CN114656441B - Asymmetric near-infrared organic fluorescent probe and synthetic method and application thereof - Google Patents
Asymmetric near-infrared organic fluorescent probe and synthetic method and application thereof Download PDFInfo
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
- A61K49/0032—Methine dyes, e.g. cyanine dyes
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
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Abstract
The invention discloses an asymmetric near-infrared organic fluorescent probe, a synthesis method and application thereof. The structural general formula of the asymmetric near-infrared organic fluorescent probe is shown as follows: The synthesis method comprises the following steps: and (3) in the presence of toluene and n-butanol, performing condensation reaction on the first intermediate with aldehyde groups at the tail ends of the probe framework, and then performing connection reaction on a mixed reaction system containing a reaction product, the second intermediate with double bonds at the tail ends, a catalyst and an organic solvent to obtain the asymmetric near-infrared organic fluorescent probe. The absorption/emission wavelengths of the asymmetric near-infrared organic fluorescent probe are all in the near-infrared region, and the asymmetric near-infrared organic fluorescent probe can be used for near-infrared fluorescent imaging and diagnosis and treatment guided by fluorescent images. The asymmetric near-infrared organic fluorescent probe can greatly increase the modifiable property of the near-infrared organic fluorescent probe, is beneficial to realizing the multifunctional application of the probe, and has wide application prospect in the fields of biological imaging and detection.
Description
Technical Field
The invention relates to an organic fluorescent probe, in particular to an asymmetric near-infrared organic fluorescent probe based on a bifunctional probe skeleton and constructed based on a xanthene structure, and a synthesis method and biological application thereof, and belongs to the technical fields of material chemistry and biology.
Background
In-situ biopsy means based on visual imaging technology have wide application in clinical diagnosis and treatment. Compared with the traditional Magnetic Resonance Imaging (MRI), ultrasonic imaging, CT imaging, PET imaging and other technologies, the fluorescence imaging has higher sensitivity and specificity, can realize rapid real-time feedback at lower cost, and is receiving more and more attention in the fields of disease diagnosis, surgical operation navigation, treatment effect, prognosis evaluation and the like.
Among various fluorescent imaging agents, organic fluorescent materials have received great attention because of their definite molecular structure, excellent biocompatibility, and rapid excretion through the liver, gall or kidney. The organic fluorescent probes reported at present are mainly designed around symmetrical skeleton structures, and the molecular construction is mainly carried out around corresponding skeletons to select proper intermediates, so that the regulation and control of the optical properties of the organic fluorescent probes are realized. However, molecular frameworks which can be applied to fluorescent probe design at present are very limited, and for the molecular frameworks, symmetrical structures are often obtained in the synthesis of the probe, so that the multifunctional construction of the probe is not facilitated.
Disclosure of Invention
The invention mainly aims to provide an asymmetric near-infrared organic fluorescent probe which is easy to carry out multifunctional modification, has longer emission wavelength and is simple and convenient to prepare aiming at the defects of the structure and the performance of the existing fluorescent probe.
The invention also aims at providing application of the asymmetric near infrared organic fluorescent probe in biological imaging, optical diagnosis and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
The embodiment of the invention provides an asymmetric near-infrared organic fluorescent probe, which has a structural general formula shown in a formula (I):
wherein n is selected from 0,1 or 2, and R 1 and R 2 are each selected from any one of the following structures:
R 3 is-H or
X - is an anion, including Cl-、Br-、I-、NO3 -、ClO4 -、CH3COO-、CH3SO3 - or CF 3SO3 -;
the total number of anionic charges carried by the asymmetric near-infrared organic fluorescent probe is equal to the total number of charges carried by cations.
The embodiment of the invention also provides a synthetic method of the asymmetric near-infrared organic fluorescent probe, which comprises the following steps:
Providing a probe skeleton with a difunctional structure, wherein the structural general formula of the probe skeleton is shown as a formula (II):
wherein n is selected from 0,1 or 2, R is a halogen atom, R 3 is-H or X - is an anion, including Cl-、Br-、I-、NO3 -、ClO4 -、CH3COO-、CH3SO3 - or CF 3SO3 -;
providing a first intermediate terminating in an aldehyde group having the formula:
providing a second intermediate having a terminal double bond, the second intermediate having the structural formula:
wherein, R 1 and R 2 are selected from any one of the following structures:
In the atmosphere of anhydrous and inert gas, under the existence of toluene and n-butanol, the probe skeleton and the first intermediate with aldehyde group at the tail end are subjected to condensation reaction, and then a mixed reaction system comprising a reaction product, the second intermediate with double bond at the tail end, a catalyst and an organic solvent is subjected to connection reaction, so that the asymmetric near-infrared organic fluorescent probe is obtained.
The embodiment of the invention also provides an asymmetric near-infrared organic fluorescent probe prepared by the synthesis method.
The embodiment of the invention also provides application of the asymmetric near-infrared organic fluorescent probe in preparing near-infrared fluorescence imaging materials or optical diagnostic materials and the like.
Compared with the prior art, the invention has the advantages that:
1) The asymmetric near-infrared organic fluorescent probe can easily adjust the absorption and emission wavelength of molecules in a mode of shortening and prolonging the conjugated structure, so as to obtain probe molecules meeting the requirements. The absorption and emission of the molecules reach the near infrared region, and the self-fluorescence and scattering phenomena of organisms are weak in the near infrared region, so that the molecules can be applied to biological imaging;
2) The asymmetric near-infrared organic fluorescent probe prepared by the invention has the asymmetric structural characteristics, which provides great convenience for the multi-functionalization of molecules, and further powerfully expands the practical application range of the probe molecules; and it is easy to impart specific responsiveness to the probe by changing different response groups.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a graph showing the ultraviolet absorption spectra before and after synthesis of the probe skeleton A in example 1 of the present invention;
FIGS. 2 a-2 d are 1H-NMR spectra of styrene and benzaldehyde chains of different lengths synthesized in an embodiment of the invention.
