WO2017041642A1 - 基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用 - Google Patents

基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用 Download PDF

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WO2017041642A1
WO2017041642A1 PCT/CN2016/097320 CN2016097320W WO2017041642A1 WO 2017041642 A1 WO2017041642 A1 WO 2017041642A1 CN 2016097320 W CN2016097320 W CN 2016097320W WO 2017041642 A1 WO2017041642 A1 WO 2017041642A1
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meta
saa
compound according
hydrazinopyridazine
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French (fr)
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唐本忠
王志明
赵祖金
秦安军
王京
李小东
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香港科技大学深圳研究院
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C241/02—Preparation of hydrazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/10—Hydrazines
    • C07C243/12—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms
    • C07C243/16—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C243/18—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/88—Hydrazones having also the other nitrogen atom doubly-bound to a carbon atom, e.g. azines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence

Definitions

  • the present invention relates to the field of analysis and detection technology, and more particularly to a hydrazine-based oxazine structure compound based on meta-linking, a preparation method and application thereof.
  • alkali metals, alkaline earth metals, transition metals and heavy metal elements are widely found in nature. They play a very important role in environmental, biological, medical, and chemical sciences, and have played a huge role and role.
  • Beneficial metal ions play an important role in the life system. Lack of them will affect normal physiological activities, and organisms need appropriate intake; while harmful metal ions have strong toxicity, become potential carcinogenic and teratogenic factors, for biological cells, The toxicity of the tissue is very large, which can cause abnormalities in enzymes and biological protein synthesis related to metabolism. Therefore, rapid, simple and accurate quantitative analysis and identification of various metal ions will help to study important life processes and timely replenishment of missing metal elements and monitoring of environmental factors such as water quality and soil. And a growing point of demand for the public.
  • the fluorescent molecules Since the identification and application of most metal ions must be carried out in an aqueous environment, it is generally required that the fluorescent molecules have a certain water solubility to improve the complexation or catalytic ability with metal ions to shorten the detection time and improve the detection efficiency. .
  • most of the fluorescent chromophore's aromatic ring structure is mostly hydrophobic, and it is still in the form of aggregates (such as micelles, nanoparticles, etc.) in water or biological media, and it will exhibit typical fluorescent enthalpy.
  • the phenomenon of extinction (ACQ) causes the switching ratio of the fluorescent probe to be inconspicuous, which is not conducive to the practical application of ion sensing.
  • a pyridazine compound is a general term for a conjugated unsaturated six-membered heterocyclic or hetero atom compound containing one or several nitrogen atoms. It includes both common pyridine, pyrimidine, triazine, and thiazine structures, as well as gradual Aryl-conjugated ruthenium, osmium, and amide structures of interest. Due to the obvious lone pair electrons in the nitrogen structure of the molecular structure, it can form coordination with the outer space orbitals of many metals, and supplemented by atoms such as oxygen and sulfur in the ortho position, which is gradually active in the field of fluorescence detection. .
  • Salicylaldazine is a typical hydrazine-based azine structure with obvious AIE properties, and can recognize metal ions in aqueous systems.
  • SAA fluorescent color of SAA is mainly yellow fluorescent, which has great modification space and value compared with the potential advantages of red fluorescent probe in biological field.
  • the object of the present invention is to provide a hydrazine-based oxazine structure compound based on meta-linking, a preparation method and application thereof, and solve the problem that the hydrazine azine structure compound in the prior art is mainly yellow fluorescence and cannot be realized as red Problems with fluorescent probe applications.
  • a hydrazine-based oxazine structure compound based on a meta-link the structural formula is as follows:
  • R is selected from the group consisting of the following structures One of them, that is, the R group is defined to introduce cyanobenzene, triphenylethylene or tetraphenylethylene, diphenylamine or triphenylamine, carbazole, etc. in the aldehyde group meta position (or hydroxy para position) of salicylaldehyde.
  • An aromatic group and a derivative thereof, R 1 to R 4 each represent an arbitrary substitution position bonded to a benzene ring structure, and R 1 to R 4 are each selected from the group consisting of hydrogen, alkyl, hydroxy, alkoxy, nitro and cyanide.
  • Base amino, mercapto, halogen atom, phenyl, tolyl, naphthyl, furyl, thienyl, pyrrolyl, pyridyl, pyranyl, quinolyl, decyl, carboxylic acid or carboxylic acid derivatives, One of oxazolyl or anilino and its derivatives.
  • the alkyl group and the alkoxy group have 1 to 12 carbon atoms, respectively.
  • R is: That is, the R group is a cyanobenzene and a derivative structure thereof,
  • R 1 and R 2 are respectively at the ortho, meta or para position of the cyano group, and R 1 and R 2 are respectively selected from the group consisting of hydrogen, alkyl, hydroxy, alkoxy, nitro, cyano, amino, fluorenyl, Halogen atom, phenyl, tolyl, naphthyl, furyl, thienyl, pyrrolyl, pyridyl, pyranyl, quinolyl, decyl, carboxylic or carboxylic acid derivatives, carbazolyl or anilino One of its derivatives.
  • the alkyl group and the alkoxy group have 1 to 12 carbon atoms, respectively.
