Heptamethrin indocyanine dye, its preparation method and application

Abstract

This invention discloses a heptamethrin indocyanine dye, its preparation method, and its applications. The structural formula of the heptamethrin indocyanine dye is as follows: In the structural formula, X includes a nitrogen atom, an oxygen atom, or a sulfur atom; Y includes hydrogen, methyl, ethyl, 2-propyl, tert-butyl, phenyl, benzyl, biphenyl, 1-propyl, cyclopropyl, methylcyclopropyl, n-butyl, 2-methylpropyl, methanesulfonyl, acetyl, or 4-pyridyl; Z includes fluoride ions, chloride ions, bromide ions, iodide ions, perchlorate ions, p-toluenesulfonate ions, tetraphenylborate ions, tetrafluoroborate ions, hexafluoroborate ions, or hexafluorophosphate ions; R includes methyl, ethyl, propyl, tert-butyl, methoxymethyl, methyl formate, methoxy, or 2-acetone. Therefore, this heptamethrin indocyanine dye has wide applicability.

Description

Technical Field

[0001] This invention belongs to the field of polymethyl methacrylate indole cyanine dyes and their preparation, specifically relating to a heptamethyl methacrylate indole cyanine dye, its preparation method, and its application. Background Technology

[0002] Computer-to-plate (CTP) technology can be divided into photosensitive CTP and thermal CTP, with thermal CTP being the most mature, stable, and effective technology currently available. Thermal CTP processes include chemical treatment and chemical-free processing. With technological advancements and increasing environmental requirements, chemical-free thermal CTP is gradually becoming the mainstream technology. The principle of this technology is to use an infrared laser to scan and image the plate material. The infrared dye in the scanned area absorbs the infrared light and converts the light energy into heat energy, raising the temperature of the scanned area above a threshold temperature. This causes the photothermal acid-producing agent in the plate material to decompose, producing acid. Under the action of the acid, the thermal coating in the light-exposed areas undergoes a decomposition reaction. The decomposition products are water-soluble, and after washing, the plate base becomes the hydrophilic blank area. The thermal coating in the unexposed areas does not undergo a decomposition reaction, is not water-soluble, and remains on the plate surface after washing, becoming the oleophilic image area. Because no alkaline solutions or chemical solvents are used in this processing, this type of plate is called a "chemical-free" plate, or simply a treatment-free plate.

[0003] Infrared dyes used in pretreatment-free printing plates are key components that cause changes in the hydrophilicity of the coating. Commonly used infrared dyes to date include polymethylcyanine, squaric acid cyanine, phenolic cyanine, fluorescein, and rhodamine. Heptamethylindocyanine dye belongs to the polymethylcyanine dye family and has good structural modifiability. Currently, the intermediate structures of existing heptamethylindocyanine dyes are mostly five-membered, six-membered, and seven-membered carbon rings. The mainstream five-membered and six-membered carbon ring cycloene heptamethylindocyanine dyes are expensive, resulting in high usage costs.

[0004] Therefore, there is a need in this field to develop novel heptamethrin indolecyanine dye structures. Summary of the Invention

[0005] This invention aims to at least partially solve one of the technical problems in related technologies. Therefore, one objective of this invention is to provide a heptamethrin indole cyanine dye, its preparation method, and its applications. This heptamethrin indole cyanine dye has wide applicability and can be used to prepare treatment-free thermal CTP plates. The prepared treatment-free thermal CTP plates exhibit superior photosensitivity, plate contrast, and printing durability.

[0006] In one aspect of the present invention, a heptamethrin indolecyanine dye is provided, wherein, according to an embodiment of the present invention, the heptamethrin indolecyanine dye has the structural formula of formula (Ⅳ):

[0007]

[0008] Among them, in the structural formula (Ⅳ) of the heptamethrin indocyanine dye,

[0009] X includes nitrogen, oxygen, or sulfur atoms;

[0010] Y includes hydrogen, methyl, ethyl, 2-propyl, tert-butyl, phenyl, benzyl and biphenyl, 1-propyl, cyclopropyl, methylcyclopropyl, n-butyl, 2-methylpropyl, methanesulfonyl, acetyl or 4-pyridyl;

[0011] Z includes fluoride ions, chloride ions, bromide ions, iodide ions, perchlorate ions, p-toluenesulfonate ions, tetraphenylborate ions, tetrafluoroborate ions, hexafluoroborate ions, or hexafluorophosphate ions.

[0012] R includes methyl, ethyl, propyl, tert-butyl, methoxymethyl, methyl formate, methoxy, or 2-propanone.

[0013] The heptamethrin indocyanine dye of the present invention, compared with existing five-membered, six-membered, and seven-membered carbon ring structures, has enhanced overall electron-withdrawing properties due to the introduction of heteroatoms X and substituents Y in its structure. This counteracts the electron-withdrawing effect of more chlorine atoms, reducing electronic resistance in the seven-membered long carbon chain conjugated system, enhancing electron delocalization, and making electron transfer more rapid. Therefore, its sensing and absorption efficiency for infrared light is improved. - It is an anion, making heptamethrin indolecyanine dye an organic salt with good solubility in the system. Therefore, the heptamethrin indolecyanine dye of this invention has wide applicability.

[0014] In some embodiments of the present invention, the heptamethrin indocyanine dye comprises at least one of formulas (Ⅳ-1) to (Ⅳ-18):

[0015]

[0016]

[0017] In some embodiments of the present invention, the chlorine atom in the structure of the heptamethrin indocyanine dye may be further substituted, and the substituent groups include N,N-diphenylamino, p-toluenethiophenol, aniline or benzylamino.

[0018] In some embodiments of the present invention, the heptamethrin indocyanine dye comprises formula (Ⅳ-19) or formula (Ⅳ-20):

[0019] Therefore, this structure has advantages such as better stability and adjustable maximum absorption wavelength.

[0020] In another aspect of the present invention, a method for preparing the above-mentioned heptamethrin indolecyanine dye is provided. According to an embodiment of the present invention, the method includes:

[0021] S1: N,N-dimethylformamide and phosphorus oxychloride are mixed to obtain the first solution;

[0022] S2: Add a six-membered heterocyclic ketone to the first solution to obtain a second solution;

[0023] S3: Add the second solution to ice water and separate to obtain a six-membered heterocyclic cycloene condensing agent;

[0024] S4: Acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt and the six-membered heterocyclic condensing agent are mixed to obtain a third solution;

[0025] S5: After adding an organic solvent to the third solution and pulping, heptamethrin indocyanine dye is obtained;

[0026] The structural formula of the six-membered heterocyclic ketone is formula (Ⅰ):

[0027]

[0028] The structural formula of the six-membered heterocyclic cycloene condensing agent is formula (II):

[0029]

[0030] In the six-membered heterocyclic ketone (I) and the six-membered heterocyclic cycloene condensing agent (II), X and Y are the same as those in formula (IV).

