微波法快速合成光致变色螺(口恶)嗪

螺嗪(Ｓｐｉｒｏｘａｚｉｎｅ)是20世纪70年代在螺吡喃基础上发展起来的一类具有良好光致变色性能的化合物,具有很高的抗疲劳性和光稳定性,具有潜在的商业应用前景[1-4],可用作光信息储存材料和光致变色镜片(ＰｈｏｔｏｃｈｒｏｍｉｃＬｅｎｓ)。6 哌啶取代的吲哚啉螺萘并嗪[5-11]相对于未取代的母体化合物具有更优异的光致变色性能,但是文献中的合成方法步骤繁琐、反应时间长、产率较低。本文利用微波合成了6 哌啶基(氰基)吲哚啉螺嗪,合成路线如下:1　实验部分1.1　仪器和试剂显微熔点仪(四川大学科仪厂),温度计未经校正;美国Ｐ…     

Preparation and photochromic properties of oligomeric poly(dimethylsiloxane) with the spiropyran or spirooxazine moiety in the side chain

Spirobenzopyran 1 , with the 3-(diethoxymethylsilyl)-propyl group at the N atom, was synthesized. The condensation reaction of the spiropyran 1 and diethoxydimethylsilane gave oligomeric poly(dimethylsiloxane) with the spiropyran moiety in the side chain. The oligomer was photochromic; its colour changed from colorless to purple-red on uv irradiation and the color faded on visible irradiation or on standing in the dark. The half-decay time of the thermal decoloration was about twice that of monomeric spiropyran dissolved in the dimethylsiloxane oligomer. Photochromic poly(dimethylsiloxane) with the spirooxazine moiety in the side chain was also prepared.     

超声波辐射下光致变色螺噁嗪类化合物的快速合成

在超声波辐射条件下,以Fischer碱、1-亚硝基-2,7-二羟基萘为原料,无水乙醇为溶剂快速合成了三个螺嗪类光致变色化合物,通过1 H NMR、IR对目标产物的结构进行了表征,讨论了超声辐射时间对合成产率的影响,利用超声波法合成螺噁嗪类光致变色化合物反应速率快、产率有所提高.     

N-乙基-9′-溴丁氧基螺噁嗪的合成及其化学改性PMMA的结构与光致变色性能

合成了分子结构中含活性C—Br键的N-乙基-9′-正溴丁氧基螺噁嗪(Br-SO),利用Br-SO分子结构中的化学基团C—Br与部分水解的聚甲基丙烯酸甲酯(hPMMA)反应制备含SO的PMMA高分子化合物(SO-hPMMA)。采用1 HNMR和IR对Br-SO结构进行了表征,研究了Br-SO、SO-hPMMA的光致变色性能及其影响因素。研究表明:Br-SO、SO-hPMMA均具有良好的光致变色性能,且SO-hPMMA的热稳定性明显高于Br-SO。     

The effect of substituents and polymer media on photochromism kinetics of indolinospironaphthoxazine

The effect of substituents in indoline moiety and polymer media on photochromism and thermal decay processes of spirooxazine (ASP) was investigated. The thermal decoloration rate was decreased with increasing steric hindrance of substituents in l-position of indoline moiety. The stability of the colored forms was improved when the hydrogen in the 5-position of indoline moiety was replaced with electron-donating groups and was decreased when substituted by electron-withdrawing groups. In addition, the stability of the colored forms was related to properties of polymer media. The thermal decay rate decreased with an increase in the polarity and rigidity of polymer media. The themal decay kinetics of the colored forms obeyed biexponential decay law.     