  • R is:
  • the R group is triphenylethylene or tetraphenylethylene and a derivative structure thereof;
  • R 1 to R 4 are respectively at the ortho, meta or para position of the benzene ring, and R 1 to R 4 are each selected from the group consisting of hydrogen, alkyl, hydroxy, alkoxy, nitro, cyano, amino, Sulfhydryl, halogen atom, phenyl, tolyl, naphthyl, furyl, thienyl, pyrrolyl, pyridyl, pyranyl, quinolyl, decyl, carboxylic or carboxylic acid derivatives, carbazolyl or One of an anilino group and a derivative thereof.
  • the alkyl group and the alkoxy group have 1 to 12 carbon atoms, respectively.
  • R is:
  • the R group is diphenylamine or triphenylamine and a derivative structure thereof;
  • R 1 to R 4 are respectively at the ortho, meta or para position of the benzene ring, and R 1 to R 4 are each selected from the group consisting of hydrogen, alkyl, hydroxy, alkoxy, nitro, cyano, amino, fluorenyl, Halogen atom, phenyl, tolyl, naphthyl, furyl, thienyl, pyrrolyl, pyridyl, pyranyl, quinolyl, decyl, carboxylic or carboxylic acid derivatives, carbazolyl or anilino One of its derivatives.
  • the alkyl group and the alkoxy group have 1 to 12 carbon atoms, respectively.
  • R is:
  • the R group is a carbazole and a derivative structure thereof
  • R 1 to R 4 are respectively at the ortho, meta or para position of the benzene ring, and R 1 to R 4 are each selected from the group consisting of hydrogen, alkyl, hydroxy, alkoxy, nitro, cyano, amino, fluorenyl, Halogen atom, phenyl, tolyl, naphthyl, furyl, thienyl, pyrrolyl, pyridyl, pyranyl, quinolyl, decyl, carboxylic or carboxylic acid derivatives, carbazolyl or anilino One of its derivatives.
  • the alkyl group and the alkoxy group have 1 to 12 carbon atoms, respectively.
  • R 1 to R 4 may be respectively selected from one of the 29 species shown in the following structural formula or a hydrogen atom:
  • the above preparation method of the meta-linking-based hydrazine-based azine structure compound comprises the following steps:
  • reaction process in this step is a prior art, and details are not described herein again;
  • the salicylaldehyde derivative and hydrazine hydrate are heated to 20 ° C ⁇ 150 ° C under the reaction solvent and catalyst conditions, the reaction is cooled to room temperature after 1 hour to 24 hours, and most of the solvent is removed to precipitate crystals or powder, the column Chromatography or recrystallization to obtain a fluorenylpyridazine structure compound based on a meta link, wherein the precipitated crystal or powder is yellow or red.
  • the recrystallization solvent is preferably tetrahydrofuran, ethanol, toluene, DMF or the like, and most preferably ethanol.
  • the reaction solvent is selected from the group consisting of methanol, ethanol, acetic acid, tetrahydrofuran, toluene, benzene, chloroform, dichloromethane, N,N-dimethylformamide, N,N-dimethyl A mixed system of acetamide, N-methylpyrrolidone or a combination of the two; most preferably ethanol and a mixed system thereof with other solvents.
  • the catalyst is selected from the group consisting of a protonic acid such as dilute sulfuric acid, dilute nitric acid, hydrochloric acid or acetic acid, or a Lewis acid such as ferric chloride, titanium tetrachloride or silica gel, or a solid acid, or the above plurality of Mixed system; most preferred is acetic acid.
  • a protonic acid such as dilute sulfuric acid, dilute nitric acid, hydrochloric acid or acetic acid
  • a Lewis acid such as ferric chloride, titanium tetrachloride or silica gel, or a solid acid, or the above plurality of Mixed system; most preferred is acetic acid.
  • step S2 the heating is carried out until the temperature is from 30 ° C to 90 ° C; and the reaction time is from 6 hours to 12 hours.
  • the molar fraction of the reaction substrate in the step S2 is adjusted according to the adjustment of the final product prepared.
  • the above-described meta-linking-based hydrazine-based pyridazine structural compound can be used as a red fluorescent probe, that is, it can be used to prepare a red fluorescent probe (ie, a red fluorescent dye).
  • the meta-linking-based hydrazine-based oxazine structure compound and the preparation method and application thereof have the following beneficial effects: by introducing the meta-position of the imino group or the phenolic hydroxyl group of the classical salicylaldehyde azine (SAA) By extending the conjugated substituents, a new class of red fluorescent probe molecules is obtained, in which the R group is defined as an aryl group such as cyanobenzene, triphenylethylene or tetraphenylethylene, diphenylamine or triphenylamine or carbazole.
  • SAA salicylaldehyde azine
  • R 1 to R 4 each represent a substituent structure attached to an arbitrary substitution position on a benzene ring structure, and are respectively selected from a hydrogen group, an alkyl group, an alkoxy group, and an aromatic group, and a corresponding derivatized structure.
  • the new probe structure has excellent aggregation-induced luminescence properties, which can be used for selective quantitative identification of metal ions under water conditions.
  • red fluorescent probes have important applications and significance in the fields of chemical sensing, biological analysis, ion detection and the like.
