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.     

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.     

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.     

螺噁嗪化合物的合成及其光致变色性能的研究

合成了3种新型的螺噁嗪化合物,并通过IR,MS,1H NMR对其结构进行了表征。研究了1位和9’位上取代基对螺噁嗪光致变色性能的影响;不同溶剂对螺噁嗪最大吸收波长的影响;对螺噁嗪的热褪色速率进行了动力学的研究。结果表明,当螺噁嗪1位的取代基为柔性结构,9’位连接能形成更稳定共轭体系的取代基时有利于开环体热稳定性的提高。     

基于螺噁嗪的快速可逆力响应性聚合物的研究

机械力响应性聚合物的设计目前引起国内外广泛的关注,但力致变色聚合物中的力色团的设计仍然是巨大的挑战.本工作设计并合成了一种全新的螺噁嗪力色团结构,并将其引入以聚二甲基硅氧烷(PDMS)为基体的聚合成交联网络结构中.通过对螺噁嗪小分子溶液和聚合物的紫外光照射验证了螺噁嗪力色团结构在紫外光刺激下的响应性以及快速恢复性;拉伸...     

呜拉嗪及其衍生物的合成研究进展

稠环芳烃具有独特的电子性质和光学性质,在有机光电材料领域应用广泛.向稠环芳烃骨架中引入杂原子可改变其电子结构,进而改变其物理、化学、光、电和磁等性质.在众多的杂原子中,氮原子是稠环芳烃中最常见的掺杂原子.呜拉嗪是芘的等电子体,又称吲哚并[6,5,4,3-ija]喹啉,是一种新型氮杂稠环芳烃.近年来,呜拉嗪在染料敏化太阳能电池等领域表现出了潜在应用,随后有关呜拉嗪的合成方法研究备受关注.总结了近年来呜拉嗪及其衍生物的主要合成方法.     

螺噁嗪类光致变色化合物的合成研究进展

光致变色螺噁嗪;双光致变色螺噁嗪;螺噁嗪聚合物;合成;微波合成     

一种萘酰亚胺类荧光共振能量转移型光酸探针

合成了一种未见文献报道的键合螺噁嗪单元的1,8-萘二甲酰亚胺类化合物3,通过核磁共振谱和高分辨质谱确证了其结构.化合物在某些有机溶剂中和粉末状态下都能发射较强的荧光,研究了化合物3在二甲基亚砜中聚集诱导荧光增强(AIE)性质.在滤纸上以及用薄层层析硅胶(TLC)都能检测到螺噁嗪单元的光致变色现象;螺噁嗪单元酸致开环产物...     

新型含二茂铁基螺噁嗪类光致变色化合物的合成及其光谱研究

合成了一种新的含二茂铁基螺噁嗪类光致变色化合物，并研究了其吸收光谱和荧光光谱。发现在分子内引入二茂铁基团提高了热不可逆性，发生光致变色反应前后化合物结构的不同对其荧光特性影响很大。     

9’-(4-烯丙氧基苯甲酰氧基)吲哚啉螺萘并嗪的合成及其光谱性质

合成了 ７ 种９’羟 基吲哚啉 螺萘并 　嗪 衍 生物（ Ｈ Ｓ Ｐａ ～ｇ） 和７ 种９ ’（ ４烯丙 氧基 苯 甲酰氧基） 吲 哚啉螺 萘并　嗪 衍生物（ Ａ Ｓ Ｐａ ～ｇ） ． Ａ Ｓ Ｐａ ～ｇ 的１ Ｈ Ｎ Ｍ Ｒ 结果 表明 ，当１ 位是 苄基 或 乙基时，与 氮 相 连 的 亚 甲 基 的 ２ 个 氢 的 化 学 位 移 不 等 价， 属 Ａ Ｂ 自 旋 系 统． 此 外 随 溶 剂 极 性 增 加， Ａ Ｓ Ｐａ ～ｇ 的 萘 并 　 嗪 环 部 分 的 吸 收 发 生 蓝 移 ． 吲 哚 啉 环 氮 原 子 上 的 取 代 基 的 变 化 对 螺 　 嗪（ Ａ Ｓ Ｐａ） 在 ２９５ ｎ ｍ 处的吸收 无明显影 响， 但 当 ５ 位 上 的 氢被 甲 基和 氯 取 代时 ，此 处 的吸 收 发 生红移． 除 Ａ Ｓ Ｐｅ 的 萘并 　 嗪环 部分 的吸 收红 移外， 吲哚 环氮 原子 和５ 位上 的取 代基 的变 化对 螺 　嗪的萘并 　嗪环 部分吸收 无明显影 响，但使 成色体 的吸收红 移．     

Acidichromism of indolinospirooxazines in isopropanol

1,3,3-tnmethyl-spiro[mdolino-2,3'-[2H]naphtho[2,1-b] [1,4]oxazine(SP1) and 1,3,3-trimen-thyl-9-methoxy-spiro[indolino2,3'-[2H]naphtho[2,1-b] [ 1,4]oxazine] (SP2) react with hydrochloric acid to form the complex SP HCl in isopropanol solution at room temperature The absorption maxima of these complexes are 440 and 463 nm respectively In acidic media,the opening form of spirooxazine can react with hydrochloric acid to form the complex PMC HCl via zwittenon form The absorption spectra of PMC HCl are obviously hypsochromic shifted compared with the reported spectra of the complex in neutral media In the mean time,the thermal stability of the complex is increased.The first order kinetics for the decoloration process of the acidichromic product of the opening form was determined and the lifetimes of these products are 180 and 200 s,respectively.     

