WO2018099382A1 - Red light excited fluorescent dye, preparation method therefor, and applications thereof - Google Patents

Red light excited fluorescent dye, preparation method therefor, and applications thereof Download PDF

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WO2018099382A1
WO2018099382A1 PCT/CN2017/113465 CN2017113465W WO2018099382A1 WO 2018099382 A1 WO2018099382 A1 WO 2018099382A1 CN 2017113465 W CN2017113465 W CN 2017113465W WO 2018099382 A1 WO2018099382 A1 WO 2018099382A1
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fluorescent dye
red light
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reaction
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车团结
徐进章
赵芳
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苏州百源基因技术有限公司
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    • 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
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    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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    • 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
    • G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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Definitions

  • the invention relates to the field of optical functional materials, in particular to a red light excitation fluorescent dye and a preparation method and application thereof.
  • fluorescent dyes Dyes that strongly absorb and radiate fluorescence in the visible range are called fluorescent dyes. Fluorescent dyes emit visible fluorescence after absorption of red light by a substance molecule and absorb visible light with a longer wavelength after absorption of shorter wavelength visible light. Each molecule has a series of strict discrete energy levels. At room temperature, most of the material molecules are in the "ground state”. When these materials absorb light energy under the illumination of light, they enter a new state called “excited state”. The molecular weight of the excited state is unstable, and it can emit light to return to the ground state in a very short time of 10 -9 to 10 -7 seconds, and the process fluoresces. Since the 20th century, fluorescent dyes have been widely used in various industries such as textiles, plastic dyeing, and printing pigments.
  • fluorescent dyes have been widely used to label, detect, and/or quantify components in samples, and various methods for such detection and/or quantification include fluorescence microscopy, fluorescent immunoassays, and flow of cells. Cell count analysis, as well as a variety of other applications.
  • Organic fluorescent compounds having an electron donor group- ⁇ bridge-electron acceptor group structure Specific optical properties are exhibited.
  • the Stokes' displacement is large, and the luminescent properties vary greatly depending on the polarity and viscosity of the solvent, and the two-photon absorption ability is strong, which is receiving more and more attention.
  • They have great application value in many aspects, for example, they can be used to construct photoelectric molecular switches, light-emitting diodes, field effect transistors, information transmission and storage devices.
  • these molecules are highly sensitive to the environment and can be used as fluorescent probe materials (WO2007013601-A1) in the fields of biomarkers, immunoassays and chemical sensing (DE102004059156-A1).
  • red light-excited fluorescent dye that can ensure the stability of the spectral analysis signal, has a high molar absorptivity, has a high fluorescence quantum yield, and has certain chemical activity and easy structure modification. Therefore, its further application in the fields of biology, environment and the like is limited.
  • the invention designs and synthesizes a novel red light-excited fluorescent dye with novel structure, simple preparation method and excellent performance.
  • the technical problem to be solved by the present invention is to overcome the difficulty in synthesizing the red light-excited fluorescent dye in the prior art.
  • red light-excited fluorescent dye having a structure as shown in formula (I):
  • R 1 , R 2 and R 3 are one selected from the group consisting of hydrogen, a C 1 -C 10 hydrocarbon group, a cyano group, an aryl group or a heterocyclic ring.
  • R 1 , R 2 , and R 3 are selected from the group consisting of hydrogen, methyl, ethyl, cyano, phenyl, 2-thienyl, and 3-thienyl.
  • a method of preparing the red light-excited fluorescent dye comprising the steps of:
  • the present invention further provides the red light-excited fluorescent dye in constructing a photoelectric molecular switch, a light emitting diode, a field effect transistor, an information transmission and storage device, and also can be used as a fluorescent probe for biomarking and immunity. Analysis and areas such as chemical sensing.
  • the red light-excited fluorescent dye application method is an application of dissolving in any ratio of dimethylformamide, ethanol, hydroxyethylpiperazineethanesulfonic acid in any ratio.
  • a red light-excited fluorescent dye provided by an embodiment of the present invention, which contains a benzene ring or a hetero ring and has a conjugated double bond, and is excited when the non-bonded electron of the O or N atom is in an excited state.
  • the ⁇ * bond is characterized by expanding the large ⁇ bond of the organic fluorescent molecule, expanding the conjugated system of the entire organic fluorescent molecule, and enhancing the fluorescence of the organic molecule.
  • the fluorescent dye has simple synthesis process, high selectivity, and is not easy to be polymerized, and has a large molar extinction coefficient, high sensitivity, and fluorescence by introducing an electron withdrawing group.
  • High quantum yield and good light stability when used for the detection of substances in living organisms, can greatly reduce the self-absorption and autofluorescence interference of substances in the living body, improve the sensitivity and selectivity of detection, and reduce Damage to life.
  • Example 1 is an excitation and emission spectrum of a red light-excited fluorescent dye in ethanol of Example 1-4 of the present invention
  • the basic chemical raw materials such as reagents used in the embodiments of the present invention can be purchased in the domestic chemical product market, or can be customized in the relevant intermediate preparation factory.
  • the preparation method is as follows:
  • the red light-excited fluorescent dye (II) of the present invention is detected and characterized as follows:
  • the preparation method is as follows:
  • the red light-excited fluorescent dye (III) of the present invention is detected and characterized as follows:
  • the preparation method is as follows:
  • the red light-excited fluorescent dye (IV) of the present invention is detected and characterized as follows:
  • the preparation method is as follows:
  • the red light-excited fluorescent dye (V) of the present invention is detected and characterized as follows:
  • the fluorescence spectrum, the molar extinction coefficient and the fluorescence quantum yield are determined, and the specific determination methods of each parameter are as follows:
  • the compound to be determined was accurately weighed and prepared into a solution having a concentration of 1.0 ⁇ 10 -5 mol/L, and the absorption spectrum thereof was measured, as shown in Fig. 1.
  • the fluorescence spectrum was measured using the maximum absorption wavelength in the measured red spectrum as the excitation wavelength of the fluorescence spectrum.
  • the test compound was weighed, and an ethanol:water (50:50, v/v) solution having a concentration of 1.0 ⁇ 10 -6 mol/L was prepared, and its emission spectrum was measured, as shown in FIG.
  • A represents the absorption intensity
  • ⁇ is the molar absorption coefficient
  • c is the concentration of the compound
  • l is the thickness of the quartz cell for detection.
  • the fluorescence quantum yield of the red-excited fluorescent dye was measured at 20 ° C.
  • the quinine sulfate (0.1 M H 2 SO 4 solvent with a quantum yield of 0.56) was used as a reference to measure the red fluorescent excitation dye and
  • the fluorescence quantum yield is calculated by the fluorescence integrated intensity obtained from the dilute solution of the reference material under the same excitation conditions and the ultraviolet absorption value at the excitation wavelength.
  • the product was dissolved in absolute ethanol.
  • ⁇ is the quantum yield of the analyte
  • subscript R represents the reference.
  • I is the fluorescence integrated intensity
  • A is the ultraviolet absorption value.
  • ⁇ is the solvent refractive index.
  • the absorbances A and A R are less than 0.1.
  • the red light-excited fluorescent dye (IV) described in Example 3 has the largest absorption wavelength, and corresponds to the maximum emission wavelength of 747 nm, the maximum molar absorption coefficient of 8.9, and the maximum fluorescence quantum yield of 88.67%. , which further indicates that the compounds have advantages in constructing photoelectric molecular switches, light-emitting diodes, field effect transistors, information transmission and storage devices, and It is used as a fluorescent probe in the fields of biomarkers, immunoassays, and chemical sensing.