  • Figure 1A is a fluorescence spectrum of CN-SAA in different polar solvents
  • Figure 1B is a fluorescence spectrum of CN-SAA in a mixed system of different ratios of tetrahydrofuran and water;
  • 2A is an experiment of CN-SAA on different metal ions and interfering ions
  • 2B is a fluorescence spectrum of CN-SAA for different levels of metal ions
  • Figure 3A is a fluorescence spectrum of TPE-SAA in different polar solvents
  • Figure 3B is a fluorescence spectrum of TPE-SAA in a mixed system of different ratios of tetrahydrofuran and water;
  • Figure 4A shows the experiment of different metal ions and interfering ions by TPE-SAA
  • Figure 4B is a fluorescence spectrum of TPE-SAA for different levels of metal ions
  • Figure 5A is a fluorescence spectrum of TPA-SAA in different polar solvents
  • Figure 5B is a fluorescence spectrum of TPA-SAA in a mixed system of different ratios of tetrahydrofuran and water;
  • Figure 6A shows the experiment of different metal ions and interfering ions by TPA-SAA
  • Figure 6B is a fluorescence spectrum of TPA-SAA for different levels of metal ions
  • Figure 7A is a fluorescence spectrum of Cz-SAA in different polar solvents
  • Figure 7B is an ion experiment of Cz-SAA in a mixed system of different ratios of tetrahydrofuran and water;
  • Figure 8A shows the experiment of Cz-SAA in different metal ions and interfering ions
  • Figure 8B is a fluorescence spectrum of Cz-SAA for different levels of metal ions.
  • the object of the present invention is to propose a novel type of salicylaldehyde pyridazine (SAA)-based fluorescent probe-based material based on a meta-linked hydrazine-based azine structure compound.
  • SAA salicylaldehyde pyridazine
  • the solid-state spectrum of such oxazine derivatives is extended to the red fluorescent region by introducing a conjugated group having a certain electron-withdrawing ability at the meta-position of the salicylaldehyde oxime (or the para position of the phenolic hydroxyl group), and It exhibits excellent aggregation-induced luminescence properties and enables selective identification and quantitative detection of metal ions under water conditions.
  • the newly prepared meta-modified hydrazine-based hydrazine-based red probe has important applications and significance in the fields of chemical sensing, biological analysis, and ion detection.
  • the structural formula of the meta-linking-based hydrazine-based azine structure compound of the present invention is as follows:
  • the R group is defined to introduce a aryl group such as cyanobenzene, triphenylethylene or tetraphenylethylene, diphenylamine or triphenylamine or carbazole at the aldehyde group (or hydroxy para position) of salicylaldehyde.
  • a group or a derivative thereof, R 1 to R 4 each represent an arbitrary substitution position bonded to a benzene ring structure, and are respectively selected from the group consisting of hydrogen, alkyl, hydroxy, alkoxy, nitro, cyano, amino, fluorenyl, halogen.
  • the above salicylaldehyde derivative is condensed with hydrazine hydrate by a suitable solvent and temperature under the addition of a suitable catalyst to obtain a final product.
  • the reaction solvent is preferably methanol, ethanol, acetic acid, tetrahydrofuran, toluene, benzene, chloroform, dichloromethane, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC) and N.
  • the catalyst is preferably a protonic acid such as dilute sulfuric acid, dilute nitric acid, hydrochloric acid or acetic acid, or ferric chloride a Lewis acid such as titanium tetrachloride or silica gel, or a solid acid, or a multicomponent mixed system, most preferably acetic acid;
  • the temperature is preferably 20 ° C to 150 ° C, most preferably 30 ° C to 90 ° C; and the reaction time is preferably 1 hour. 24 hours, most preferably 6 hours to 12 hours; recrystallization solvent, preferably tetrahydrofuran, ethanol, toluene, DMF, etc., most preferably ethanol.
  • Figure 1A shows the fluorescence spectra of CN-SAA at different polarities. With the change of polarity, the ratio of alcohol-type emission (near 426 nm) and ketone emission (near 579 nm) of CN-SAA changes significantly.
  • 2A and 2B show the experimental results of the selection of different metal ions in aqueous solution by CN-SAA. It is found by comparison that the fluorescent probe has a specific response to copper ions, and its fluorescence intensity near 579 nm is significantly reduced. There is a certain linear relationship; by interfering with the experimental results, it can be seen that the presence of other ions has little effect on the detection of copper ions.
  • TPE-SAA tetrastyryl salicylaldazine
  • Figure 3A shows the fluorescence spectra of TPE-SAA at different polarities.
  • the aggregate state is mostly ketone emission, so the aggregation luminescence phenomenon at this point is detected.
  • FIG. 1 shows the fluorescence spectra of TPE-SAA at different polarities.
  • ESIPT launch For the ESIPT molecule, the aggregate state is mostly ketone emission, so the aggregation luminescence phenomenon at this point is detected.
  • TPE-SAA has AIE properties.
  • the ESIPT and AIE properties suggest that TPE-SAA has the potential for fluorescent probes.