[0031] According to an embodiment of the present invention, a method for preparing heptamethrin indocyanine dye involves the reaction of N,N-dimethylformamide and phosphorus oxychloride to generate a Vilsmeier-Haack reagent. In this reaction, the disubstituted formamide and phosphorus oxychloride provide chloroimine ions. The reaction mechanism is as follows:

[0032] Subsequently, a six-membered heterocyclic ketone is added for reaction. The ketone undergoes chlorination with phosphorus oxychloride, and the chlorinated product reacts with the Vilsmeier-Haack reagent. Ice water is then added, generating a six-membered heterocyclic cycloene condensing agent. The six-membered heterocyclic ketone can introduce heteroatoms such as nitrogen, oxygen, and sulfur into the six-membered cycloene. Acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt, and the six-membered heterocyclic condensing agent undergo an aldol condensation reaction. The addition of an organic solvent allows the product to be fully extracted, ultimately yielding a heptamethrin indole cyanine dye composed of a six-membered cycloene structure containing heteroatoms. The synthetic route for heptamethrin indole cyanine dye is as follows:

[0033] Therefore, the method for preparing heptamethrin indolecyanine dye of the present invention has a short synthetic route, simple process, and does not require precious metal catalysis, which can improve the preparation efficiency and realize low-cost mass production.

[0034] In addition, the method for preparing heptamethrin indocyanine dye according to the above embodiments of the present invention may also have the following additional technical features:

[0035] In some embodiments of the present invention, the six-membered heterocyclic ketone comprises at least one of formulas (I-1) to (I-18):

[0036]

[0037] In some embodiments of the present invention, the six-membered heterocyclic cycloene condensing agent comprises at least one of formulas (II-1) to (II-18):

[0038]

[0039] In some embodiments of the present invention, the benzoindole quaternary ammonium salt has the structural formula of formula (Ⅲ):

[0040]

[0041] In the structural formula (Ⅲ) of the benzoindole quaternary ammonium salt, Z and R are the same as those in formula (Ⅳ).

[0042] In some embodiments of the present invention, the benzoindole quaternary ammonium salt comprises at least one of formulas (III-1) to (III-8):

[0043]

[0044] In some embodiments of the present invention, in steps S1 and S2, the molar ratio of N,N-dimethylformamide, phosphorus oxychloride, and the six-membered heterocyclic ketone is 10:8:(1-8). This improves product yield and increases raw material utilization.

[0045] In some embodiments of the present invention, in step S1, the first reaction temperature of the mixture of N,N-dimethylformamide and phosphorus oxychloride is 0°C-5°C, and the first reaction time is 0.8h-1.2h. This improves the preparation efficiency.

[0046] In some embodiments of the present invention, in step S2, the second reaction temperature for adding the six-membered heterocyclic ketone to the first solution is 40°C-60°C, and the second reaction time is 4h-8h. This improves the preparation efficiency.

[0047] In some embodiments of the present invention, in step S3, the stirring time for adding ice water to the second solution is 6-12 hours. This improves the preparation efficiency.

[0048] In some embodiments of the present invention, in step S4, the molar ratio of the six-membered heterocyclic cycloene condensing agent, benzoindole quaternary ammonium salt, and anhydrous sodium acetate is 1:(2-3):(3-6). This improves product yield and increases raw material utilization.

[0049] In some embodiments of the present invention, in step S4, the third reaction temperature for mixing the acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt, and the six-membered heterocyclic condensing agent is 60°C-100°C, and the third reaction time is 2h-10h. This improves the preparation efficiency.

[0050] In another aspect, the present invention provides a treatment-free thermal CTP plate. According to an embodiment of the present invention, the treatment-free thermal CTP plate comprises the aforementioned heptamethrin indole cyanine dye or heptamethrin indole cyanine dye prepared by the aforementioned method. Therefore, the treatment-free thermal CTP plate exhibits superior photosensitivity, plate contrast, and printing durability. Those skilled in the art will understand that the features and advantages described above for the heptamethrin indole cyanine dye and its preparation method also apply to this treatment-free thermal CTP plate, and will not be repeated here.

[0051] In another aspect, the present invention provides a near-infrared fluorescent probe. According to an embodiment of the present invention, the near-infrared fluorescent probe comprises the aforementioned heptamethrin indolecyanine dye or the heptamethrin indolecyanine dye prepared by the aforementioned method. Similarly, the features and advantages described above for the heptamethrin indolecyanine dye and its preparation method also apply to this near-infrared fluorescent probe, and will not be repeated here. Attached Figure Description

[0052] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0053] Figure 1This is a flowchart of a method for preparing heptamethrin indolecyanine dye according to some embodiments of the present invention;

[0054] Figure 2 The NMR spectrum of heptamethrin indocyanine dye (Ⅳ-2) prepared in Example 1;

[0055] Figure 3 The NMR spectrum of heptamethrin indocyanine dye (Ⅳ-7) prepared in Example 2;

[0056] Figure 4 The NMR spectrum of heptamethrin indocyanine dye (Ⅳ-8) prepared in Example 10. Detailed Implementation

[0057] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0058] In a first aspect, the present invention provides a heptamethrin indolecyanine dye, the structural formula of which is formula (Ⅳ):

[0059]

[0060] Among them, the structural formula (Ⅳ) of heptamethrin indocyanine dye,

[0061] X includes nitrogen, oxygen, or sulfur atoms;

[0062] Y includes hydrogen, methyl, ethyl, 2-propyl, tert-butyl, phenyl, benzyl and biphenyl, 1-propyl, cyclopropyl, methylcyclopropyl, n-butyl, 2-methylpropyl, methanesulfonyl, acetyl or 4-pyridyl;

[0063] Z includes fluoride ions, chloride ions, bromide ions, iodide ions, perchlorate ions, p-toluenesulfonate ions, tetraphenylborate ions, tetrafluoroborate ions, hexafluoroborate ions, or hexafluorophosphate ions.

[0064] R includes methyl, ethyl, propyl, tert-butyl, methoxymethyl, methyl formate, methoxy, or 2-propanone.

[0065] The inventors discovered that, compared to existing five-membered, six-membered, and seven-membered carbon ring structures, the heteroatom X and substituent Y introduced in this invention enhance the overall electron-withdrawing properties of XY, offsetting the electron-withdrawing effect of more chlorine atoms. This reduces the electronic resistance in the seven-membered long carbon chain conjugated system, enhances the electron delocalization effect, and makes electron transfer more rapid. Therefore, the sensing and absorption efficiency of infrared light is improved. - It is an anion, making heptamethrin indolecyanine dye an organic salt with good solubility in the system. Therefore, the heptamethrin indolecyanine dye of this invention has wide applicability.