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Abstract

The present invention relates to the field of optical function materials, and specifically, to a red light excited fluorescent dye having a structure represented by formula (I). The red light excited fluorescent dye provided in the present invention has a very broad excitation spectrum, good light stability and high stability in trace detection, can be used in different application fields such as cell imaging, fluorescence probes, laser dyes and fluorescence sensors, and has good practicability. The preparation method provided in the present invention has low raw material costs, does not produce pollution, needs simple technologies and has a high yield; the prepared fluorescent dye has a novel structure and good performance, and is suitable for being widely used in the fields such as biology and environments.

Description

一种红光激发荧光染料及其制备方法与应用Red light excitation fluorescent dye and preparation method and application thereof
交叉引用cross reference
本申请要求在2016年11月30日提交中国专利局、申请号为201611085796.0、发明名称为“一种红光激发荧光染料及其制备方法与应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims priority to Chinese Patent Application No. 201611085796.0, entitled "A red-light-excited fluorescent dye, and its preparation method and application", which is filed on November 30, 2016. The citations are incorporated herein by reference.
技术领域Technical field
本发明涉及光功能材料领域，具体涉及一种红光激发荧光染料及其制备方法与应用。The invention relates to the field of optical functional materials, in particular to a red light excitation fluorescent dye and a preparation method and application thereof.
背景技术Background technique
在可见光范围内能强烈吸收并辐射出荧光的染料称之为荧光染料，荧光染料在物质分子吸收红光后会发出的可见荧光以及吸收波长较短的可见光后发出波长较长的可见荧光。每个分子具有一系列严格的分立能级，室温下物质分子大部分处于“基态”，当这些物质在光的照射下吸收光能后，进入新的状态，称为“激发态”，处于“激发态”的分子量是不稳定的，它可以通过10-9～10-7秒的极短时间内发射光量子回到基态，这一过程便发出荧光。20世纪以来，荧光染料被广泛应用于纺织、塑料染色、印刷用颜料等多种行业。近年来，荧光染料被广泛用于标记、检测、和/或定量样品中的组分，用于这样的检测和/或定量的多种方法包括荧光显微术、荧光免疫测定、细胞的流式细胞计数分析、以及多种其他应用。Dyes that strongly absorb and radiate fluorescence in the visible range are called fluorescent dyes. Fluorescent dyes emit visible fluorescence after absorption of red light by a substance molecule and absorb visible light with a longer wavelength after absorption of shorter wavelength visible light. Each molecule has a series of strict discrete energy levels. At room temperature, most of the material molecules are in the "ground state". When these materials absorb light energy under the illumination of light, they enter a new state called "excited state". The molecular weight of the excited state is unstable, and it can emit light to return to the ground state in a very short time of 10 -9 to 10 -7 seconds, and the process fluoresces. Since the 20th century, fluorescent dyes have been widely used in various industries such as textiles, plastic dyeing, and printing pigments. In recent years, fluorescent dyes have been widely used to label, detect, and/or quantify components in samples, and various methods for such detection and/or quantification include fluorescence microscopy, fluorescent immunoassays, and flow of cells. Cell count analysis, as well as a variety of other applications.
具有电子给体基团-π桥-电子受体基团结构的有机荧光化合物常表 现出特异的光学性质，例如，Stokes’位移大，发光性质随溶剂的极性、粘度不同会发生很大变化，双光子吸收能力强等，从而受到越来越多的关注。它们在很多方面具有很大的应用价值，例如，它们可用于构筑光电分子开关，发光二极管，场效应晶体管，信息传输和存储器件等。此外，这些分子具有对环境高度敏感的特点，因而可以作为荧光探针材料(WO2007013601-A1)应用于生物标记、免疫分析以及化学传感(DE102004059156-A1)等领域。Organic fluorescent compounds having an electron donor group-π bridge-electron acceptor group structure Specific optical properties are exhibited. For example, the Stokes' displacement is large, and the luminescent properties vary greatly depending on the polarity and viscosity of the solvent, and the two-photon absorption ability is strong, which is receiving more and more attention. They have great application value in many aspects, for example, they can be used to construct photoelectric molecular switches, light-emitting diodes, field effect transistors, information transmission and storage devices. In addition, these molecules are highly sensitive to the environment and can be used as fluorescent probe materials (WO2007013601-A1) in the fields of biomarkers, immunoassays and chemical sensing (DE102004059156-A1).
在很多情况下，寻找一种荧光分析过程中能保证光谱分析信号稳定性、具有摩尔吸光系数较高、荧光量子产率高且具有一定化学活性、结构易于修饰的红光激发荧光染料较为困难，因而限制了其在生物、环境等领域的进一步应用。本发明设计合成了一种结构新颖、制备方法简单、性能优良的新型红光激发荧光染料。In many cases, it is difficult to find a red light-excited fluorescent dye that can ensure the stability of the spectral analysis signal, has a high molar absorptivity, has a high fluorescence quantum yield, and has certain chemical activity and easy structure modification. Therefore, its further application in the fields of biology, environment and the like is limited. The invention designs and synthesizes a novel red light-excited fluorescent dye with novel structure, simple preparation method and excellent performance.
发明内容Summary of the invention
因此，本发明要解决的技术问题在于克服现有技术中的红光激发荧光染料合成困难缺陷。Therefore, the technical problem to be solved by the present invention is to overcome the difficulty in synthesizing the red light-excited fluorescent dye in the prior art.
为了解决上述技术问题，本发明采用的技术方案如下：In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:
根据本发明的一个方面，提供一种红光激发荧光染料，具有如式(Ⅰ)所示的结构： According to an aspect of the invention, there is provided a red light-excited fluorescent dye having a structure as shown in formula (I):
Figure PCTCN2017113465-appb-000001
Figure PCTCN2017113465-appb-000001
其中，among them,
R1、R2、R3选自氢、C1-C10烃基、氰基、芳香基或杂环中的一种。R 1 , R 2 and R 3 are one selected from the group consisting of hydrogen, a C 1 -C 10 hydrocarbon group, a cyano group, an aryl group or a heterocyclic ring.
可选的，R1、R2、R3选自氢、甲基、乙基、氰基、苯基、2-噻吩基、3-噻吩基中的一种。Optionally, R 1 , R 2 , and R 3 are selected from the group consisting of hydrogen, methyl, ethyl, cyano, phenyl, 2-thienyl, and 3-thienyl.
可选的，其结构式如(Ⅱ)(Ⅲ)(Ⅳ)(Ⅴ)所示： Alternatively, the structural formula is as shown in (II) (III) (IV) (V):
Figure PCTCN2017113465-appb-000002
Figure PCTCN2017113465-appb-000002
根据本发明的另一个方面，提供制备所述红光激发荧光染料的方法，包括如下步骤： According to another aspect of the present invention, there is provided a method of preparing the red light-excited fluorescent dye, comprising the steps of:
Figure PCTCN2017113465-appb-000003
Figure PCTCN2017113465-appb-000003
(1)中间体1-Ⅰ制备(1) Preparation of intermediate 1-I
在氮气保护下，反应瓶中加入无水CuI和THF，冷却至-45℃～-55℃，滴加ClCH2CH＝CHLi，搅拌30min～45min，继续冷却至-75℃～-80℃，滴加2-氯-4-甲基-2H-吡咯的四氢呋喃溶液，反应结束后，用乙二醇二甲醚稀释，采用去离子水洗涤，浓缩，得到中间体1-Ⅰ。Under nitrogen protection, add anhydrous CuI and THF to the reaction flask, cool to -45 ° C ~ -55 ° C, add ClCH 2 CH = CHLi, stir for 30 min ~ 45 min, continue cooling to -75 ° C ~ -80 ° C, drop A solution of 2-chloro-4-methyl-2H-pyrrole in tetrahydrofuran was added, and after completion of the reaction, it was diluted with dimethyl ether (hexane), washed with de-ion water and concentrated to give Intermediate 1-I.
