Synthesis of Long-Chain SpirobenzopyransBearing a Monoazacrown ether

Two new long-chain spirobenzopyrans and their crowned derivatives were designed and synthesized.

Synthesis of Spirobenzopyrans Carrying a Monoaza-benzo-15-C-5 at the 8-position

Synthesis of spirobenzopyrans bearing monoazacrown at the 8-position is described.

Synthesis and Characterization of a New Bifunctional Dye Containing Spirobenzopyran and Cinnamoyl Moiety

A novel bifunctional dye containing spirobenzopyran and cinnaznoyl moiety has been prepared and its photochromic behavior following irradiation at different wavelengths of monochrome UV light was investigated.The colourless bifunctional dye in film or solution exhibits unusual photochromism through structural and geometrical transformation from spirobenzopyran to merocyanine accompanying with photocrosslinking reaction in cinnamoyl moieties. Two kinds of photochemical reaction were achieved by irradiation at the different wavelengths of monochrome UV light (275 nm, 365 nm) selectively. The photochromic process of the bifunctional dye was discussed and the dynamic behaviors of the decolorization process were investigated.

Preparation and study of photoswitchable fluorescence nanoparticles based on spirobenzopyran

The preparation and performance characterization of〈50 nm spirobenzopyran-based photochromic nanocomposites with photoswitchable fluorescence are presented.The nanocomposites were fabricated by means of a modifed miniemulsion polymerization process,in which the hydrophobic spirobenzopyran was covalently attached to the polymer chains and the matched fluorescent dyes were noncovalently embedded in the nanoscale cross-linked polymeric matrix,respectively.The obtained nanocomposites with a high relative fluorescence quantum yield（Q）exhibited superior fluorescent photoswitchable performance due to the effective photo-induced intermolecular energy transfer.The stability of photomerocyanine was also improved.

聚乙二醇支载的螺吡喃类光致变色化合物的合成及其逆光致变色性质

采用DCC缩合的方法,将吲哚啉螺苯并吡喃的衍生物和聚乙二醇相缩合,以聚乙二醇末端的羟基和吲哚啉螺苯并吡喃衍生物的羧基为反应活性基团,实现了带有羧基的螺吡喃类光致变色化合物支载到了聚乙二醇两端.通过引入亲水基团得到了水溶性较好的螺环类光致变色化合物.通过对产物的紫外-可见光谱的研究发现,产物具有良好的光致变色性质,在乙醇、丙酮和乙酸乙酯中皆具有良好的光致生色现象;产物可溶于水,在紫外光(波长365nm)照射时产生了光消色现象,具有明显的逆光致变色性质.该方法原料易得,反应条件容易控制,为光致变色新材料的研究和开发提供了新方法.

铜(Ⅱ)和水合肼双功能螺吡喃探针的合成及应用

以4-甲基-2,6-二甲酰基苯酚和1,3,3-三甲基-2-亚甲基吲哚啉为原料合成了能同时识别Cu^(2+)和水合肼的螺吡喃双功能探针L,其结构经~1H NMR、^(13)C NMR、FT-IR和H RMS进行了表征。通过紫外-可见光谱法、荧光光谱法、核磁共振和质谱研究了探针L在p H=7.40的Tris-HCl-乙醇溶液(1∶1,V/V)中与19种金属离子、18种阴离子及9种胺类化合物的识别特性。结果表明,在p H=7.40的Tris-HCl-乙醇溶液(1∶1,V/V)中,相对于其它干扰离子,L对Cu^(2+)和水合肼具有特异选择性和专一性,制成试纸能够实现肉眼识别检测含μmol/L Cu^(2+)的水样。尤为重要的是,制备的含L的TLC板能实现在紫外灯下对液体和气体水合肼的肉眼识别。将L应用于水样和药物中Cu^(2+)或水合肼测定的回收率在83.5%~111.0%之间,相对标准偏差(RSD)<4%,说明L适用于环境污染监测和药物分析检测,具有潜在的应用前景。