[0066] Furthermore, the heptamethrin indolecyanine dye includes at least one of formulas (Ⅳ-1) to (Ⅳ-18):

[0067] When X is a nitrogen atom, Y is a hydrogen atom, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-1;

[0068] When X is a nitrogen atom, Y is a methyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound with structure IV-2;

[0069] When X is a nitrogen atom, Y is an ethyl atom, Z is an iodine atom, and R is a methyl atom, the heptamethrin indocyanine dye is a compound having structure IV-3;

[0070] When X is a nitrogen atom, Y is a 2-propyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-4;

[0071] When X is a nitrogen atom, Y is a tert-butyl atom, Z is an iodine atom, and R is a methyl atom, the heptamethrin indocyanine dye is a compound having structure IV-5;

[0072] When X is a nitrogen atom, Y is a phenyl atom, Z is an iodine atom, and R is a methyl atom, the heptamethrin indocyanine dye is a compound having structure IV-6;

[0073] When X is a nitrogen atom, Y is a benzyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-7;

[0074] When X is a nitrogen atom, Y is a biphenyl atom, Z is an iodine atom, and R is a methyl atom, the heptamethrin indocyanine dye is a compound having structure IV-8;

[0075] When X is an oxygen atom, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-9;

[0076] When X is a sulfur atom, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-10;

[0077] When X is a nitrogen atom, Y is a 1-propyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-11;

[0078] When X is a nitrogen atom, Y is a cyclopropyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-12;

[0079] When X is a nitrogen atom, Y is a methylcyclopropyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-13;

[0080] When X is a nitrogen atom, Y is a n-butyl atom, Z is an iodine atom, and R is a methyl atom, the heptamethrin indocyanine dye is a compound having structure IV-14;

[0081] When X is a nitrogen atom, Y is a 2-methylpropyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-15;

[0082] When X is a nitrogen atom, Y is a methanesulfonyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-16;

[0083] When X is a nitrogen atom, Y is an acetyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-17;

[0084] When X is a nitrogen atom, Y is a 4-pyridyl group, Z is an iodine atom, and R is a methyl group, the heptamethrin indocyanine dye is a compound having structure IV-18;

[0085] The structural formulas of the compounds shown as examples IV-1 to IV-18 are as follows:

[0086]

[0087] According to some embodiments of the present invention, the chlorine atom in the structure of heptamethrin indocyanine dye can be further substituted, with substituents including N,N-diphenylamino, p-toluenethiophenol, aniline, or benzylamino. Therefore, this structure has advantages such as better stability and tunable maximum absorption wavelength.

[0088] Furthermore, the heptamethrin indocyanine dyes with chlorine atoms substituted include formulas (Ⅳ-19) or (Ⅳ-20):

[0089]

[0090] According to another aspect of the present invention, the present invention provides a method for preparing the above-mentioned heptamethrin indolecyanine dye. The method for preparing heptamethrin indolecyanine dye proposed in the embodiments of the present invention is described below with reference to the accompanying drawings.

[0091] like Figure 1 As shown, the method includes the following steps:

[0092] Step S1: Mix N,N-dimethylformamide and phosphorus oxychloride to obtain the first solution.

[0093] Specifically, N,N-dimethylformamide is mixed and stirred with a solvent, and then phosphorus oxychloride is slowly added dropwise to react and obtain a first solution containing the Vilsmeier-Haack reagent. The solvent (e.g., acetonitrile) primarily serves as a diluent and reaction solvent. The solvent is not limited here; those skilled in the art can choose flexibly according to the actual situation, as long as it does not participate in the reaction and is soluble in water.

[0094] According to some embodiments of the present invention, the first reaction temperature of the mixture of N,N-dimethylformamide and phosphorus oxychloride is 0°C-5°C, for example, 0°C, 1°C, 2°C, 3°C, 4°C, and 5°C, and the first reaction time is 0.8h-1.2h, for example, 0.8h, 0.9h, 1.0h, 1.1h, and 1.2h. This improves the preparation efficiency.

[0095] Step S2: Add a six-membered heterocyclic ketone to the first solution to obtain the second solution.

[0096] Specifically, the aforementioned six-membered heterocyclic ketone is reacted by slowly adding it dropwise to the first solution after being mixed with a solvent (e.g., acetonitrile). The volume ratio of solvent to phosphorus oxychloride in the reaction system is (2.5-3.5):1. Specifically, the total amount of solvent can be added in half in steps S1 and S2 respectively, and the amount of solvent can be added or reduced according to the viscosity of the reaction.

[0097] According to some embodiments of the present invention, the structural formula of the above-mentioned six-membered heterocyclic ketone is formula (Ⅰ):

[0098]

[0099] In the six-membered heterocyclic ketone, X and Y are the same as those in formula (IV) above.

[0100] Furthermore, the six-membered heterocyclic ketone includes at least one of formulas (I-1) to (I-18):

[0101]

[0102] The addition of a six-membered heterocyclic ketone can introduce an intermediate structure of a six-membered carbon ring and introduce heteroatoms such as nitrogen, oxygen, and sulfur into the structure.

[0103] According to some embodiments of the present invention, in steps S1 and S2, the molar ratio of N,N-dimethylformamide, phosphorus oxychloride, and the six-membered heterocyclic ketone is 10:8:(1-8), for example, 10:8:1, 10:8:2, 10:8:3, 10:8:4, 10:8:5, 10:8:6, 10:8:7, and 10:8:8. A preferred molar ratio is 10:8:(2-5). This improves product yield and increases raw material utilization.

[0104] According to some embodiments of the present invention, in step S2, the second reaction temperature for adding the six-membered heterocyclic ketone to the first solution is 40°C-60°C, for example, 40°C, 45°C, 50°C, 55°C, and 60°C, and the second reaction time is 4h-8h, for example, 4h, 5h, 6h, 7h, and 8h. Preferably, the reaction temperature is 50°C-60°C and the reaction time is 5h-7h. This improves the preparation efficiency.

[0105] The heating and heat preservation equipment used in the reaction process of step S2 is not limited here. Those skilled in the art can choose flexibly according to the actual situation, as long as it meets the process requirements of this invention. As an example, the heating and heat preservation equipment is an oil bath.

[0106] Step S3: Add the second solution to ice water and separate to obtain the six-membered heterocyclic cycloene condensing agent.

[0107] Specifically, the second solution, cooled to room temperature, was slowly added dropwise to ice water while stirring. After filtration, washing with water until neutral, and drying under reduced pressure to constant weight, a pale yellow solid product, a six-membered heterocyclic cycloene condensing agent, was obtained. The mass ratio of ice water to phosphorus oxychloride was (8-16):1.