(2)中间体2-Ⅰ制备(2) Preparation of intermediate 2-I
在反应瓶中加入无水氯化铝，二氯甲烷，置于冰盐浴中，搅拌，降温至0℃～-3℃，加入中间体1-Ⅰ，继续降温至-3℃～-10℃，开始滴加氯乙酰氯，控制温度不超过-2℃～-7℃，反应10～12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.0～8.0，三氯 甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即中间体2-Ⅰ。Add anhydrous aluminum chloride, dichloromethane in the reaction flask, place in ice salt bath, stir, cool to 0 ° C ~ -3 ° C, add intermediate 1-I, continue to cool to -3 ° C ~ -10 ° C Start adding chloroacetyl chloride dropwise, control the temperature does not exceed -2 ° C ~ -7 ° C, reaction for 10 to 12 hours; slowly pour the reaction solution into saturated sodium bicarbonate solution, add deionized water, and adjust with sodium carbonate pH 7.0 to 8.0, trichloro The methane was extracted three times, and the organic phase was collected, dried over anhydrous magnesium sulfate for 3 hr, filtered, and evaporated to give a yellow solid.
(3)中间体3-Ⅰ制备(3) Preparation of intermediate 3-I
将三氟化硼***和三乙胺缓慢滴加到步骤(2)所得中间体2-Ⅰ的二氯甲烷溶液中，不断搅拌，控制温度在15℃～20℃，反应4～6小时，直接蒸出溶剂，得到油状物，采用异丙醇和石油醚(体积比为1:8～1:10)重结晶得到类白色固体，即中间体3-Ⅰ。The boron trifluoride diethyl ether and triethylamine are slowly added dropwise to the dichloromethane solution of the intermediate 2-I obtained in the step (2), and the mixture is continuously stirred, and the temperature is controlled at 15 ° C to 20 ° C for 4 to 6 hours. The solvent was evaporated to give an oily material which crystallised from isopropyl alcohol and petroleum ether (1:8 to 1:10) to give an off-white solid, intermediate 3-I.
(4)化合物Ⅰ制备(4) Preparation of Compound I
在反应瓶中加入无水氯化铝，二氯甲烷，置于冰盐浴中，搅拌，降温至0℃～-3℃，加入R1，R2，R3取代的1,2,3-苯三酚，继续降温至-3℃～-10℃，开始滴加中间体3-Ⅰ的二氯甲烷溶液，控制温度不超过0℃～-7℃，反应10～12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.0～8.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即化合物Ⅰ。Add anhydrous aluminum chloride, dichloromethane to the reaction flask, place in an ice salt bath, stir, cool to 0 ° C ~ -3 ° C, add 1 , 1 , 2 , 3 substituted by R 1 , R 2 , R 3 Pyrogallol, continue to cool down to -3 ° C ~ -10 ° C, began to add dropwise the intermediate 3-I dichloromethane solution, control the temperature does not exceed 0 ° C ~ -7 ° C, the reaction 10 ~ 12 hours; the reaction liquid is slow Pour into saturated sodium bicarbonate solution, add deionized water, adjust the pH value of 7.0-8.0 with sodium carbonate, extract three times with chloroform, collect the organic phase, dry with anhydrous magnesium sulfate for 3 hours, suction filtration, steaming The organic solvent gave a yellow solid, Compound I.
根据本发明的另一个方面，本发明还提供所述红光激发荧光染料在构筑光电分子开关，发光二极管，场效应晶体管，信息传输和存储器件，还可以作为荧光探针应用于生物标记、免疫分析以及化学传感等领域。According to another aspect of the present invention, the present invention further provides the red light-excited fluorescent dye in constructing a photoelectric molecular switch, a light emitting diode, a field effect transistor, an information transmission and storage device, and also can be used as a fluorescent probe for biomarking and immunity. Analysis and areas such as chemical sensing.
可选的，红光激发荧光染料应用方法为以任意比例溶解于二甲酰胺、乙醇、羟乙基哌嗪乙磺酸中的应用。Optionally, the red light-excited fluorescent dye application method is an application of dissolving in any ratio of dimethylformamide, ethanol, hydroxyethylpiperazineethanesulfonic acid in any ratio.
本发明的上述技术方案具有以下优点：The above technical solution of the present invention has the following advantages:
1.本发明实施例提供的一种红光激发荧光染料，由于含有苯环或杂环并带有共轭双键，由于O或N原子的非成键电子在激发态时，会被激发 到π*键，表现为扩大了有机荧光分子的大π键，使整个有机荧光分子的共轭体系扩大，起到增强有机分子荧光作用。1. A red light-excited fluorescent dye provided by an embodiment of the present invention, which contains a benzene ring or a hetero ring and has a conjugated double bond, and is excited when the non-bonded electron of the O or N atom is in an excited state. The π * bond is characterized by expanding the large π bond of the organic fluorescent molecule, expanding the conjugated system of the entire organic fluorescent molecule, and enhancing the fluorescence of the organic molecule.
2.本发明实施例提供的一种红光激发荧光染料，该荧光染料合成工艺简单，具有很高的选择性，不容易聚合，通过引入吸电子基团，摩尔消光系数大，灵敏度高，荧光量子产率高，而且光稳定性好，在用于生物体内物质的检测时，可以极大的降低生物体内物质的自吸收和自发荧光的干扰，提高检测的灵敏度和选择性，同时还能减少对生命的损伤。2. A red light-excited fluorescent dye provided by an embodiment of the present invention, the fluorescent dye has simple synthesis process, high selectivity, and is not easy to be polymerized, and has a large molar extinction coefficient, high sensitivity, and fluorescence by introducing an electron withdrawing group. High quantum yield and good light stability, when used for the detection of substances in living organisms, can greatly reduce the self-absorption and autofluorescence interference of substances in the living body, improve the sensitivity and selectivity of detection, and reduce Damage to life.
附图说明DRAWINGS
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings to be used in the specific embodiments or the description of the prior art will be briefly described below, and obviously, the attached in the following description The drawings are some embodiments of the present invention, and those skilled in the art can obtain other drawings based on these drawings without any creative work.
图1是本发明实施例1-4红光激发荧光染料在乙醇中的激发和发射光谱；1 is an excitation and emission spectrum of a red light-excited fluorescent dye in ethanol of Example 1-4 of the present invention;
具体实施方式detailed description
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互 结合。The technical solutions of the present invention will be clearly and completely described in the following with reference to the accompanying drawings. It is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention. Furthermore, the technical features involved in the different embodiments of the present invention described below may be mutually exclusive as long as they do not form a conflict with each other. Combine.
本发明实施例所用的试剂等基础化工原料，均可在国内化工产品市场买到，或在有关中间体制备厂定做。The basic chemical raw materials such as reagents used in the embodiments of the present invention can be purchased in the domestic chemical product market, or can be customized in the relevant intermediate preparation factory.