  • Example 8 ESIPT and AIE properties of TPA-SAA
  • the fluorescence spectra of TPA-SAA at different polarities show a significant change in the ratio of alcoholic emission (near 438 nm) and ketone emission (near 632 nm) of TPA-SAA as a function of polarity.
  • the aggregate state is mostly ketone emission, so the aggregation luminescence phenomenon at this point is detected.
  • TPA-SAA has AIE properties.
  • the nature of ESIPT and AIE suggests that TPA-SAA has the potential for fluorescent probes.
  • the experimental results of the selection of different metal ions in the aqueous solution of TPA-SAA show that the fluorescent probe has a specific response to copper ions, and the fluorescence intensity near 627 nm is significantly reduced. There is a certain linear relationship; by interfering with the experimental results, it can be seen that the presence of other ions has little effect on the detection of copper ions.
  • the fluorescence spectra of Cz-SAA at different polarities vary with polarity, but due to the relatively poor solubility of Cz-SAA, the fluorescence process is relatively complex, and alcoholic emission can still be observed (418nm).
  • the ratio of ketone emission (near to 600 nm) and ketone emission (near 600 nm) changed significantly, which is a typical ESIPT emission.
  • the aggregate state is mostly ketone emission, so the aggregation luminescence phenomenon at this point is detected.
  • Fig. 7A the fluorescence spectra of Cz-SAA at different polarities vary with polarity, but due to the relatively poor solubility of Cz-SAA, the fluorescence process is relatively complex, and alcoholic emission can still be observed (418nm).
  • the ratio of ketone emission (near to 600 nm) and ketone emission (near 600 nm) changed significantly, which is a typical ESIPT emission.
  • the aggregate state
  • Example 12 Responsiveness of Cz-SAA to metal ions
  • the fluorescent probe has a specific response to copper and iron ions (ultraviolet absorption spectrum can distinguish the two) ), its fluorescence intensity near 600nm is significantly reduced, and there is a certain linear relationship; by interference experiment results, it can be seen that the presence of other ions has little effect on the detection of copper ions.

Abstract

提供一种基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用，该化合物可以作为红色探针，具有优异的聚集诱导发光特性，能够用于水系条件下对金属离子的选择性定量识别；利用具有取代基团推拉电子能力变化，实现了固态荧光有效红移和对此类ESIPT型分子醇酮比例、离子选择性及检测限的调节，此类红色荧光探针在化学传感、生物分析、离子检测等领域具有重要用途和意义。

Description

基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用 技术领域
本发明涉及分析和检测技术领域，更具体地说，涉及一种基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用。
背景技术