[0108] According to some embodiments of the present invention, in step S3, the stirring time for adding the second solution to ice water is 6h-12h, for example, 6h, 7h, 8h, 9h, 10h, 11h, and 12h. Preferably, it is 8h-12h. This improves the preparation efficiency.

[0109] According to some embodiments of the present invention, the structural formula of the above-mentioned six-membered heterocyclic cycloene condensing agent is formula (II):

[0110]

[0111]

[0112] In the six-membered heterocyclic cycloene condensing agent, X and Y are the same as those in the above formula (IV).

[0113] Furthermore, the six-membered heterocyclic cycloene condensing agent includes at least one of formulas (II-1) to (II-18):

[0114]

[0115] Step S4: Mix acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt and a six-membered heterocyclic condensing agent to obtain a third solution.

[0116] In this step, acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt, and the six-membered heterocyclic condensing agent obtained in step S3 are mixed to undergo an aldol condensation reaction to obtain the third solution. Specifically, acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt, and the six-membered heterocyclic condensing agent are mixed and stirred to react, resulting in the third solution. After the reaction is completed, the third solution is evaporated to dryness under reduced pressure.

[0117] The mixing order of the acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt, and six-membered heterocyclic condensing agent is not limited; they can be mixed simultaneously or sequentially. As an example, the acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt, and six-membered heterocyclic condensing agent are added and mixed sequentially.

[0118] According to some embodiments of the present invention, the structural formula of the benzoindole quaternary ammonium salt is formula (Ⅲ):

[0119]

[0120] In the benzoindole quaternary ammonium salt, Z and R are the same as those in formula (IV) above. This simplifies the process route, eliminates the need for precious metal catalysis, and improves preparation efficiency.

[0121] Furthermore, the benzoindole quaternary ammonium salt comprises at least one of formulas (III-1) to (III-8):

[0122]

[0123] According to some embodiments of the present invention, in step S4, the molar ratio of the six-membered heterocyclic cycloene condensing agent, benzoindole quaternary ammonium salt, and anhydrous sodium acetate is 1:(2-3):(3-6), for example 1:2:3, 1:2:4, 1:2:5, 1:2:6, 1:2.5:4, 1:3:3, 1:3:4, 1:3:5, and 1:3:6. A preferred molar ratio is 1:(2.2-2.8):(3-5). This improves product yield and increases raw material utilization.

[0124] The mass ratio of the acetic anhydride to the total amount of solids added is (3-6):1, wherein the total amount of solids added refers to the total amount of the six-membered heterocyclic cycloene condensing agent, benzoindole quaternary ammonium salt and anhydrous sodium acetate added.

[0125] According to some embodiments of the present invention, in step S4, the third reaction temperature for mixing acetic anhydride, anhydrous sodium acetate, benzoindole quaternary ammonium salt, and the six-membered heterocyclic condensing agent is 60℃-100℃, for example, 60℃, 70℃, 80℃, 90℃, and 100℃, and the third reaction time is 2h-10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, and 10h. Preferably, the reaction temperature is 70℃-90℃, and the reaction time is 4h-8h. This improves the preparation efficiency.

[0126] The chlorine atom in the structure of the above-mentioned heptamethrin indolecyanine dye can be further substituted. The preparation method is as follows: dissolve the heptamethrin indolecyanine dye and the substituted product (e.g., a substituted product with N,N-diphenylamine, p-toluenethiophenol, aniline or benzylamino groups) in a solvent (e.g., methanol), add a methanol solution of sodium hydroxide dropwise, reflux for 0.8 h to 1.2 h, and after the reaction is complete, post-treatment is performed to obtain the substituted product.

[0127] Step S5: After adding an organic solvent to the third solution and pulping, heptamethrin indocyanine dye is obtained.

[0128] Specifically, an organic solvent is added to the third solution, and after slurrying at room temperature, the product is fully separated. After filtration and drying under reduced pressure to constant weight, the dark green product, heptamethrin indolecyanine dye, is obtained. As an example, the synthetic route of heptamethrin indolecyanine dye is as follows:

[0129]

[0130] The aforementioned pulping organic solvent includes at least one selected from petroleum ether, n-hexane, diethyl ether, acetone, and ethyl acetate. Hexane and ethyl acetate are preferred. In some specific embodiments, a mixture of ethyl acetate and n-hexane is used as the pulping organic solvent, with a volume ratio of ethyl acetate to n-hexane of 3:4. This allows for complete product extraction.

[0131] The theoretical mass ratio of the above-mentioned organic solvent to the product heptamethrin indolecyanine dye is (4-8):1. The theoretical value is calculated using the reaction equation based on the amount of experimental raw materials added.

[0132] The preparation apparatus of this invention is not limited herein, and those skilled in the art can flexibly choose one according to the actual situation, as long as it meets the process requirements of this invention. As an example, a three-necked flask equipped with a stirrer and a thermometer is selected as the preparation apparatus.

[0133] Therefore, the method for preparing heptamethrin indolecyanine dye of the present invention has a short synthetic route, simple process, and does not require precious metal catalysis, which can improve the preparation efficiency and realize low-cost mass production.

[0134] According to another aspect of the present invention, a treatment-free thermal CTP plate is provided. According to an embodiment of the present invention, the treatment-free thermal CTP plate comprises the above-described heptamethrin indole cyanine dye or heptamethrin indole cyanine dye prepared by the above-described method. Therefore, the treatment-free thermal CTP plate has superior photosensitivity, plate contrast, and printing durability. Those skilled in the art will understand that the features and advantages described above for the heptamethrin indole cyanine dye and its preparation method also apply to the treatment-free thermal CTP plate, and will not be repeated here.

[0135] The aforementioned heptamethrin indocyanine dye possesses infrared imaging capabilities and can also be used to prepare near-infrared fluorescent probes. The infrared fluorescent probes include the aforementioned heptamethrin indocyanine dye or heptamethrin indocyanine dye prepared using the aforementioned method. Similarly, the features and advantages described above regarding the heptamethrin indocyanine dye and its preparation method also apply to this near-infrared fluorescent probe, and will not be repeated here.

[0136] The embodiments of the present invention are described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. In addition, unless otherwise specified, all reagents used in the following embodiments are commercially available or can be synthesized according to the methods described herein or known to others. For reaction conditions not listed, they are also readily available to those skilled in the art.