实施例1Example 1
本实施例提供的红光激发荧光染料(Ⅱ)的制备方法：The preparation method of the red light-excited fluorescent dye (II) provided by the embodiment:
具有式(Ⅱ)结构：With the structure of formula (II):
Figure PCTCN2017113465-appb-000004
Figure PCTCN2017113465-appb-000004
其制备方法如下： The preparation method is as follows:
Figure PCTCN2017113465-appb-000005
Figure PCTCN2017113465-appb-000005
(1)中间体1-Ⅱ制备(1) Preparation of intermediate 1-II
在氮气保护下，向250ml反应瓶中加入无水CuI 1.9g(0.01mol)和20ml THF，冷却至-55℃，滴加ClCH2CH＝CHLi 1.23g(0.015mol)，搅拌35min，继续冷却至-80℃，滴加2-氯-4-甲基-2H-吡咯0.58g(0.005mol)的60ml四氢呋喃溶液，反应结束后，用50ml乙二醇二甲醚稀释，采用去离子水洗涤，浓缩，得到中间体1-Ⅱ。Under a nitrogen atmosphere, anhydrous CuI 1.9 g (0.01 mol) and 20 ml of THF were added to a 250 ml reaction flask, cooled to -55 ° C, ClCH 2 CH=CHLi 1.23 g (0.015 mol) was added dropwise, stirred for 35 min, and cooling was continued until -80 ° C, dropwise addition of 2-chloro-4-methyl-2H-pyrrole 0.58 g (0.005 mol) in 60 ml of tetrahydrofuran solution, after completion of the reaction, diluted with 50 ml of ethylene glycol dimethyl ether, washed with deionized water, concentrated , Intermediate 1-II was obtained.
(2)中间体2-Ⅱ制备(2) Preparation of intermediate 2-II
在50ml反应瓶中加入无水氯化铝1.2g(0.009mol)，二氯甲烷24ml，置于冰盐浴中，搅拌，降温至0℃，加入中间体1-Ⅱ 0.47g(0.003mol)，继续降温至-10℃，滴加氯乙酰氯0.5g(0.0045mol)，控制温度-2℃～-4℃， 反应12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值8.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即中间体2-Ⅱ。Add 1.2 g (0.009 mol) of anhydrous aluminum chloride, 24 ml of dichloromethane to a 50 ml reaction flask, place in an ice salt bath, stir, cool to 0 ° C, add intermediate 1-II 0.47 g (0.003 mol), Continue to cool down to -10 ° C, add 0.5 g (0.0045 mol) of chloroacetyl chloride, control the temperature -2 ° C ~ -4 ° C, The reaction was slowly poured into a saturated sodium bicarbonate solution, deionized water was added, and the pH was adjusted to 8.0 with sodium carbonate. The organic phase was extracted three times with trichloromethane and dried over anhydrous magnesium sulfate for three hours. Filtration and evaporation of the organic solvent gave a yellow solid, Intermediate 2-II.
(3)中间体3-Ⅱ制备(3) Preparation of intermediate 3-II
将三氟化硼***30ml和三乙胺3ml缓慢滴加到步骤(2)所得中间体2-Ⅱ的50ml二氯甲烷溶液中，不断搅拌，控制温度在28℃～30℃，反应5小时，直接蒸出溶剂，得到油状物，采用乙酸乙酯和石油醚(体积比为1:8)重结晶得到类白色固体，即中间体3-Ⅱ。30 ml of boron trifluoride etherate and 3 ml of triethylamine were slowly added dropwise to a solution of the intermediate 2-II obtained in the step (2) in 50 ml of dichloromethane, stirring was continued, and the temperature was controlled at 28 ° C to 30 ° C for 5 hours. The solvent was distilled off to give an oily material which crystallised from ethyl acetate and petroleum ether (1:8) to give an off white solid, Intermediate 3-II.
(4)化合物Ⅱ制备(4) Preparation of Compound II
在50ml反应瓶中加入无水氯化铝2.4g(0.018mol)，二氯甲烷20ml，置于冰盐浴中，搅拌，降温至-2℃，加入1,2,3-苯三酚0.76g(0.006mol)，继续降温至-5℃，开始滴加中间体3-Ⅱ 0.42g(0.001mol)的10ml二氯甲烷溶液，控制温度-2℃～-5℃，反应12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值8.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即化合物Ⅱ。Add anhydrous aluminum chloride 2.4g (0.018mol), 20ml of dichloromethane in a 50ml reaction flask, place in an ice salt bath, stir, cool to -2 ° C, add 1,2,3-benzenetriol 0.76g (0.006 mol), continue to cool to -5 ° C, start dropwise addition of intermediate 3-II 0.42g (0.001mol) of 10ml dichloromethane solution, control the temperature -2 ° C ~ -5 ° C, the reaction for 12 hours; Slowly pour into saturated sodium bicarbonate solution, add deionized water, adjust pH 8.0 with sodium carbonate, extract chloroform three times, collect organic phase, dry with anhydrous magnesium sulfate for 3 hours, filter, and distill out organic The solvent gave a yellow solid, Compound II.
本实施例中，对本发明红光激发荧光染料(Ⅱ)进行检测及表征数据如下：In this embodiment, the red light-excited fluorescent dye (II) of the present invention is detected and characterized as follows:
元素分析计算值(CHBFNO):C33H29BF2N2O9 Elemental Analysis Calculated Value (CHBFNO): C 33 H 29 BF 2 N 2 O 9
质谱(MS+)：646.40(M+)Mass Spectrum (MS+): 646.40 (M+)
m/z:646.19(100.0％),647.20(38.4％),645.20(24.8％),646.20(9.0％),648.20(8.4％),649.20(1.4％) m/z: 646.19 (100.0%), 647.20 (38.4%), 645.20 (24.8%), 646.20 (9.0%), 648.20 (8.4%), 649.20 (1.4%)
元素分析:C,61.32；H,4.52；B,1.67；F,5.88；N,4.33；O,22.28。Elemental analysis: C, 61.32; H, 4.52; B, 1.67; F, 5.88; N, 4.33; O, 22.28.
实施例2Example 2
本实施例提供的红光激发荧光染料(Ⅲ)的制备方法：The preparation method of the red light excitation fluorescent dye (III) provided by the embodiment:
具有式(Ⅲ)结构：Has the structure of formula (III):
Figure PCTCN2017113465-appb-000006
Figure PCTCN2017113465-appb-000006
其制备方法如下： The preparation method is as follows:
Figure PCTCN2017113465-appb-000007
Figure PCTCN2017113465-appb-000007
(1)中间体1-Ⅲ制备(1) Preparation of Intermediate 1-III
在氮气保护下，向500ml反应瓶中加入无水CuI 5.7g(0.03mol)和50ml THF，冷却至-50℃，滴加ClCH2CH＝CHLi 4.1g(0.05mol)，搅拌40min，继续冷却至-78℃，滴加2-氯-4-甲基-2H-吡咯1.7g(0.015mol)的200ml四氢呋喃溶液，反应结束后，用200ml乙二醇二甲醚稀释，采用去离子水洗涤，浓缩，得到中间体1-Ⅲ。Under a nitrogen atmosphere, add anhydrous CuI 5.7 g (0.03 mol) and 50 ml of THF to a 500 ml reaction flask, cool to -50 ° C, add ClCH 2 CH=CHLi 4.1 g (0.05 mol), stir for 40 min, continue cooling to At -78 ° C, a solution of 1.7 g (0.015 mol) of 2-chloro-4-methyl-2H-pyrrole in 200 ml of tetrahydrofuran was added dropwise. After completion of the reaction, it was diluted with 200 ml of ethylene glycol dimethyl ether, washed with deionized water and concentrated. , Intermediate 1-III is obtained.