自然界中广泛存在着多种碱金属、碱土金属、过渡金属和重金属元素等，它们在环境、生物、医学、化学科学中都扮演了非常重要的角色，发挥了巨大的功能和作用。有益金属离子在生命体系中具有重要作用，缺乏它们将影响正常的生理活动，生物体需要适量摄入；而有害金属离子具有较强的毒性，成为潜在致癌和致畸性因子，对生物细胞、组织的毒性非常大，可使与新陈代谢相关的酶、生物蛋白质合成等出现异常。因此，对各种金属离子快速、简便、准确地定量分析和识别，将有助于研究重要的生命过程及对所缺金属元素及时补充和对水质、土壤等环境因素的监控，已成为科学界和大众需求的一个增长点。
目前，在实验室范围内主要采用原子吸收光谱法、原子发射光谱法、ICP-质谱法、X射线荧光光谱法、离子选择性电极和伏安法及库仑计法等，虽然对金属离子的检测限都可以达ppb(10-9)级，但是这些仪器分析方法的分析步骤较为繁杂、分析仪器较为昂贵、采样频率较低、存在费时、不具代表性及样品不易保存等。例如，在有些情况下，需要及时知道水环境污染情况，以便及时迅速的制定相应的处理对策，这种过度依赖大型仪器的方法受到了限制。相对于复杂的流程，方便、快捷、直观、可视化的荧光分子探针法逐步受到重视，并通过结构的不断优化，实现对对特定金属离子的选择性识别和定量分析。
由于大部分金属离子的识别与应用研究都必须在水系环境下进行，所以一般要求荧光分子要适当地具有一定水溶性，以提高与金属离子络合或催化能力，以缩短检测时间，提高检测效率。但是，大部分荧光生色团的芳香环结构多为疏水基元，在水系或生物介质中仍然是以聚集体形式存在的(如胶束、纳米粒子等形式)，都会表现出典型的荧光猝灭现象(ACQ)，导致荧光探针的开关比不明显，不利于离子传感的实际应用。2001年，唐本忠院士提出“聚集诱导发光(AIE)”的新观念，通过控制分子的聚集形态实现对其荧光性质的有效调节。基于此，大部分具有高效率开关比的“淬灭型”和“点亮型”AIE型探针被不断开发出来。
吖嗪类化合物是对包含有一个或几个氮原子的共轭不饱和六元杂环或杂原子化合物的总称，它既包括常见的吡啶、嘧啶、三嗪和噻嗪类结构，也包含逐渐受到关注的芳基共轭型的腙、肼、酰胺类结构。由于分子结构中氮原子存在明显的孤对电子，能够和许多金属的外层空轨道形成配位作用，再辅以邻位的氧、硫等原子，其在荧光检测领域的中研究逐渐活跃起来。水杨醛吖嗪(SAA)为典型的联肼基吖嗪结构，具有明显的AIE性质，在水系体系下能够实现对金属离子的识别。但是在荧光传感和生物成像等应用领域存在明显不足：如，SAA的荧光颜色主要黄色荧光，相对于红色荧光探针在生物领域潜在优势来讲，其有很大的改性空间和价值。
发明内容
本发明的目的在于提供一种基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用，解决了现有技术中的联肼基吖嗪结构化合物主要为黄色荧光而无法实现作为红色荧光探针应用的问题。
本发明解决技术问题所采用的技术方案是：一种基于间位链接的联肼基吖嗪结构化合物，其结构式如下：
Figure PCTCN2016097320-appb-000001
其中，R选自下述结构的基团
Figure PCTCN2016097320-appb-000002
Figure PCTCN2016097320-appb-000003
中的一种，即R基被限定为在水杨醛的醛基间位(或羟基对位)引入氰基苯、三苯基乙烯或四苯基乙烯、二苯胺或三苯胺、咔唑等芳香基团及其衍生结构，R1～R4分别表示连接在苯环结构中的任意取代位置，且R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。优选地，烷基和烷氧基的碳原子数分别为1～12。
在本发明的联肼基吖嗪结构化合物中，R为：
Figure PCTCN2016097320-appb-000004
即R基为氰基苯及其衍生结构，
其中，R1和R2分别位于氰基的邻位、间位或对位，R1和R2分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。优选地，烷基和烷氧基的碳原子数分别为1～12。当R基为氰基苯及其衍生结构时，其优选的结构的化合物为：
Figure PCTCN2016097320-appb-000005
在本发明的联肼基吖嗪结构化合物中，R为：
Figure PCTCN2016097320-appb-000006
即R基为三苯基乙烯或四苯基乙烯及其衍生结构；
其中，取代基R1～R4分别位于苯环的邻位、间位或对位，R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。优选地，烷基和烷氧 基的碳原子数分别为1～12。当R基为三苯基乙烯或四苯基乙烯及其衍生结构时，其优选的结构化合物为：
Figure PCTCN2016097320-appb-000007
在本发明的联肼基吖嗪结构化合物中，R为：
Figure PCTCN2016097320-appb-000008
即R基为二苯胺或三苯胺及其衍生结构；
其中，R1～R4分别位于苯环的邻位、间位或对位，R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。优选地，烷基和烷氧基的碳原子数分别为1～12。当R基为二苯胺或三苯胺及其衍生结构时，其优选的结构化合物为：
Figure PCTCN2016097320-appb-000009
在本发明的联肼基吖嗪结构化合物中，R为：
Figure PCTCN2016097320-appb-000010
即R基为咔唑及其衍生结构；
其中，R1～R4分别位于苯环的邻位、间位或对位，R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。优选地，烷基和烷氧基的碳原子数分别为1～12。当R基为咔唑及其衍生结构时，其优选的结构化合物为：
Figure PCTCN2016097320-appb-000011
需要说明的是，上述所有结构式中，其中R1～R4优选结构可以分别选自下述结构式中所示29种中的一种或氢原子：
Figure PCTCN2016097320-appb-000012
上述的基于间位链接的联肼基吖嗪结构化合物的制备方法，包括如下步骤：
S1、通过耦联、取代和缩合反应得到水杨醛衍生物：
Figure PCTCN2016097320-appb-000013
需要说明的是，该步骤反应过程为现有技术，这里不再进行详细赘述；