[0137] Example 1

[0138] Synthesize heptamethrin indocyanine (Ⅳ-2) according to the following synthetic route:

[0139]

[0140] A method for preparing heptamethrin indolecyanine (Ⅳ-2) includes the following steps:

[0141] (1) Add 31.2g (0.442mol, 5eq) DMF and 50mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 54.2g (0.353mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0142] (2) Slowly add 10.0 g (0.088 mol, 1 eq) of N-methyl-4-piperidinone (Ⅰ-2) and 50 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0143] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 12.6 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-2), with a yield of 75.9%.

[0144] (4) Add 50 mL of acetic anhydride, 2.5 g (30.32 mmol, 4 eq) of anhydrous sodium acetate, 2.0 g (10.65 mmol, 1 eq) of the product of step (3) and 7.9 g (18.96 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0145] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added as mixed solvents. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 5.4 g of the dark green product heptamethrin indolecyanine dye (Ⅳ-2), with a yield of 81.8%; MS (ESI) m / z = 499, consistent with the theoretical value; its NMR spectrum is shown below. Figure 2 As shown, the NMR data are:

[0146] H-NMR{CDCl3,(1.71ppm,12H),(3.69ppm,6H),(3.75ppm,4H),(3.98ppm,2H),(5.98pp m,2H),(7.12ppm,2H),(7.23ppm,2H),(7.38ppm,2H),(7.48ppm,3H),(8.29ppm,2H)}.

[0147] Example 2

[0148] Synthesize heptamethrin indocyanine (Ⅳ-7) according to the following synthetic route:

[0149]

[0150] A method for preparing heptamethrin indolecyanine (Ⅳ-7) includes the following steps:

[0151] (1) Add 38.6g (0.528mol, 5eq) DMF and 100mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 64.8g (0.422mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0152] (2) Slowly add 20.0 g (0.105 mol, 1 eq) of N-benzylpiperidone (Ⅰ-7) and 100 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0153] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 21.4 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-7), with a yield of 79.3%.

[0154] (4) Add 50 mL of acetic anhydride, 2.5 g (30.32 mmol, 4 eq) of anhydrous sodium acetate, 2.0 g (7.58 mmol, 1 eq) of the product of step (3) and 5.6 g (18.96 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0155] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added as mixed solvents. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 4.5 g of the dark green product heptamethrin indolecyanine dye (Ⅳ-7), with a yield of 84.9%; MS (ESI) m / z = 574, consistent with the theoretical value; its NMR spectrum is as follows. Figure 3 As shown, the NMR data are:

[0156] H-NMR{CDCl3,(0.91ppm,3H),(1.71ppm,12H),(3.69ppm,3H),(3.76ppm,4H),(3.99ppm,2H), (5.99ppm,2H),(7.16ppm,2H),(7.20ppm,4H),(7.35ppm,5H),(7.41ppm,2H),(8.20ppm,2H)}.

[0157] Example 3

[0158] Synthesize heptamethrin indocyanine (Ⅳ-9) according to the following synthetic route:

[0159]

[0160] A method for preparing heptamethrin indolecyanine (Ⅳ-9) includes the following steps:

[0161] (1) Add 36.5g (0.499mol, 5eq) DMF and 100mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 61.2g (0.399mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0162] (2) Slowly add 10.0 g (0.099 mol, 1 eq) of tetrahydropyranone (Ⅰ-9) and 100 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0163] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 6.8 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-9), with a yield of 39.0%.

[0164] (4) Add 50 mL of acetic anhydride, 3.7 g (45.84 mmol, 4 eq) of anhydrous sodium acetate, 2.0 g (11.46 mmol, 1 eq) of the product of step (3) and 8.6 g (28.65 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0165] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 5.6 g of the dark green product heptamethrin indole cyanine dye (Ⅳ-9), with a yield of 80.1%; MS (ESI) m / z = 485, which is consistent with the theoretical value; its NMR data are: H-NMR {CDCl3, (0.93ppm, 3H), (1.76ppm, 12H), (2.72ppm, 3H), (3.85ppm, 4H), (4.99ppm, 2H), (6.13ppm, 2H), (7.12ppm, 2H), (7.24ppm, 2H), (7.44ppm, 2H), (7.58ppm, 2H)}.

[0166] Example 4

[0167] Synthesize heptamethrin indocyanine (Ⅳ-7) according to the following synthetic route:

[0168]

[0169] A method for preparing heptamethrin indolecyanine (Ⅳ-7) includes the following steps:

[0170] (1) Add 97.0g (1.32mol, 5eq) DMF and 100mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 170g (1.10mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0171] (2) Slowly add 50.0 g (0.26 mol, 1 eq) of N-benzylpiperidone (Ⅰ-7) and 100 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0172] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 1000 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 54.7 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-7), with a yield of 78.5%.

[0173] (4) Add 200 mL of acetic anhydride, 18.6 g (227.46 mmol, 6 eq) of anhydrous sodium acetate, 10.0 g (37.91 mmol, 1 eq) of the product of step (3) and 34.2 g (113.73 mmol, 3 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0174] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (150 mL) and n-hexane (200 mL) were added as mixed solvents. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 23.1 g of the dark green product heptamethrin indolecyanine dye (Ⅳ-7), with a yield of 86.7%. Its NMR data are as follows:

[0175] H-NMR{CDCl3,(0.91ppm,3H),(1.71ppm,12H),(3.69ppm,3H),(3.76ppm,4H),(3.99ppm,2H), (5.99ppm,2H),(7.16ppm,2H),(7.20ppm,4H),(7.35ppm,5H),(7.41ppm,2H),(8.20ppm,2H)}.

[0176] Example 5

[0177] Synthesize heptamethrin indocyanine (Ⅳ-1) according to the following synthetic route:

[0178]

[0179] A method for preparing heptamethrin indolecyanine (Ⅳ-1) includes the following steps:

[0180] (1) Add 31.2g (0.442mol, 5eq) DMF and 50mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 54.2g (0.353mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0181] (2) After slowly adding 8.8 g (0.088 mol, 1 eq) of 4-piperidinone (Ⅰ-1) and 50 mL of acetonitrile mixture to the solution in step (1), react in an oil bath at 50 °C for 5 h.

[0182] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 7.0 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-1), with a yield of 45.5%.

[0183] (4) Add 50 mL of acetic anhydride, 2.5 g (30.32 mmol, 4 eq) of anhydrous sodium acetate, 1.9 g (10.65 mmol, 1 eq) of the product of step (3), and 7.9 g (18.96 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0184] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 3.4 g of the dark green product heptamethrin indole cyanine dye (Ⅳ-1), with a yield of 53%; MS (ESI) m / z = 485, which is consistent with the theoretical value; its NMR data are: H-NMR {CDCl3, (0.92ppm, 3H), (1.77ppm, 12H), (2.75ppm, 3H), (3.95ppm, 4H), (4.90ppm, 2H), (6.03ppm, 2H), (7.11ppm, 2H), (7.24ppm, 2H), (7.46ppm, 2H), (7.55ppm, 2H)}.