(2)中间体2-Ⅲ制备(2) Preparation of intermediate 2-III
在反应瓶中加入无水氯化铝3.3g(0.025mol)，二氯甲烷66ml，置于冰盐浴中，搅拌，降温至-3℃，加入中间体1-Ⅲ 1.6g(0.01mol)，继续降温至-7℃，开始滴加氯乙酰氯1.7g(0.015mol)，控制温度在-3℃～-5℃，反应10小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用 碳酸钠调节pH值7.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即中间体2-Ⅲ。Add 3.3 g (0.025 mol) of anhydrous aluminum chloride, 66 ml of dichloromethane to the reaction flask, place in an ice salt bath, stir, cool to -3 ° C, and add intermediate 1-III 1.6 g (0.01 mol). Continue to cool down to -7 ° C, start adding 1.7 g (0.015 mol) of chloroacetyl chloride, control the temperature at -3 ° C ~ -5 ° C, the reaction for 10 hours; slowly pour the reaction solution into saturated sodium bicarbonate solution, add Deionized water and used The sodium carbonate was adjusted to pH 7.0, and the chloroform was extracted three times. The organic phase was collected, dried over anhydrous magnesium sulfate for 3 hrs, filtered, and evaporated to give a yellow solid.
(3)中间体3-Ⅲ制备(3) Preparation of intermediate 3-III
将三氟化硼***100ml和三乙胺10ml缓慢滴加到步骤(2)所得中间体2-Ⅲ的150ml二氯甲烷溶液中，不断搅拌，控制温度在27℃～29℃，反应4小时，直接蒸出溶剂，得到油状物，采用异丙醇和石油醚(体积比为1:9)重结晶得到类白色固体，即中间体3-Ⅲ。100 ml of boron trifluoride diethyl ether and 10 ml of triethylamine were slowly added dropwise to a solution of the intermediate 2-III obtained in the step (2) in 150 ml of dichloromethane, stirring continuously, and the temperature was controlled at 27 ° C to 29 ° C for 4 hours. The solvent was distilled off to give an oily material which crystallised from isopropyl alcohol and petroleum ether (1:9) to give an off-white solid, intermediate 3-III.
(4)化合物Ⅲ制备(4) Preparation of Compound III
在250ml反应瓶中加入无水氯化铝4.0g(0.03mol)，二氯甲烷40ml，置于冰盐浴中，搅拌，降温至0℃，加入1-氰氧基-2-乙氧基-3-甲氧基苯1.9g(0.01mol)，继续降温至-3℃，开始滴加中间体3-Ⅲ0.83g(0.002mol)的20ml二氯甲烷溶液，控制温度-3℃～-6℃，反应11小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.5，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即化合物Ⅲ。Anhydrous aluminum chloride 4.0g (0.03mol), 40ml of dichloromethane was added to a 250ml reaction flask, placed in an ice salt bath, stirred, cooled to 0 ° C, and added 1-cyanooxy-2-ethoxy- 3-methoxybenzene 1.9g (0.01mol), continue to cool to -3 ° C, began to add dropwise 3-MC 0.83g (0.002 mol) of 20ml dichloromethane solution, control temperature -3 ° C ~ -6 ° C The reaction was carried out for 11 hours; the reaction solution was slowly poured into a saturated sodium carbonate solution, deionized water was added, and the pH was adjusted to 7.5 with sodium carbonate. The chloroform was extracted three times, and the organic phase was collected and dried over anhydrous magnesium sulfate. After an hour, suction filtration and evaporation of the organic solvent gave a yellow solid, Compound III.
本实施例中，对本发明红光激发荧光染料(Ⅲ)进行检测及表征数据如下：In this embodiment, the red light-excited fluorescent dye (III) of the present invention is detected and characterized as follows:
元素分析计算值(CHBFNO):C45H44BF2N5O9 Elemental Analysis Calculated Value (CHBFNO): C 45 H 44 BF 2 N 5 O 9
质谱(MS+)：847.32(M+)Mass Spectrum (MS+): 847.32 (M+)
m/z:847.32(100.0％),848.32(50.9％),846.32(24.7％),849.33(12.7％),847.33(12.2％),848.33(3.9％),850.33(2.9％),849.32(2.8％)m/z: 847.32 (100.0%), 848.32 (50.9%), 846.32 (24.7%), 849.33 (12.7%), 847.33 (12.2%), 848.33 (3.9%), 850.33 (2.9%), 849.32 (2.8%) )
元素分析:C,63.76；H,5.23；B,1.28；F,4.48；N,8.26；O,16.99。 Elemental analysis: C, 63.76; H, 5.23; B, 1.28; F, 4.48; N, 8.26; O, 16.99.
实施例3Example 3
本实施例提供的红光激发荧光染料(Ⅳ)的制备方法：The preparation method of the red light-excited fluorescent dye (IV) provided by the embodiment:
具有式(Ⅳ)结构：Has the structure of formula (IV):
Figure PCTCN2017113465-appb-000008
Figure PCTCN2017113465-appb-000008
其制备方法如下： The preparation method is as follows:
Figure PCTCN2017113465-appb-000009
Figure PCTCN2017113465-appb-000009
(1)中间体1-Ⅳ制备(1) Preparation of intermediate 1-IV
在氮气保护下，向1000ml反应瓶中加入无水CuI 9.5g(0.05mol)和100mlTHF，冷却至-50℃，滴加ClCH2CH＝CHLi 6.2g(0.075mol)，搅拌30min，继续冷却至-75℃，滴加2-氯-4-甲基-2H-吡咯2.9g(0.025mol)的300ml四氢呋喃溶液，反应结束后，用250ml乙二醇二甲醚稀释，采用去离子水洗涤，浓缩，得到中间体1-Ⅳ。Under a nitrogen atmosphere, anhydrous CuI 9.5 g (0.05 mol) and 100 ml of THF were added to a 1000 ml reaction flask, cooled to -50 ° C, ClCH 2 CH=CHLi 6.2 g (0.075 mol) was added dropwise, stirred for 30 min, and cooling was continued until - At 75 ° C, a solution of 2.9 g (0.025 mol) of 2-chloro-4-methyl-2H-pyrrole in 300 ml of tetrahydrofuran was added dropwise. After completion of the reaction, it was diluted with 250 ml of ethylene glycol dimethyl ether, washed with deionized water and concentrated. Intermediate 1-IV was obtained.
(2)中间体2-Ⅳ制备(2) Preparation of intermediate 2-IV
在反应瓶中加入无水氯化铝5.3g(0.04mol)，二氯甲烷130ml，置于冰盐浴中，搅拌，降温至-2℃，加入中间体2-Ⅳ 7.4g(0.02mol)，继续降温至-5℃，开始滴加氯乙酰氯3.4g(0.03mol)，控制温度在-5℃～-6℃， 反应10小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即中间体2-Ⅳ。Add 5.3 g (0.04 mol) of anhydrous aluminum chloride, 130 ml of dichloromethane to the reaction flask, place in an ice salt bath, stir, cool to -2 ° C, and add intermediate 2-IV 7.4 g (0.02 mol). Continue to cool down to -5 ° C, start adding 3.4 μg of chloroacetyl chloride (0.03 mol), control the temperature at -5 ° C ~ -6 ° C, The reaction was carried out for 10 hours; the reaction solution was slowly poured into a saturated sodium carbonate solution, deionized water was added, and the pH was adjusted to 7.0 with sodium carbonate. The organic phase was extracted three times and then dried over anhydrous magnesium sulfate for three hours. Filtration and evaporation of the organic solvent gave a yellow solid, Intermediate 2-IV.