S2、将水杨醛衍生物与水合肼在反应溶剂和催化剂条件下，加热至20℃～150℃，反应1小时～24小时后冷却至室温，处理掉大部分溶剂后析出晶体或粉末，柱层析或重结晶后得到基于间位链接的联肼基吖嗪结构化合物，其中析出的晶体或粉末呈黄色或红色，
Figure PCTCN2016097320-appb-000014
需要说明的是，如果采用重结晶方式，重结晶溶剂优选四氢呋喃、乙醇、甲苯、DMF等，最优选乙醇。
进一步优选地，在步骤S2中，所述反应溶剂选自甲醇、乙醇、乙酸、四氢呋喃、甲苯、苯、氯仿、二氯甲烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮或其二者、三者的混合体系；最优选乙醇及其与其它溶剂的混合体系。
进一步优选地，在步骤S2中，所述催化剂选自稀硫酸、稀硝酸、盐酸、醋酸等质子酸、或三氯化铁、四氯化钛、硅胶等路易斯酸、或固体酸、或上述多元混合体系；最优选醋酸。
进一步优选地，在步骤S2中，加热至温度为30℃～90℃；反应时间为6小时～12小时。
需要说明的是，步骤S2中反应底物的摩尔分数比根据所制备的终产物进行调节实现。
上述基于间位链接的联肼基吖嗪结构化合物可以作为红色荧光探针的应用，即可以用于制备红色荧光探针(即红色荧光染色剂)。
实施本发明的基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用，具有以下有益效果：通过在经典的水杨醛吖嗪(SAA)的亚氨基间位或酚羟基的对位引入拓展共轭的取代基，获得了一类新型的红色荧光探针分子，其中R基被限定为氰基苯、三苯基乙烯或四苯基乙烯、二苯胺或三苯胺、咔唑等芳香基团或其衍生结构；R1～R4分别表示连接在苯环结构上的任意取代位置的取代基结构，分别选自氢、烷基、烷氧基及芳香基团及相应的衍生结构。新的探针结构具有优异的聚集诱导发光特性，能够用于水系条件下对金属离子的 选择性定量识别；利用具有取代基团推拉电子能力变化，实现了固态荧光有效红移和对此类ESIPT(激发态下分子内质子转移)型分子醇酮比例、离子选择性及检测限的调节，此类红色荧光探针在化学传感、生物分析，离子检测等领域具有重要用途和意义。
附图说明
图1A为CN-SAA在不同极性溶剂中的荧光光谱；
图1B为CN-SAA在不同比例四氢呋喃和水的混合体系中的荧光光谱；
图2A为CN-SAA对不同金属离子及干扰离子实验；
图2B为CN-SAA对不同含量金属离子的荧光光谱；
图3A为TPE-SAA在不同极性溶剂中的荧光光谱；
图3B为TPE-SAA在不同比例四氢呋喃和水的混合体系中的荧光光谱；
图4A为TPE-SAA对不同金属离子及干扰离子实验；
图4B为TPE-SAA对不同含量金属离子的荧光光谱；
图5A为TPA-SAA在不同极性溶剂中的荧光光谱；
图5B为TPA-SAA在不同比例四氢呋喃和水的混合体系中的荧光光谱；
图6A为TPA-SAA对不同金属离子及干扰离子实验；
图6B为TPA-SAA对不同含量金属离子的荧光光谱；
图7A为Cz-SAA在不同极性溶剂中的荧光光谱；
图7B为Cz-SAA在不同比例四氢呋喃和水的混合体系中离子实验；
图8A为Cz-SAA在不同金属离子及干扰离子实验；
图8B为Cz-SAA对不同含量金属离子的荧光光谱。
具体实施方式
下面结合附图和实施例，对本发明的基于间位链接的联肼基吖嗪结构化合物及其制备方法和应用作进一步说明：
本发明的目的提出基于间位链接的联肼基吖嗪结构化合物，一类新型的基于水杨醛吖嗪(SAA)的荧光探针类材料。通过在水杨醛联肼的亚氨基间位(或酚羟基的对位)引入具有一定吸推电子能力的共轭基团，将此类吖嗪类衍生物的固态光谱被拓展到红色荧光区域，并且展现了优异的聚集诱导发光特性，能够实现在水系条件下对金属离子的选择性识别和定量检测。新制备间位修饰联肼类吖嗪结构红色探针在化学传感、生物分析、离子检测等领域具有重要用途和意义。
本发明的基于间位链接的联肼基吖嗪结构化合物的结构通式如下：
Figure PCTCN2016097320-appb-000015
其中，如上结构，R基被限定为在水杨醛的醛基间位(或羟基对位)引入氰基苯、三苯基乙烯或四苯基乙烯、二苯胺或三苯胺、咔唑等芳香基团或其衍生结构，R1～R4分别表示连接在苯环结构中的任意取代位置，分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种，进一步地，其中烷基或烷氧基的碳原子数为1～12。
具体合成过程：
(1)通过各种耦联、取代和缩合等反应得到水杨醛衍生物结构，需要说明的是，该反应步骤为现有技术，这里不再进行详细赘述；
(2)
Figure PCTCN2016097320-appb-000016
将上述水杨醛衍生物采用适当的溶剂和温度，在添加适当催化剂的条件下，与水合肼缩合得到最终产物。
具体操作：将适量水杨醛衍生物与水合肼在适量溶剂和催化剂条件下，加热至适当温度，反应一段时间后冷却至室温，处理掉大部分溶剂后析出黄色或红色晶体或粉末，柱层析或重结晶后即得到目标产物。其中，反应溶剂优选甲醇、乙醇、乙酸、四氢呋喃、甲苯、苯、氯仿、二氯甲烷、N,N-二甲基甲酰胺(DMF)，N,N-二甲基乙酰胺(DMAC)和N-甲基吡咯烷酮(NMP)等或二者、三者的混合体系，最优选乙醇及其与其他溶剂的混合体系；催化剂优选稀硫酸、稀硝酸、盐酸和醋酸等质子酸，或三氯化铁、四氯化钛、硅胶等路易斯酸等，或者固体酸，或上述多元混合体系，最优选醋酸；温度优选20℃至150℃，其中最优选为30℃至90℃；反应时间优选1小时至24小时，其中最优选6小时至12小时；重结晶溶剂，优选四氢呋喃、乙醇、甲苯、DMF等，最优选乙醇。
实施例1：氰基水杨醛吖嗪的合成(CN-SAA)
Figure PCTCN2016097320-appb-000017
将0.5g对氰基苯水杨醛与水合肼在25ml乙醇下回流4h(加入乙酸作为催化剂)，冷却后减压除去乙醇后萃取，有机相干燥后采用柱分离，得到淡黄 固体0.52g，即为CN-SAA结构。MALDI-TOF(m/z):[M+]calcd.C28H18N4O2,442.143；found,443.15.Anal Calc.for C28H18N4O2:C,76.01；H,4.10；N,12.66；O,7.23.Found:C,75.78；H,4.04；N,12.33；O,7.05.