[0185] Example 6

[0186] Synthesize heptamethrin indocyanine (Ⅳ-3) according to the following synthetic route:

[0187]

[0188] A method for preparing heptamethrin indolecyanine (Ⅳ-3) includes the following steps:

[0189] (1) Add 31.2g (0.442mol, 5eq) DMF and 50mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 54.2g (0.353mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0190] (2) Slowly add 11.2 g (0.088 mol, 1 eq) of N-ethyl-4-piperidinone (Ⅰ-3) and 50 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0191] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 14.1 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-3), with a yield of 79.9%.

[0192] (4) Add 50 mL of acetic anhydride, 2.5 g (30.32 mmol, 4 eq) of anhydrous sodium acetate, 2.2 g (10.65 mmol, 1 eq) of the product of step (3) and 7.9 g (18.96 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0193] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added as mixed solvents. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 4.4 g of the dark green product heptamethrin indocyanine dye (Ⅳ-3), with a yield of 65.5%; MS (ESI) m / z = 513, consistent with the theoretical value; its NMR data were: H-NMR {CDCl3, (0.82ppm, 3H), (1.77ppm, 15H), (2.71ppm, 3H), (3.26ppm, 2H), (3.98ppm, 4H),

[0194] (4.90ppm,2H),(6.09ppm,2H),(7.18ppm,2H),(7.24ppm,2H),(7.41ppm,2H),(7.59ppm,2H)}.

[0195] Example 7

[0196] Synthesize heptamethrin indocyanine (Ⅳ-4) according to the following synthetic route:

[0197]

[0198] A method for preparing heptamethrin indolecyanine (Ⅳ-4) includes the following steps:

[0199] (1) Add 31.2g (0.442mol, 5eq) DMF and 50mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 54.2g (0.353mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0200] (2) Slowly add 12.5 g (0.088 mol, 1 eq) of N-isopropyl-4-piperidinone (Ⅰ-4) and 50 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0201] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 11.9 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-4), with a yield of 62.9%.

[0202] (4) Add 50 mL of acetic anhydride, 2.5 g (30.32 mmol, 4 eq) of anhydrous sodium acetate, 2.3 g (10.65 mmol, 1 eq) of the product of step (3), and 7.9 g (18.96 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0203] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added as mixed solvents. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 3.7 g of the dark green product heptamethrin indocyanine dye (Ⅳ-4), with a yield of 53.5%; MS (ESI) m / z = 527, consistent with the theoretical value; its NMR data were: H-NMR {CDCl3, (0.87ppm, 3H), (1.89ppm, 18H), (2.65ppm, 3H), (3.24ppm, 2H), (3.92ppm, 2H),

[0204] (4.15ppm,1H),(4.90ppm,2H),(6.01ppm,2H),(7.13ppm,2H),(7.25ppm,2H),(7.36ppm,2H),(7.45pp m,2H)}.

[0205] Example 8

[0206] Synthesize heptamethrin indocyanine (Ⅳ-5) according to the following synthetic route:

[0207]

[0208] A method for preparing heptamethrin indolecyanine (Ⅳ-5) includes the following steps:

[0209] (1) Add 31.2g (0.442mol, 5eq) DMF and 50mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 54.2g (0.353mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0210] (2) Slowly add 13.8 g (0.088 mol, 1 eq) of 1-tert-butylpiperidin-4-one (Ⅰ-5) and 50 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0211] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 13.3 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-5), with a yield of 65.9%.

[0212] (4) Add 50 mL of acetic anhydride, 2.5 g (30.32 mmol, 4 eq) of anhydrous sodium acetate, 2.5 g (10.65 mmol, 1 eq) of the product of step (3) and 7.9 g (18.96 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0213] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added as mixed solvents. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 5.4 g of the dark green product heptamethrin indocyanine dye (Ⅳ-5), with a yield of 76.3%; MS (ESI) m / z = 541, consistent with the theoretical value; its NMR data were: H-NMR {CDCl3, (0.82ppm, 3H), (1.83ppm, 21H), (2.61ppm, 3H), (3.22ppm, 2H), (3.91ppm, 2H),}

[0214] (4.96ppm,2H),(6.11ppm,2H),(7.16ppm,2H),(7.28ppm,2H),(7.34ppm,2H),(7.49ppm,2H)}.

[0215] Example 9

[0216] Synthesize heptamethrin indocyanine (Ⅳ-6) according to the following synthetic route:

[0217]

[0218] A method for preparing heptamethrin indolecyanine (Ⅳ-6) includes the following steps:

[0219] (1) Add 31.2g (0.442mol, 5eq) DMF and 50mL acetonitrile to a dry three-necked flask, stir at 0℃, slowly add 54.2g (0.353mol, 4eq) phosphorus oxychloride, and stir at 0℃ for 1h.

[0220] (2) Slowly add 15.5 g (0.088 mol, 1 eq) of N-phenyl-4-piperidinone (Ⅰ-6) and 50 mL of acetonitrile mixture to the solution in step (1), and react in an oil bath at 50 °C for 5 h.

[0221] (3) Cool the solution from step (2) to room temperature, slowly add it dropwise to 500 mL of ice water, stir for 10 h, filter, wash with water until neutral, dry under reduced pressure to constant weight, and obtain 16.8 g of the pale yellow solid product, six-membered heterocyclic cycloene condensing agent (Ⅱ-6), with a yield of 66.9%.

[0222] (4) Add 50 mL of acetic anhydride, 2.5 g (30.32 mmol, 4 eq) of anhydrous sodium acetate, 2.7 g (10.65 mmol, 1 eq) of the product of step (3), and 7.9 g (18.96 mmol, 2.5 eq) of 1,2,3,3-tetramethyl-3H-indolium iodide to a dry three-necked flask, and stir at 80 °C for 6 h.

[0223] (5) The solution after the reaction in step (4) was evaporated to dryness under reduced pressure, and then ethyl acetate (15 mL) and n-hexane (20 mL) were added. The mixture was stirred and slurryed at room temperature, filtered, and dried under reduced pressure to constant weight to obtain 5.2 g of the dark green product heptamethrin indolecyanine dye (Ⅳ-6), with a yield of 75.5%; MS (ESI) m / z = 561, which is consistent with the theoretical value; its NMR data are: H-NMR {CDCl3, (0.92ppm, 3H), (1.73ppm, 12H), (2.74ppm, 3H), (3.86ppm, 4H), (4.93ppm, 2H), (6.11ppm, 2H), (7.12ppm, 2H), (7.21ppm, 4H), (7.43ppm, 5H), (7.59ppm, 2H)}.