新型杯[4]芳烃衍生物的合成及其对镧系金属离子的识别研究

The synthesis of the novel host compound carrying two spirobenzopyran groups was described.Its structure was confirmed by（）1H NMR,IR and elemental analysis.It was shown that the novel host can recognize lanthanide ions selectively with significant spectral shifts in visible region and enhanced absorbance.Thus,the compound can be used to recognize lanthanide ions by naked eyes. The selectivity was relative to size-fit effect.The order of spectral changes was Yb3+>Er3+>Gd3+>Dy3+>Eu3+>Pr3+>La3+,which is opposite to the order of the radii of lanthanide ions.We discussed the possible binding mechanism with analyzing the different UV-Vis spectral changes resulted by addition of the investigated ions.

冠醚螺吡喃化合物的合成和光致变色性质

合成了四个新的6位带不同取代基的含冠醚结构单元吲哚啉螺苯并吡喃化合物(5a～5d),研究了其光致变色性质和离子诱导光致变色作用及取代基的影响.结果表明冠醚能稳定螺吡喃开环形式,碱金属离子对冠醚螺吡喃的生色有诱导作用;6位为吸电子基团时,螺吡喃开环形式的稳定性增加,而6位为推电子基团时,螺吡喃开环形式的稳定性降低.另外,就稳定螺吡喃开环体的作用来说,吲哚吡环上的取代基效应和苯并吡喃环上的正好相反.

6′-对位取代苯乙烯基吲哚啉螺吡喃的合成

利用2-亚甲基吲哚啉和取代水杨醛缩合得到十三种新的烷基苯乙烯基吲哚啉螺苯并吡喃。在苯并吡喃部分含有硝基的螺吡喃显示出逆光致变色行为,其它的则为普通光致变色化合物。同时,结果表明,化合物异构体的稳定性不仅取决于化合物本身的结构,而且还取决于介质环境的影响。

1,3,3,5-四甲基-6-硝基吲哚啉螺苯并吡喃的合成

以水杨醛、对甲基苯胺、3-甲基-2-丁酮等为初始原料,利用2-亚甲基吲哚啉中间体和5-硝基水杨醛缩合得到一种新的标题化合物,产率达到84.5%。该化合物通过红外、质谱、核磁共振表征其结构,初步证明该化合物具有光致变色性质。

1,3,3-三甲基-6'-(β-对氰基苯乙烯基)-8'-硝基吲哚啉螺吡喃的合成

通过相转移催化Ｗｉｔｔｉｎｇ反应合成５－（β－对氰基苯乙烯基）水杨醛衍生物（Ⅳ）；利用Ｆｉｓｈｅｒ碱与所得水杨醛衍生物缩合即得到题示化合物（Ⅴ）．化合物（Ⅳ）和（Ⅴ）未见文献报道，它们的结构通过元素分析、紫外可见光谱、红外光谱、氢核磁共振和已知反应等手段得到表征．初步考察螺吡喃单体在各种溶剂中的光致变色行为，结果表明，题示化合物（Ⅴ）在乙醇溶液中有明显光致变色性质．

6′－对位取代苯乙烯基吲哚啉吡喃紫外可见光谱

讨论了题示化合物在紫外可见光谱中的取代基效应，得到γ＿１（１／λ＿１）与｜σ＿ｐ｜相关性良好的线性关系。另外，通过对该类化合物部花菁稳定性的研究表明，８′－硝基对开环式的稳定性起着重要的作用。

螺环光致变色材料研究进展

本文首先介绍了螺共轭效应的基本理论。详细叙述了一螺化合物(螺吡喃、螺噁嗪)、双螺环、偶极螺σ-体系等光致变色化合物的合成及应用方面的研究进展,并对今后的研究方向提出了建议。

螺环光致变色材料研究进展(续)

本文首先介绍了螺共轭效应的基本理论。详细叙述了一螺化合物(螺吡喃、螺噁嗪)、双螺环、偶极螺σ-体系等光致变色化合物的合成及应用方面的研究进展,并对今后的研究方向提出了建议。