实施例2：CN-SAA的ESIPT和AIE性质研究
如图1A为CN-SAA在不同极性下的荧光光谱，随着极性的变化，CN-SAA的醇式发射(426nm附近)和酮式发射(579nm附近)的比例发生明显变化，为典型的ESIPT发射。对于ESIPT分子，聚集态多为酮式发射，所以我们检测了该处的聚集发光现象。如图1B所示，向CN-SAA的四氢呋喃溶剂中(溶解单分子态)不断加入一定比例的水，CN-SAA由于溶解度问题慢慢聚集成纳米颗粒，醇式荧光强度逐渐下降，酮式强度增加，二者比例随着含水量的增加而上升，说明CN-SAA具有AIE性质。ESIPT和AIE性质暗示CN-SAA具有荧光探针的潜质。
实施例3：CN-SAA的对金属离子的响应性研究
如图2A和2B所示为CN-SAA在水溶液中对不同金属离子的选择实验结果，通过对比发现，该荧光探针对铜离子存在特异性性响应，其在579nm附近的荧光强度明显降低，并存在一定线性关系；通过干扰实验结果，可以看出，其他离子存在时对铜离子的检测影响不大。
实施例4：四苯乙烯基水杨醛吖嗪的合成(TPE-SAA)
Figure PCTCN2016097320-appb-000018
将1g四苯乙烯基水杨醛与水合肼在25ml乙醇下回流4h(加入乙酸作为催化剂)，冷却后减压除去乙醇后萃取，有机相干燥后采用柱分离，得到淡黄 固体0.68g，即为TPE-SAA结构。MALDI-TOF(m/z):[M+]calcd.C54H40N2O2,748.309；found,749.32.Anal Calc.for C54H40N2O2:C,86.60；H,5.38；N,3.74；O,4.27Found:C,86.32；H,5.21；N,3.65；O,4.13.
实施例5：TPE-SAA的ESIPT和AIE性质研究
图3A为TPE-SAA在不同极性下的荧光光谱，随着极性的变化，TPE-SAA的醇式发射(443nm附近)和酮式发射(610nm附近)的比例发生明显变化，为典型的ESIPT发射。对于ESIPT分子，聚集态多为酮式发射，所以检测了该处的聚集发光现象。如图3B所示，向TPE-SAA的四氢呋喃溶剂中(溶解单分子态)不断加入一定比例的水，TPE-SAA由于溶解度问题慢慢聚集成纳米颗粒，醇式荧光强度逐渐下降，酮式强度增加，二者比例随着含水量的增加而上升，说明TPE-SAA具有AIE性质。ESIPT和AIE性质暗示TPE-SAA具有荧光探针的潜质。
实施例6：TPE-SAA的对金属离子的响应性研究
如图4A和4B所示，为TPE-SAA在水溶液中对不同金属离子的选择实验结果，通过对比发现，该荧光探针对铜离子存在特异性性响应，其在624nm附近的荧光强度明显降低，并存在一定线性关系；通过干扰实验结果，可以看出，其他离子存在时对铜离子的检测影响不大。
实施例7：三苯胺基水杨醛吖嗪的合成(TPA-SAA)
Figure PCTCN2016097320-appb-000019
将1g三苯胺基水杨醛与水合肼在25ml乙醇下回流4h(加入乙酸作为催化剂)，冷却后减压除去乙醇后萃取，有机相干燥后采用柱分离，得到淡黄固 体0.90g，即为TPA-SAA结构。MALDI-TOF(m/z):[M+]calcd.C50H38N4O2,727.2995；found,727.38.Anal Calc.for C50H38N4O2:C,82.62；H,5.27；N,7.71；O,4.40Found:C,82.23；H,5.16；N,7.56；O,4.24.
实施例8：TPA-SAA的ESIPT和AIE性质研究
如图5A所示为TPA-SAA在不同极性下的荧光光谱，随着极性的变化，TPA-SAA的醇式发射(438nm附近)和酮式发射(632nm附近)的比例发生明显变化，为典型的ESIPT发射。对于ESIPT分子，聚集态多为酮式发射，所以检测了该处的聚集发光现象。如图5B所示，向TPA-SAA的四氢呋喃溶剂中(溶解单分子态)不断加入一定比例的水，TPA-SAA由于溶解度问题慢慢聚集成纳米颗粒，醇式荧光强度逐渐下降，酮式强度增加，二者比例随着含水量的增加而上升，说明TPA-SAA具有AIE性质。ESIPT和AIE性质暗示TPA-SAA具有荧光探针的潜质。
实施例9：TPA-SAA的对金属离子的响应性研究
如图6A和6B所示为TPA-SAA在水溶液中对不同金属离子的选择实验结果，通过对比发现，该荧光探针对铜离子存在特异性性响应，其在627nm附近的荧光强度明显降低，并存在一定线性关系；通过干扰实验结果，可以看出，其他离子存在时对铜离子的检测影响不大。
实施例10：咔唑基水杨醛吖嗪的合成(Cz-SAA)
Figure PCTCN2016097320-appb-000020
将1g咔唑基水杨醛与水合肼在25ml乙醇下回流4h(加入乙酸作为催化剂)，冷却后过滤，采用适当溶剂重结晶，得到淡黄固体0.88g，即为Cz-SAA 结构。MALDI-TOF(m/z):[M+]calcd.C50H34N4O2,722.2682；found,723.24.Anal Calc.for C50H34N4O2:C,83.08；H,4.74；N,7.75；O,4.43Found:C,82.18；H,4.33；N,7.43；O,4.20.