[0224] Example 10

[0225] The difference from the preparation method in Example 1 is that in step (2), CAS: 57391-13-6(Ⅰ-8) was used instead of N-methyl-4-piperidinone to obtain compound IV-8. Its NMR spectrum is shown below. Figure 4 As shown, its NMR data are:

[0226] H-NMR{CDCl3,(0.94ppm,6H),(1.03ppm,4H),(1.16ppm,12H),(1.36ppm,4H),(2.92ppm,2H),( 3.38ppm,4H),(5.86ppm,1H),(7.09ppm,4H),(7.12ppm,4H),(7.32ppm,10H),(7.49ppm,2H)}.

[0227] Example 11

[0228] The preparation method differs from that in Example 1 in that tetrahydrothiaran-4-one (Ⅰ-10) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-10; its NMR data are as follows:

[0229] H-NMR{CDCl3,(0.83ppm,3H),(1.70ppm,12H),(2.79ppm,3H),(3.88ppm,4H),(4.91pp m,2H),(6.13ppm,2H),(7.11ppm,2H),(7.20ppm,2H),(7.41ppm,2H),(7.78ppm,2H)}.

[0230] Example 12

[0231] The preparation method differs from that in Example 1 in that N-propyl-4-piperidinone (Ⅰ-11) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-11; its NMR data are as follows:

[0232] H-NMR{CDCl3,(0.89ppm,3H),(1.82ppm,15H),(2.65ppm,3H),(3.22ppm,2H),(3.92ppm,2H),

[0233] (4.10ppm,2H),(4.90ppm,2H),(6.03ppm,2H),(7.15ppm,2H),(7.29ppm,2H),(7.38ppm,2H),(7.55pp m,2H)}.

[0234] Example 13

[0235] The preparation method differs from that in Example 1 in that 1-cyclopropyl-4-piperidinone (Ⅰ-12) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-12; its NMR data are as follows:

[0236] H-NMR{CDCl3,(0.88ppm,3H),(1.81ppm,12H),(2.67ppm,3H),(3.21ppm,2H),(3.98ppm,2H),

[0237] (4.19ppm,5H),(4.93ppm,2H),(6.05ppm,2H),(7.15ppm,2H),(7.28ppm,2H),(7.39ppm,2H),(7.59pp m,2H)}.

[0238] Example 14

[0239] The preparation method differs from that in Example 1 in that 1-(cyclopropylmethyl)piperidin-4-one (Ⅰ-13) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-13; its NMR data are as follows:

[0240] H-NMR{CDCl3,(0.83ppm,3H),(1.89ppm,12H),(2.61ppm,3H),(3.22ppm,2H),(3.78ppm,4H),

[0241] (4.16ppm,5H),(4.95ppm,2H),(6.15ppm,2H),(7.18ppm,2H),(7.29ppm,2H),(7.38ppm,2H),(7.57pp m,2H)}.

[0242] Example 15

[0243] The preparation method differs from that in Example 1 in that 1-butyl-4-piperidinone (Ⅰ-14) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-14; its NMR data are as follows:

[0244] H-NMR{CDCl3,(0.85ppm,3H),(1.86ppm,15H),(2.66ppm,3H),(3.21ppm,2H),(3.95ppm,2H),

[0245] (4.18ppm,4H),(4.91ppm,2H),(6.09ppm,2H),(7.16ppm,2H),(7.29ppm,2H),(7.36ppm,2H),(7.51pp m,2H)}.

[0246] Example 16

[0247] The preparation method differs from that in Example 1 in that 1-(2-methylpropyl)-4-piperidinone (Ⅰ-15) is used instead of N-methyl-4-piperidinone in step (2), yielding compound Ⅳ-15; its NMR data are as follows:

[0248] H-NMR{CDCl3,(0.88ppm,3H),(1.85ppm,18H),(2.67ppm,3H),(3.22ppm,2H),(3.91ppm,2H),

[0249] (4.11ppm,1H),(4.92ppm,2H),(6.01ppm,2H),(7.12ppm,2H),(7.28ppm,2H),(7.38ppm,2H),(7.56pp m,2H)}.

[0250] Example 17

[0251] The preparation method differs from that in Example 1 in that 1-N-methanesulfonyl-4-piperidinone (Ⅰ-16) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-16; its NMR data are as follows:

[0252] H-NMR{CDCl3,(1.21ppm,3H),(1.74ppm,12H),(3.68ppm,6H),(3.79ppm,4H),(3.99ppm,2H), (5.93ppm,2H),(7.10ppm,2H),(7.21ppm,2H),(7.39ppm,2H),(7.46ppm,3H),(8.21ppm,2H)}.

[0253] Example 18

[0254] The preparation method differs from that in Example 1 in that N-acetyl-4-piperidinone (Ⅰ-17) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-17; its NMR data are as follows:

[0255] H-NMR{CDCl3,(1.01ppm,3H),(1.76ppm,12H),(3.61ppm,6H),(3.71ppm,4H),(3.92ppm,2H), (5.97ppm,2H),(7.11ppm,2H),(7.22ppm,2H),(7.39ppm,2H),(7.48ppm,3H),(8.26ppm,2H)}.

[0256] Example 19

[0257] The preparation method differs from that in Example 1 in that 1-((pyridin-4-yl)methyl-4-piperidinone (Ⅰ-18) is used instead of N-methyl-4-piperidinone in step (2) to obtain compound Ⅳ-18; its NMR data are as follows:

[0258] H-NMR{CDCl3,(0.93ppm,3H),(1.72ppm,12H),(3.66ppm,3H),(3.77ppm,4H),(3.92ppm,2H), (5.93ppm,2H),(7.12ppm,2H),(7.29ppm,4H),(7.36ppm,4H),(7.44ppm,2H),(8.15ppm,2H)}.

[0259] Application examples

[0260] Application of heptamethrin indocyanine dye in treatment-free CTP thermal printing plates:

[0261] A1050 rolled aluminum plate with a purity of 99.5% and a thickness of 0.3 mm was etched in a 5 wt% sodium hydroxide aqueous solution at 70°C for 20 seconds. After rinsing with running water, it was immediately neutralized with a 1 wt% nitric acid aqueous solution, and then etched in a 1 wt% hydrochloric acid aqueous solution at 40°C with a sinusoidal alternating current of 50 A / dm². 2 The surface was roughened by electrolysis at a current density of 16 seconds, followed by neutralization with a 5 wt% sodium hydroxide aqueous solution at 40°C for 10 seconds, then washed with water, and finally subjected to electrolysis with a 20 wt% sulfuric acid aqueous solution at 30°C at 15 A / dm³. 2 The current density was adjusted, and anodizing was performed for 20 seconds, followed by water washing. Then, the pores were sealed with a 5wt% sodium silicate aqueous solution at 80℃ for 18 seconds, followed by water washing and drying to obtain the substrate. The average thickness of the centerline of this substrate was 0.5 μm, and the oxide film weight was 3.0 g / dm². 2 .