(3)中间体3-Ⅳ制备(3) Preparation of intermediate 3-IV
将三氟化硼***120ml和三乙胺15ml缓慢滴加到步骤(2)所得中间体2-Ⅳ的200ml二氯甲烷溶液中，不断搅拌，控制温度在25℃～27℃，反应6小时，直接蒸出溶剂，得到油状物，采用异丙醇和石油醚(体积比为1:10)重结晶得到类白色固体，即中间体3-Ⅳ。120 ml of boron trifluoride diethyl ether and 15 ml of triethylamine were slowly added dropwise to a solution of the intermediate 2-IV obtained in the step (2) in 200 ml of dichloromethane, stirring was continued, and the temperature was controlled at 25 ° C to 27 ° C for 6 hours. The solvent was distilled off to give an oily material which crystallised from isopropyl alcohol and petroleum ether (1:10) to give an off-white solid, intermediate 3-IV.
(4)化合物Ⅳ制备(4) Preparation of Compound IV
在500ml反应瓶中加入无水氯化铝20.0g(0.15mol)，二氯甲烷250ml，置于冰盐浴中，搅拌，降温至-3℃，加入(2-氰氧基-3-苯氧基苯氧基)噻吩15.5g(0.05mol)，继续降温至-10℃，开始滴加中间体3-Ⅳ4.2g(0.01mol)的50ml二氯甲烷溶液，控制温度0℃～-4℃，反应11小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即化合物Ⅳ。Add 20.0g (0.15mol) of anhydrous aluminum chloride to 250ml reaction flask, 250ml of dichloromethane, put in ice salt bath, stir, cool down to -3 °C, add (2-cyanooxy-3-phenoxy) 15.5g (0.05mol) of phenoxy)thiophene, continue to cool down to -10 ° C, began to add dropwise to the intermediate 3-IV 4.2g (0.01mol) of 50ml dichloromethane solution, control temperature 0 ° C ~ -4 ° C, The reaction was slowly poured into a saturated sodium carbonithocarbonate solution, deionized water was added, and the pH was adjusted to 7.0 with sodium carbonate. The organic phase was extracted three times and then dried over anhydrous magnesium sulfate for three hours. Filtration and evaporation of the organic solvent gave a yellow solid, Compound IV.
本实施例中，对本发明红光激发荧光染料(Ⅳ)进行检测及表征数据如下：In this embodiment, the red light-excited fluorescent dye (IV) of the present invention is detected and characterized as follows:
元素分析计算值(CHBFNOS):C66H44BF2N5O9S3 Elemental Analysis Calculated Value (CHBFNOS): C 66 H 44 BF 2 N 5 O 9 S 3
质谱(MS+)：1196.09(M+)Mass Spectrum (MS+): 1196.09 (M+)
m/z:1195.24(100.0％),1196.24(66.7％),1197.24(27.7％),1194.24(20.9％),1197.23(11.5％),1198.24(11.2％),1198.25(5.4％),1196.25(5.4％), 1199.24(3.4％),1197.25(2.0％),1199.25(1.6％),1196.23(1.6％)m/z: 1195.24 (100.0%), 1192.24 (66.7%), 1197.24 (27.7%), 1194.24 (20.9%), 1197.23 (11.5%), 1192.24 (11.2%), 1192.25 (5.4%), 1192.25 (5.4%) ), 1199.24 (3.4%), 1197.25 (2.0%), 1192.25 (1.6%), 1196.23 (1.6%)
元素分析:C,66.27；H,3.71；B,0.90；F,3.18；N,5.86；O,12.04；S,8.04。Elemental analysis: C, 66.27; H, 3.71; B, 0.90; F, 3.18; N, 5.86; O, 12.04; S, 8.04.
实施例4Example 4
本实施例提供的红光激发荧光染料(Ⅴ)的制备方法：The preparation method of the red light-excited fluorescent dye (V) provided by the embodiment:
具有式(Ⅴ)结构：Has the structure of formula (V):
Figure PCTCN2017113465-appb-000010
Figure PCTCN2017113465-appb-000010
其制备方法如下： The preparation method is as follows:
Figure PCTCN2017113465-appb-000011
Figure PCTCN2017113465-appb-000011
(1)中间体1-Ⅴ制备(1) Preparation of intermediate 1-V
在氮气保护下，在2000ml反应瓶中加入无水CuI 19.0g(0.1mol)和250mlTHF，冷却至-45℃，滴加ClCH2CH＝CHLi 16.4g(0.2mol)，搅拌45min，继续冷却至-76℃，滴加2-氯-4-甲基-2H-吡咯5.6g(0.05mol)的550ml四氢呋喃溶液，反应结束后，用450ml乙二醇二甲醚稀释，采用去离子水洗涤，浓缩，得到中间体1-Ⅴ。Under a nitrogen atmosphere, anhydrous CuI 19.0 g (0.1 mol) and 250 ml of THF were added to a 2000 ml reaction flask, cooled to -45 ° C, and ClCH 2 CH=CHLi 16.4 g (0.2 mol) was added dropwise, stirred for 45 min, and cooling was continued until - A solution of 5.6 g (0.05 mol) of 2-chloro-4-methyl-2H-pyrrole in 550 ml of tetrahydrofuran was added dropwise at 76 ° C. After completion of the reaction, it was diluted with 450 ml of ethylene glycol dimethyl ether, washed with deionized water and concentrated. Intermediate 1-V was obtained.
(2)中间体2-Ⅴ制备(2) Preparation of intermediate 2-V
在反应瓶中加入无水氯化铝13.3g(0.1mol)，二氯甲烷260ml，置于冰盐浴中，搅拌，降温至-1℃，加入中间体1-Ⅴ 6.2g(0.04mol)，继续降温至-3℃，开始滴加氯乙酰氯9.0g(0.08mol)，控制温度不高于-6℃～-7℃， 反应12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.5，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即中间体2-Ⅴ。Anhydrous aluminum chloride (13.3 g (0.1 mol), dichloromethane 260 ml was added to the reaction flask, placed in an ice salt bath, stirred, cooled to -1 ° C, and intermediate 1-V 6.2 g (0.04 mol) was added. Continue to cool down to -3 ° C, start adding chloroacetyl chloride 9.0g (0.08mol), control temperature is not higher than -6 ° C ~ -7 ° C, The reaction was slowly poured into a saturated sodium bicarbonate solution, deionized water was added, and the pH was adjusted to 7.5 with sodium carbonate. The organic phase was extracted three times with trichloromethane and dried over anhydrous magnesium sulfate for three hours. Filtration and evaporation of the organic solvent gave a yellow solid, Intermediate 2-V.
(3)中间体3-Ⅴ制备(3) Preparation of intermediate 3-V
将三氟化硼***400ml和三乙胺40ml缓慢滴加到步骤(2)所得中间体2-Ⅰ的500ml二氯甲烷溶液中，不断搅拌，控制温度在26℃～28℃，反应5小时，直接蒸出溶剂，得到油状物，采用异丙醇和石油醚(体积比为1:9)重结晶得到类白色固体，即中间体3-Ⅴ。400 ml of boron trifluoride diethyl ether and 40 ml of triethylamine were slowly added dropwise to a solution of the intermediate 2-I obtained in the step (2) in 500 ml of dichloromethane, stirring was continued, and the temperature was controlled at 26 ° C to 28 ° C for 5 hours. The solvent was distilled off to give an oily material which crystallised from isopropyl alcohol and petroleum ether (1:9) to give an off-white solid, intermediate 3-V.
