenerative ion‐exchange membrane for adsorption and desorption processes of anionic compounds in response to the temperature change. The thermally regenerative ion‐exchange properties of the ePTFE‐g‐PDMAEMA films was superior to that of the PE‐g‐PDMAEMA films reported in our previous article in the fact that the total degree of desorption was higher for the ePTFE‐g‐PDMAEMA films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of 5‐sulfosalicylic acid‐intercalated layered double hydroxide and its effects on wood flour/polypropylene composites during accelerated UV weathering

In this study, 5‐sulfosalicylic acid (SA) anions have been intercalated into Mg₃Al‐NO₃ layered double hydroxide (LDH) to synthesize SA‐intercalated Mg₃Al‐NO₃‐LDH (LDH‐SA) by ion‐exchange reaction. Then, the effects of LDH, SA, and LDH‐SA on the photostability of wood flour/polypropylene (WF/PP) composites during accelerated ultraviolet (UV) weathering were investigated. The surface color, surface gloss, and mechanical properties of the composites during weathering were tested, accompanied by characterizations using SEM, ATR‐FTIR, and TG. The results showed that (1) SA anions completely replaced the anions in LDH and the thermal stability of LDH‐SA was considerably enhanced; (2) composites with LDH or LDH‐SA exhibited less color change, fewer surface cracks, better thermal stability, and less losses of mechanical properties than the control group; (3) LDH‐SA showed a long‐term efficiency and alleviated the photo‐oxidation of WF/PP composites successfully; (4) LDH‐SA blocked UV light by physical shield effect of the layer sheets, as well as the chemical absorbability of the interlayer anions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44597.     

二(三氯甲基)碳酸酯"一锅法"合成磺酰脲类除草剂

报道了以双(三氯甲基)碳酸酯(俗称三光气、固体光气,简称BTC)为起始原料合成磺酰脲类的方法.通过这些化合物与不同的胺反应,合成了9种新的磺酰脲化合物,并给出了这些化合物的红外光谱、核磁共振氢谱、元素分析等实验数据.原料2-甲氧羰基苯磺酰胺先与BTC反应生成邻甲氧羰基苯磺酰基异氰酸酯,再与2-(N-丁基)氨基-4-二甲胺基-6-甲氧基-1,3,5-均三嗪反应生成磺酰脲类化合物.避免了传统路线的种种缺点,具有收率高、含量高、成本低的特点.以2-甲氧羰基苯磺酰胺计,总收率为91.7%,原药纯度达96.4%.