[0262] Photosensitive layer coating: The photosensitive liquid with the following composition is applied by extrusion coating onto the substrate obtained above, and then dried at 100°C for 60 seconds to obtain a dry weight of 10 mg / dm³. 2 The coating;

[0263] The photosensitive solution comprises: polymer M, polyester acrylate prepolymer, polypentanetetrafluoroethylene acrylate, iodonium salt photoinitiator, infrared dye, BYK-333 and 1-methoxy-2-propanol, wherein compounds IV-1 to IV-18 are used as infrared dyes to prepare the photosensitive solution, and the composition is shown in Table 1.

[0264] Table 1

[0265]

[0266]

[0267] The structure of polymer M in Table 1 above:

[0268]

[0269] Performance evaluation:

[0270] The plates, prepared using photosensitive solutions of heptamethrin indocyanine dyes IV-1 to IV-18, were first tested on a Kodak Allwinner thermal CTP plate-making machine using its built-in test strips to determine the minimum exposure energy. Then, the plates were exposed at appropriate energy. Finally, the plates were directly mounted onto a Heidelberg SM52 printing press, the press was started, and the entire plate was dampened with dampening solution for 10 seconds before paper was fed and printing began. The performance characteristics are listed in Table 2 below.

[0271] Table 2

[0272]

[0273]

[0274] As can be seen from the test results of each embodiment in Table 2, the treatment-free thermal CTP plates prepared by the heptamethrin indolecyanine dye in Examples 1 to 18 have excellent photosensitivity, plate contrast and printing durability.

[0275] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0276] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A processless heat sensitive CTP plate characterized in that, The processing-free heat-sensitive CTP plate comprises a heptamethine indolium cyanine dye, and a structural formula of the heptamethine indolium cyanine dye is formula (IV): Formula (IV) In the structural formula (IV) of the heptamethine indolium cyanine dye, X comprises a nitrogen atom, an oxygen atom or a sulfur atom; Y comprises hydrogen, a methyl group, an ethyl group, a 2-propyl group, a tert-butyl group, a phenyl group, a benzyl group and a biphenyl group, a 1-propyl group, a cyclopropyl group, a methylcyclopropyl group, a n-butyl group, a 2-methylpropyl group, a methylsulfonyl group, an acetyl group or a 4-pyridyl group; When X is an oxygen atom or a sulfur atom, there is no Y substituent in formula (IV); Z comprises a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a p-toluenesulfonate ion, a tetraphenylborate ion, a tetrafluoroborate ion, a hexafluoroborate ion or a hexafluorophosphate ion; R comprises a methyl group, an ethyl group, a propyl group, a tert-butyl group, a methoxymethyl group, a methyl formate group, a methoxy group or a 2-propanone group.

2. The processless heat-sensitive CTP plate according to claim 1, characterized in that, The heptamethine indolium cyanine dye comprises at least one of formula (IV-1) to (IV-18): 。 3. The processless heat-sensitive CTP plate according to claim 1 or 2, characterized in that The chlorine atom in the structure of the heptamethine indolium cyanine dye can be further substituted, and the substituent group comprises an N,N-diphenylamine group, a p-toluenesulfenyl group, an aniline group or a benzylamine group.

4. The processless thermal CTP printing plate according to claim 3, characterized in that, The heptamethine indolium cyanine dye comprises formula (IV-19) or formula (IV-20): 。 5. The processless thermal CTP printing plate according to claim 1, wherein The preparation steps of the heptamethine indolium cyanine dye comprise: S1: mixing N,N-dimethylformamide and phosphorus oxychloride to obtain a first solution; S2: adding a six-membered heterocyclic ketone to the first solution to obtain a second solution; S3: adding the second solution into ice water to separate a six-membered heterocyclic ring alkenyl condensing agent; S4: mixing acetic anhydride, anhydrous sodium acetate, a benzindole quaternary ammonium salt and the six-membered heterocyclic condensing agent to obtain a third solution; S5: after adding an organic solvent to the third solution and beating, a heptamethine indolium cyanine dye is obtained; The structural formula of the six-membered heterocyclic ketone is formula (I): Formula (I) The structural formula of the six-membered heterocyclic ring alkenyl condensing agent is formula (II): Formula (II) In the structural formula (I) of the six-membered heterocyclic ketone and the structural formula (II) of the six-membered heterocyclic ring alkenyl condensing agent, X and Y are the same as those in formula (IV).

6. The processless thermal CTP printing plate according to claim 5, wherein The six-membered heterocyclic ketone comprises at least one of formula (I-1) to (I-18): 。 7. The processless thermal CTP printing plate according to claim 5, wherein The six-membered heterocyclic ring alkenyl condensing agent comprises at least one of formula (II-1) to (II-18): 。 8. The processless thermal CTP printing plate according to claim 5, wherein, The structural formula of the benzindole quaternary ammonium salt is formula (III): Formula (III) In the structural formula (III) of the benzindole quaternary ammonium salt, Z and R are the same as those in formula (IV).

9. The processless thermal CTP printing plate according to claim 8, wherein, The benzindole quaternary ammonium salt comprises at least one of formula (III-1) to (III-8): 。 10. The processless thermal CTP printing plate according to claim 5, wherein, In steps S1 and S2, the molar ratio of the N,N-dimethylformamide, the phosphorus oxychloride and the six-membered heterocyclic ketone is 10:8:(1-8).

11. The processless thermal CTP printing plate according to claim 10, wherein In step S1, the first reaction temperature for mixing the N,N-dimethylformamide and the phosphorus oxychloride is 0-5°C, and the first reaction time is 0.8-1.2 h.

12. The processless thermal CTP printing plate according to claim 10, wherein, In step S2, the second reaction temperature for adding the six-membered heterocyclic ketone to the first solution is 40-60°C, and the second reaction time is 4-8 h.

13. The processless thermal CTP printing plate according to claim 5, wherein, The stirring time of the second solution in ice water in step S3 is 6-12 hours.

14. The processless thermal CTP printing plate according to claim 5, wherein, In step S4, the molar ratio of the six-membered heterocyclic ring olefin condensing agent, benzindole quaternary ammonium salt and anhydrous sodium acetate is 1:(2-3):(3-6).

15. The processless thermal CTP printing plate according to claim 14, wherein In step S4, the third reaction temperature of the mixture of acetic anhydride, anhydrous sodium acetate, benzindole quaternary ammonium salt and the six-membered heterocyclic ring condensing agent is 60-100°C, and the third reaction time is 2-10 hours.

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