实施例11：Cz-SAA的ESIPT和AIE性质研究
如图7A所示为Cz-SAA在不同极性下的荧光光谱，随着极性的变化，但是由于Cz-SAA溶解性相对较差，荧光过程相对复杂，仍然可以观察到醇式发射(418nm附近，仅甲苯中出现)和酮式发射(600nm附近)的比例发生明显变化，为典型的ESIPT发射。对于ESIPT分子，聚集态多为酮式发射，所以检测了该处的聚集发光现象。如图7B所示，向Cz-SAA的四氢呋喃溶剂中(溶解单分子态)不断加入一定比例的水，Cz-SAA由于溶解度问题慢慢聚集成纳米颗粒，酮式强度增加，说明Cz-SAA具有AIE性质。ESIPT和AIE性质暗示Cz-SAA具有荧光探针的潜质。
实施例12：Cz-SAA的对金属离子的响应性研究
如图8A和8B所示为Cz-SAA在水溶液中对不同金属离子的选择实验结果，通过对比发现，该荧光探针对铜、铁离子存在特异性性响应(紫外吸收光谱可以将二者区分)，其在600nm附近的荧光强度明显降低，并存在一定线性关系；通过干扰实验结果，可以看出，其他离子存在时对铜离子的检测影响不大。
应当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进或变换都应属于本发明所附权利要求的保护范围之内。

Claims (10)

  1. 一种基于间位链接的联肼基吖嗪结构化合物，其特征在于，其结构式如下：
    Figure PCTCN2016097320-appb-100001
    其中，R选自下述结构基团
    Figure PCTCN2016097320-appb-100002
    Figure PCTCN2016097320-appb-100003
    中的一种，R1～R4分别表示连接在苯环结构中的任意取代位置，且R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。
  2. 根据权利要求1所述的联肼基吖嗪结构化合物，其特征在于，R为：
    Figure PCTCN2016097320-appb-100004
    其中，R1和R2分别位于氰基的邻位、间位或对位，R1和R2分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。
  3. 根据权利要求1所述的联肼基吖嗪结构化合物，其特征在于，R为：
    Figure PCTCN2016097320-appb-100005
    其中，取代基R1～R4分别位于苯环的邻位、间位或对位，R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。
  4. 根据权利要求1所述的联肼基吖嗪结构化合物，其特征在于，R为：
    Figure PCTCN2016097320-appb-100006
    其中，R1～R4分别位于苯环的邻位、间位或对位，R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。
  5. 根据权利要求1所述的联肼基吖嗪结构化合物，其特征在于，R为：
    Figure PCTCN2016097320-appb-100007
    其中，R1～R4分别位于苯环的邻位、间位或对位，R1～R4分别选自氢、烷基、羟基、烷氧基、硝基、氰基、氨基、巯基、卤素原子、苯基、甲苯基、萘基、呋喃基、噻吩基、吡咯基、吡啶基、吡喃基、喹啉基、吲哚基、羧酸或羧酸衍生物、咔唑基或苯胺基及其衍生物中的一种。
  6. 一种权利要求1-5中任一权利要求所述的基于间位链接的联肼基吖嗪结构化合物的制备方法，其特征在于，包括如下步骤：
    S1、通过耦联、取代和缩合反应得到水杨醛衍生物：
    Figure PCTCN2016097320-appb-100008
    S2、将水杨醛衍生物与水合肼在反应溶剂和催化剂条件下，加热至20℃～150℃，反应1小时～24小时后冷却至室温，处理掉大部分溶剂后析出晶体或粉末，柱层析或重结晶后得到基于间位链接的联肼基吖嗪结构化合物，
    Figure PCTCN2016097320-appb-100009
  7. 根据权利要求6所述的联肼基吖嗪结构化合物的制备方法，其特征在于，在步骤S2中，所述反应溶剂选自甲醇、乙醇、乙酸、四氢呋喃、甲苯、苯、氯仿、二氯甲烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷 酮或其二者、三者的混合体系。
  8. 根据权利要求6所述的联肼基吖嗪结构化合物的制备方法，其特征在于，在步骤S2中，所述催化剂选自稀硫酸、稀硝酸、盐酸、醋酸、或三氯化铁、四氯化钛、硅胶、或固体酸、或上述多元混合体系。
  9. 根据权利要求6所述的联肼基吖嗪结构化合物的制备方法，其特征在于，在步骤S2中，加热至温度为30℃～90℃；反应时间为6小时～12小时。
  10. 一种权利要求1-5中任一权利要求所述的基于间位链接的联肼基吖嗪结构化合物作为红色荧光探针的应用。
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