(4)化合物Ⅴ制备(4) Preparation of Compound V
在反应瓶中加入无水氯化铝46.7g(0.35mol)，二氯甲烷500ml，置于冰盐浴中，搅拌，降温至0℃，加入1-(环戊-1,3-二烯-1-基甲基)-3-(环戊-1,3-二烯-1-基氧基)-2-甲氧基苯39.9g(0.15mol)，继续降温至-8℃，开始滴加中间体3-Ⅴ 8.4g(0.02mol)的200ml二氯甲烷溶液，控制温度-4℃～-7℃，反应12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值8.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即化合物Ⅴ。46.7 g (0.35 mol) of anhydrous aluminum chloride and 500 ml of dichloromethane were added to the reaction flask, placed in an ice salt bath, stirred, cooled to 0 ° C, and 1-(cyclopenta-1,3-diene- 39.9 g (0.15 mol) of 1-ylmethyl)-3-(cyclopenta-1,3-dien-1-yloxy)-2-methoxybenzene, continue to cool down to -8 ° C, start to add dropwise Intermediate 3-V 8.4g (0.02mol) in 200ml dichloromethane solution, control temperature -4 ° C ~ -7 ° C, reaction for 12 hours; slowly pour the reaction solution into saturated sodium bicarbonate solution, add deionized water The pH was adjusted to 8.0 with sodium carbonate, and the chloroform was extracted three times. The organic phase was collected, dried over anhydrous magnesium sulfate for 3 hr, filtered, and evaporated to give a yellow solid, Compound V.
本实施例中，对本发明红光激发荧光染料(Ⅴ)进行检测及表征数据如下：In this embodiment, the red light-excited fluorescent dye (V) of the present invention is detected and characterized as follows:
元素分析计算值(CHBFNOS):C60H47BF2N2O9S6 Elemental Analysis Calculated Value (CHBFNOS): C 60 H 47 BF 2 N 2 O 9 S 6
质谱(MS+)：1181.22(M+)Mass Spectrum (MS+): 1181.22 (M+)
m/z:1180.17(100.0％),1181.17(66.9％),1182.17(26.6％),1182.16 (23.1％),1179.17(21.1％),1183.17(18.8％),1184.17(6.6％),1181.18(4.5％),1183.18(4.2％),1184.16(2.9％),1185.16(1.9％),1185.17(1.8％),1183.16(1.7％),1182.18(1.7％),1184.18(1.4％)m/z: 1180.17 (100.0%), 1181.17 (66.9%), 1182.17 (26.6%), 1182.16 (23.1%), 1117.17 (21.1%), 1183.17 (18.8%), 1184.17 (6.6%), 1181.18 (4.5%), 1183.18 (4.2%), 1184.16 (2.9%), 1185.16 (1.9%), 1185.17 (1.8) %), 1183.16 (1.7%), 1182.18 (1.7%), 1184.18 (1.4%)
元素分析::C,61.01；H,4.01；B,0.92；F,3.22；N,2.37；O,12.19；S,16.29Elemental analysis: C, 61.01; H, 4.01; B, 0.92; F, 3.22; N, 2.37; O, 12.19; S, 16.29
实验例Experimental example
为验证本发明所述的红光激发荧光染料的荧光性能，对其荧光光谱及摩尔消光系数、荧光量子产率进行测定，各参数的具体测定方法如下：In order to verify the fluorescence performance of the red-excited fluorescent dye of the present invention, the fluorescence spectrum, the molar extinction coefficient and the fluorescence quantum yield are determined, and the specific determination methods of each parameter are as follows:
实验例1.红光激发荧光染料的吸收光谱测定Experimental Example 1. Determination of absorption spectrum of red light-excited fluorescent dye
准确称取待测定化合物，配制成浓度为1.0×10-5mol/L的溶液，测定其吸收光谱，如图一所示。The compound to be determined was accurately weighed and prepared into a solution having a concentration of 1.0×10 -5 mol/L, and the absorption spectrum thereof was measured, as shown in Fig. 1.
实验例2.红光激发荧光染料的荧光光谱测定Experimental Example 2. Fluorescence Spectrometric Determination of Red Light-Excited Fluorescent Dyes
利用测定的红光谱中的最大吸收波长，作为荧光光谱的激发波长，测定荧光光谱。称量待测化合物，配制浓度为1.0×10-6mol/L的乙醇：水(50:50，v/v)溶液，测定其发射光谱，如图一所示。The fluorescence spectrum was measured using the maximum absorption wavelength in the measured red spectrum as the excitation wavelength of the fluorescence spectrum. The test compound was weighed, and an ethanol:water (50:50, v/v) solution having a concentration of 1.0×10 -6 mol/L was prepared, and its emission spectrum was measured, as shown in FIG.
实验例3.红光激发荧光染料的摩尔消光系数测定Experimental Example 3. Determination of molar extinction coefficient of red light-excited fluorescent dye
利用紫外可见吸收光谱测定化合物的摩尔消光系数。计算式如式(1)所示：The molar extinction coefficient of the compound was determined by UV-visible absorption spectroscopy. The calculation formula is as shown in equation (1):
A＝εcl     式(1)A=εcl (1)
其中，A代表吸收强度，ε为摩尔吸光系数，c是化合物的浓度，l为检测用的石英池的厚度。 Wherein A represents the absorption intensity, ε is the molar absorption coefficient, c is the concentration of the compound, and l is the thickness of the quartz cell for detection.
实验例4.红光激发荧光染料的荧光量子产率测定Experimental Example 4. Fluorescence quantum yield determination of red light-excited fluorescent dye
在20℃下测定红光激发荧光染料的荧光量子产率，以硫酸奎宁(溶剂为0.1M的H2SO4，量子产率为0.56)作为参比物，通过测量红光激发荧光染料和参比物质的稀溶液在相同激发条件下得到的荧光积分强度和该激发波长下的紫外吸收值，来计算荧光量子产率。产物溶解于无水乙醇中。The fluorescence quantum yield of the red-excited fluorescent dye was measured at 20 ° C. The quinine sulfate (0.1 M H 2 SO 4 solvent with a quantum yield of 0.56) was used as a reference to measure the red fluorescent excitation dye and The fluorescence quantum yield is calculated by the fluorescence integrated intensity obtained from the dilute solution of the reference material under the same excitation conditions and the ultraviolet absorption value at the excitation wavelength. The product was dissolved in absolute ethanol.
计算公式如式(2)所示：The calculation formula is as shown in equation (2):
Figure PCTCN2017113465-appb-000012
Figure PCTCN2017113465-appb-000012
其中，其中Φ为待测物的量子产率，下标R代表参比物。I为荧光积分强度，A为紫外吸收值。η为溶剂折射率。一般要求吸光度A、AR均小于0.1。Where Φ is the quantum yield of the analyte, and subscript R represents the reference. I is the fluorescence integrated intensity, and A is the ultraviolet absorption value. η is the solvent refractive index. Generally, the absorbances A and A R are less than 0.1.
表1实施例1-6所述红光激发荧光染料的光谱学性质Table 1 Spectroscopic properties of red light-excited fluorescent dyes described in Examples 1-6
Figure PCTCN2017113465-appb-000013
Figure PCTCN2017113465-appb-000013
如表1所示，实施例3所述的红光激发荧光染料(Ⅳ)具有最大的吸收波长，同时对应着最大的发射波长747nm、最大的摩尔吸光系数8.9和最大的荧光量子产率88.67％，进而表明该类化合物具有在构筑光电分子开关、发光二极管、场效应晶体管、信息传输和存储器件等领域的优势，还可以 作为荧光探针应用于生物标记、免疫分析以及化学传感等领域。As shown in Table 1, the red light-excited fluorescent dye (IV) described in Example 3 has the largest absorption wavelength, and corresponds to the maximum emission wavelength of 747 nm, the maximum molar absorption coefficient of 8.9, and the maximum fluorescence quantum yield of 88.67%. , which further indicates that the compounds have advantages in constructing photoelectric molecular switches, light-emitting diodes, field effect transistors, information transmission and storage devices, and It is used as a fluorescent probe in the fields of biomarkers, immunoassays, and chemical sensing.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。 It is apparent that the above-described embodiments are merely illustrative of the examples, and are not intended to limit the embodiments. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. There is no need and no way to exhaust all of the implementations. Obvious changes or variations resulting therefrom are still within the scope of the invention.