芬太尼类化合物的分子静电势研究

本文应用INDO波函数计算了三个芬太尼类化合物的分子静电势。酰胺氧原子周围均存在一个势阱很深的宽广的负电势区域, 是最重要的负电中心。 哌啶环4-位引入甲氧甲基后,增加了新的负电势区域。哌啶环1-位芳环周围具有宽广的正电势区域。 哌啶氮原子和酰胺氮原子附近存在较小的负电势区域。 基于计算出的静电势推测了三个化合物的镇痛作用的可能机理及药物结构与毒性的关系。     

An organic photochromic compound: (2S)‐2′‐ethoxy‐1,3,3‐trimethyl‐6′‐(piperidin‐1‐yl)spiro[indoline‐2,3′‐3′H‐naphtho[2,1‐b][1,4]oxazine]

In the course of our synthesis of hybrid photochromic compounds, the unexpected new organic photochromic title compound, C₂₉H₃₃N₃O₂, (I), was obtained. It is a derivative of the parent spirooxazine 1,3,3‐trimethyl‐6′‐(piperidin‐1‐yl)spiro[indoline‐2,3′‐3′H‐naphtho[2,1‐b][1,4]oxazine], (II). The 2′‐ethoxy group gives (I) different photochromic properties from its parent spirooxazine (II).     

Diethyl N,N-dimethylaminomethylenemalonate in the synthesis of fused heterocyclic systems

The reactions of diethyl N,N-dimethylaminomethylenemalonate ( 3 ) with N- and C- nucleophiles were studied. In the reaction of 3 with heterocyclic amines 4 , with the amino group attached at α-position in respect to the ring nitrogen atom, substitution of the dimethylamino group in 3 with the heterocyclic amino took place to give diethyl heteroarylaminomethylenemalonates 5 , which can cyclize into fused azino- 6 or azolopyrimidinones 7 . In the reaction of 3 with the compound with an active methylene group attached at α-position in regard to the ring nitrogen atom, such as pyridinylacetonitrile ( 8 ), ethyl pyridinyl- ( 9 ), and quinolinylacetate ( 10 ), fused quinolizines 11 and 12 , and benzo[c]quinolizine 13 were formed, respectively. Heterocyclic systems with an active or potentially active methylene group incorporated in the ring system, such as pyrazole 14 , pyrimidine 15 , and pyridine derivative 18 , gave with 3 fused pyranones 16, 17 , and 19 , and dihydroxynaphthalenes 22 and 23 naphtho[2,1-b]pyranones 24 and 25 .     

Hydrogen bond effect on the molecular vibrations of indole

On the basis of both a solvent effect study on the infrared spectrum and CNDO/2 calculations, the existence and structure of at least two dimeric species of indole is proposed. The shortest distance between the nitrogen atom and the pyrrole ring of the nearest indole in dimers is about 2.8 Å. Some fundamental bands sensitive to the NH…π interaction were assigned.     

Regiochemistry of nucleophilic substitution of 4-phenylsulfonyl tetrafluoropyridine with unequal bidentate nucleophiles

The regiochemistry of nucleophilic substitution of 4-phenylsulfonyl tetrafluoropyridine with unequal bidentate nucleophiles was investigated. The first nucleophilic substitution occurs at the 2-position of the pyridine ring by nitrogen nucleophile site (secondary or primary amine) followed by intermolecular ring closure at the geometrically accessible 3-position of the pyridine ring (by S, O and N nucleophiles). From this investigation, difluorinated tetrahydropyrido[3,4-b][1,4]oxazine, thiazine and pyrazine scaffolds were synthesized very readily by a one-pot annelation reaction of 4-phenylsulfonyl tetrafluoropyridine with appropriate unequal bidentate nucleophiles.     

Reactivities of vinyl derivatives of 3-mercaptoindole in reactions with alcohols

The addition of alcohols to 1-vinyl-3-vinylmercapto- and 1-vinyl-3-ethylmercaptoindole was accomplished in the presence of cobalt chloride. It was established that in the case of the divinyl derivative the addition of alcohols takes place only at the vinyl group attached to the nitrogen atom to give 1-(α-alkoxyethyl)-3-vinylmercaptoindoles. The relative reactivities of the vinylmercaptoindoles as a function of the substituent in the 3-position of the indole ring were studied kinetically. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 766–768, June, 1980.     

Cyclization of 2- and 3-indolythioalkanoic acids to novel indole-containing tricyclic ring systems

A series of 2- and 3-indolylthioalkanoic acids of various chain lengths were cyclized under dehydrative conditions affording tricyclic indole-containing ring systems wherein the third ring contains a sulfur atom attached to the 2- or 3-position of the indole ring. This methodology affords entry into the novel thiepino[3,2-b]indole, thiocino[2,3-b]indole and thiocino[3,2-b]indole ring systems.     

Spiropyrans and spirooxazines 9. Photochromism of novel cationic spirooxazines

Novel photochromic spirooxazinoquinolines, their cationic derivatives, and cationic spirooxazine containing pyridinium cation in the aliphatic side chain of the oxazine moiety of the molecule were synthesized. Quaternization of the quinoline fragment leads to a substantial increase in the thermal stability of the merocyanine isomers of cationic spirooxazines and a decrease in the efficiency of photocoloration. Pyridinium cation in the aliphatic side chain of the spirooxazine does not exert a substantial effect on the kinetics of photocoloration and thermal bleaching.