Synthesis and properties of photochromic liquid-crystalline polyacrylates containing a spirooxazine group

The novel photochromic liquid-crystalline polyacrylates containing a spirooxazine group were synthesized. The photochromic polymer containing (4-penta- methyleneoxy)biphenylene moiety at the 5-position of spironaphthoxazine showed nematic phase from 122.9 to 133.8°C. The photochromic polymer containing undeca- methylene instead of pentamethylene showed smectic phase from 93.1 to 169.7°C. On the other hand, the photochromic polymer containing both undecamethylene as a spacer and spironaphthoxazine-bound biphenylene moiety at 9′-position did not show any liquid crystallinity. All spirooxazine-containing liquid-crystalline polymers showed photochromism in the solid state at room temperature. Because the shape of the absorption spectra of the photochromic quenched liquid-crystalline polymer films was almost the same as those of the photochromic amorphous polymer films, the photochromic properties did not depend on the mesophase in the polymers examined. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3513–3522, 1999     

8′-取代吲哚螺噁嗪光致变色化合物的合成及光谱性质

通过在螺噁嗪结构中的萘环8′-位上引入不同的取代基,合成了三种螺噁嗪光致变色化合物;对三种产物的光谱性质进行了对比研究,并考察了其光照褪色速率和抗疲劳性能.结果表明:改变8′-位取代基,合成化合物的闭环吸收峰的位置几乎不受影响,但开环吸收峰发生显著变化,随着取代基极性增加明显红移.增加溶剂的极性,可使同一化合物的开环吸收峰红移.     

Crystal Structure and Photochromism in Paint of 1,3,3-Trimethyl-6'-dihydro-indolinyl- spiro[2,3'-[3H]-naphtho[2,1-b][1,4]]oxazine

The title compound 2 (C30H27N3O, Mr = 445.55) has been synthesized and its structure was determined by X-ray crystallography method. The crystal is of monoclinic, space group P21/c with a = 17.520(15), b = 8.640(7), c = 15.439(13) , β = 98.642(14)°, V = 2310(3) 3, Dc = 1.281 g/cm3, μ = 0.780 mm-1, F(000) = 944, Z = 4, the final R = 0.0671 and wR = 0.1790 for 1952 observed reflections with I > 2σ(I). X-ray analysis revealed that the interatomic distance of C(20)O(1) is 1.464(4) , longer than that of the normal CO bond (1.41～1.43 ) in the six-membered heterocycle, but this kind of change coincides with other spiro compounds. The six-membered heterocycle containing spiro Csp3O is nonplanar. The UV-vis spectra of the title compound in polymer films showed that it exhibits excellent photochromic property.     

螺噁嗪光致变色反应机理研究进展

20世纪80年代中期以来, 关于螺噁嗪在光致变色过程中的光化学和光物理现象的研究非常活跃. 综述了近20年来对溶液中的螺噁嗪、晶体螺噁嗪以及固体介质中的螺噁嗪的光致变色机理研究结果, 同时介绍了实验研究方法和理论研究方法在螺噁嗪光致变色过程研究中的应用, 分析了取代基对光致变色性质的影响. 阐述了机理研究对新型螺噁嗪设计合成的重要指导意义.     

Enhancement of the Photochromic Performance of Spirooxazine in Sol-Gel Derived Organic-Inorganic Hybrid Matrices by Additives

Organic-inorganic hybrid materials synthesized via sol-gel processing are excellent solid matrices for photochromic dyes like spirooxazine, and the photochromic performance can be further enhanced by introducing suitable additives. This work describes the effects of additives on the photochromic intensity (ΔA ₀), decolouration rate (k) and photostability of spirooxazine in sol-gel derived organic-inorganic hybrid matrices. They include fluoroalkylsilane (FAS), bisphenolA (BPA) and methyl-imidazole (MI). FAS enhances both ΔA ₀ and photostability, but has little effect onk. The higher the content of BPA, the higher the ΔA ₀ and the higher the photostability, but the lower thek. The effect of MI on ΔA ₀ andk is not so considerable as that of BPA and is a little complicated, while significant improvement in photostability is achieved by the addition of MI at an optimum concentration with the presence of BPA at a higher content.