Claims (6)

  1. 一种红光激发荧光染料，其特征在于，具有如式(Ⅰ)结构：A red light-excited fluorescent dye characterized by having the structure of formula (I):
    Figure PCTCN2017113465-appb-100001
    Figure PCTCN2017113465-appb-100001
    其中，among them,
    R1、R2、R3选自氢、C1-C10烃基、氰基、芳香基或杂环中的一种。R 1 , R 2 and R 3 are one selected from the group consisting of hydrogen, a C 1 -C 10 hydrocarbon group, a cyano group, an aryl group or a heterocyclic ring.
  2. 根据权利要求1所述的一种红光激发荧光染料，其特征在于，R1、R2、R3选自氢、甲基、乙基、氰基、苯基、2-噻吩基、3-噻吩基中的一种。A red light-excited fluorescent dye according to claim 1, wherein R 1 , R 2 and R 3 are selected from the group consisting of hydrogen, methyl, ethyl, cyano, phenyl, 2-thienyl, and 3- One of the thienyl groups.
  3. 根据权利要求1或2所述的一种红光激发荧光染料，其特征在于，其结构式如所示： A red light-excited fluorescent dye according to claim 1 or 2, wherein the structural formula is as follows:
    Figure PCTCN2017113465-appb-100002
    Figure PCTCN2017113465-appb-100002
  4. 一种制备权利要求1-3任一项所述的一种红光激发荧光染料的方法，其特征在于，包括如下步骤： A method for preparing a red light-excited fluorescent dye according to any one of claims 1 to 3, comprising the steps of:
    Figure PCTCN2017113465-appb-100003
    Figure PCTCN2017113465-appb-100003
    (1)中间体1-Ⅰ制备(1) Preparation of intermediate 1-I
    在氮气保护下，反应瓶中加入无水CuI和THF，冷却至-45℃～-55℃，滴加ClCH2CH＝CHLi，搅拌30min～45min，继续冷却至-75℃～-80℃，滴加2-氯-4-甲基-2H-吡咯的四氢呋喃溶液，反应结束后，用乙二醇二甲醚稀释，采用去离子水洗涤，浓缩，得到中间体1-Ⅰ。Under nitrogen protection, add anhydrous CuI and THF to the reaction flask, cool to -45 ° C ~ -55 ° C, add ClCH 2 CH = CHLi, stir for 30 min ~ 45 min, continue cooling to -75 ° C ~ -80 ° C, drop A solution of 2-chloro-4-methyl-2H-pyrrole in tetrahydrofuran was added, and after completion of the reaction, it was diluted with dimethyl ether (hexane), washed with de-ion water and concentrated to give Intermediate 1-I.
    (2)中间体2-Ⅰ制备(2) Preparation of intermediate 2-I
    在反应瓶中加入无水氯化铝，二氯甲烷，置于冰盐浴中，搅拌，降温至0℃～-3℃，加入中间体1-Ⅰ，继续降温至-3℃～-10℃，开始滴加氯乙酰氯，控制温度-2℃～-7℃，反应10～12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.0～8.0，三氯甲烷萃 取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即中间体2-Ⅰ。Add anhydrous aluminum chloride, dichloromethane in the reaction flask, place in ice salt bath, stir, cool to 0 ° C ~ -3 ° C, add intermediate 1-I, continue to cool to -3 ° C ~ -10 ° C Start adding dropwise chloroacetyl chloride, control the temperature -2 ° C ~ -7 ° C, reaction for 10 to 12 hours; slowly pour the reaction solution into saturated sodium bicarbonate solution, add deionized water, and adjust the pH with sodium carbonate 7.0 to 8.0, chloroform extraction After taking three times, the organic phase was collected, dried over anhydrous magnesium sulfate for 3 hr, filtered, and evaporated.
    (3)中间体3-Ⅰ制备(3) Preparation of intermediate 3-I
    将三氟化硼***和三乙胺缓慢滴加到步骤(2)所得中间体2-Ⅰ的二氯甲烷溶液中，不断搅拌，控制温度在25℃～30℃，反应4～6小时，直接蒸出溶剂，得到油状物，采用异丙醇和石油醚(体积比为1:8～1:10)重结晶得到类白色固体，即中间体3-Ⅰ。The boron trifluoride diethyl ether and triethylamine are slowly added dropwise to the dichloromethane solution of the intermediate 2-I obtained in the step (2), and the mixture is continuously stirred, and the temperature is controlled at 25 ° C to 30 ° C for 4 to 6 hours. The solvent was evaporated to give an oily material which crystallised from isopropyl alcohol and petroleum ether (1:8 to 1:10) to give an off-white solid, intermediate 3-I.
    (4)化合物Ⅰ制备(4) Preparation of Compound I
    在反应瓶中加入无水氯化铝，二氯甲烷，置于冰盐浴中，搅拌，降温至0℃～-3℃，加入R1，R2，R3取代的1,2,3-苯三酚，继续降温至-3℃～-10℃，开始滴加中间体3-Ⅰ的二氯甲烷溶液，控制温度0℃～-7℃，反应10～12小时；将反应液缓慢倒入饱和碳素氢钠溶液中，加入去离子水，并采用碳酸钠调节pH值7.0～8.0，三氯甲烷萃取三次，收集有机相，采用无水硫酸镁干燥3小时，抽滤，蒸出有机溶剂，得到黄色固体，即化合物Ⅰ。Add anhydrous aluminum chloride, dichloromethane to the reaction flask, place in an ice salt bath, stir, cool to 0 ° C ~ -3 ° C, add 1 , 1 , 2 , 3 substituted by R 1 , R 2 , R 3 Pyrogallol, continue to cool to -3 ° C ~ -10 ° C, began to add dropwise the intermediate 3-I dichloromethane solution, control the temperature 0 ° C ~ -7 ° C, the reaction for 10 to 12 hours; slowly pour the reaction solution Add saturated water to the saturated sodium carbonate solution, adjust the pH value of 7.0-8.0 with sodium carbonate, extract the chloroform three times, collect the organic phase, dry with anhydrous magnesium sulfate for 3 hours, filter with suction, and distill off the organic solvent. , a yellow solid, Compound I, was obtained.
  5. 权利要求1-4任一项所述的一种红光激发荧光染料在构筑光电分子开关，发光二极管，场效应晶体管，信息传输和存储器件，还可以作为荧光探针应用于生物标记、免疫分析以及化学传感等领域。A red light-exciting fluorescent dye according to any one of claims 1 to 4 for constructing a photoelectric molecular switch, a light emitting diode, a field effect transistor, an information transmission and storage device, and also as a fluorescent probe for biomarker and immunoassay. And areas such as chemical sensing.
  6. 根据权利要求5所述的红光激发荧光染料的应用，其特征在于，包括如下方法：The use of the red light-excited fluorescent dye according to claim 5, comprising the following method:
    将荧光染料分子溶解于二甲酰胺、乙醇、羟乙基哌嗪乙磺酸以任意比例混合的应用。 The use of a fluorescent dye molecule in a mixture of dimethylformamide, ethanol, and hydroxyethylpiperazineethanesulfonic acid in any ratio.
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