Detailed Description
Aiming at a plurality of defects in the prior art, the inventor of the present invention has provided a technical scheme of the present invention through long-term research and a great deal of practice, and mainly adopts a probe framework with a difunctional structure and a side chain condensation design with different structures to synthesize an asymmetric near-infrared organic fluorescent probe. The technical scheme, the implementation process, the principle and the like are further explained as follows.
As one aspect of the technical scheme of the invention, the asymmetric near-infrared organic fluorescent probes are formed by condensing an asymmetric probe skeleton with an intermediate containing aldehyde groups and then reacting and connecting the intermediate containing double bonds, and the structural general formula of the asymmetric near-infrared organic fluorescent probes is shown as the formula (I):
wherein n is selected from 0, 1 or 2, R 1 and R 2 are property regulating groups, the functional structures are interchangeable and freely combined, and the functional structures are selected from any one of the following structures:
R 3 is-H or
X - is an anion, which can be Cl-、Br-、I-、NO3 -、ClO4 -、CH3COO-、CH3SO3 -, CF 3SO3 -, or the like.
Further, the asymmetric near infrared organic fluorescent probe has balanced charges, i.e. the total number of charges of anions carried is equal to the total number of charges of cations carried.
The mechanism of the asymmetric near-infrared organic fluorescent probe is as follows: after the probe skeleton with two different reaction sites is connected with the intermediate with different types of property regulating groups, the probe shows various properties, and the multifunctional application requirement of the probe is met.
Further, the absorption/emission wavelengths of the asymmetric near-infrared organic fluorescent probes are all in the near-infrared region, and the asymmetric near-infrared organic fluorescent probes can be used for near-infrared fluorescent imaging and diagnosis and treatment guided by fluorescent images.
As another aspect of the technical scheme of the invention, the invention relates to a synthetic method of an asymmetric near-infrared organic fluorescent probe, which comprises the following steps:
providing a probe skeleton with a difunctional structure, wherein the structural general formula of the probe skeleton is shown as a formula (II):
wherein n is selected from 0, 1 or2, R is a halogen atom, and may include: F. cl, br, I, etc.;
R 3 is-H or X - is an anion, which may include Cl-、Br-、I-、NO3 -、ClO4 -、CH3COO-、CH3SO3 - or CF 3SO3 -, etc.;
providing a first intermediate terminating in an aldehyde group having the formula:
providing a second intermediate having a terminal double bond, the second intermediate having the structural formula:
wherein, R 1 and R 2 are selected from any one of the following structures:
In the atmosphere of anhydrous and inert gas, under the existence of toluene and n-butanol, the probe skeleton and the first intermediate with aldehyde group at the tail end are subjected to condensation reaction, and then a mixed reaction system comprising a reaction product, the second intermediate with double bond at the tail end, a catalyst and an organic solvent is subjected to connection reaction, so that the asymmetric near-infrared organic fluorescent probe is obtained.
In some embodiments, the catalyst may be a combination of palladium acetate and triethylamine, and the molar ratio of palladium acetate to triethylamine is from 1:1000 to 1:500.
In some embodiments, the volume ratio of toluene to n-butanol is from 1:1 to 3:1.
In some embodiments, the molar ratio of the probe scaffold to the first intermediate is from 1:1 to 1:2.
In some embodiments, the molar ratio of the reaction product of the first intermediate to the second intermediate is from 1:1 to 1:2.
In some embodiments, the molar ratio of the reaction product of the first intermediate to triethylamine is from 1:1 to 1:2.
In some embodiments, the temperature of the ligation reaction is between 110 and 140 ℃ for a period of between 12 and 18 hours.
In some embodiments, the condensation reaction is at a temperature of 90 to 100 ℃ for a time of 2 to 3 hours.
In some preferred embodiments, the method for synthesizing the asymmetric near-infrared organic fluorescent probe may specifically include the following steps:
In the presence of toluene and n-butanol, the first intermediate with aldehyde group at the tail end and the first probe skeleton are subjected to condensation reaction; and then in the anhydrous nitrogen atmosphere, palladium acetate and triethylamine are used as catalysts, DMF is used as a reaction solvent, and the reaction product of the previous step and a second intermediate containing double bonds are reacted to obtain the asymmetric near infrared organic fluorescent probe.
In some preferred embodiments, the method for synthesizing a class of asymmetric near infrared organic fluorescent probes comprises the steps of:
Firstly, synthesizing a probe framework A; and condensing the probe skeleton A with an intermediate B containing aldehyde groups (namely, the first intermediate with the end being aldehyde groups) to obtain an intermediate C, and finally, reacting the intermediate C with an intermediate D containing double bonds (namely, the second intermediate with the end being double bonds) to obtain the corresponding asymmetric near-infrared organic fluorescent dye.
In some preferred embodiments, the asymmetric near infrared organic fluorescent probe is synthesized by the following route:
Wherein R, R 1、R2、R3、n、X- is as defined in the formulae hereinbefore described.
Further, another aspect of an embodiment of the present invention also provides an asymmetric organic probe scaffold.
In some preferred embodiments, the method of preparing an asymmetric organic probe scaffold comprises:
adding cyclic ketone dropwise into concentrated sulfuric acid under ice bath condition, and adding compound And after stirring uniformly, heating to 60-90 ℃ to react for 1-3 h, thus obtaining the asymmetric organic probe skeleton. The reaction has the following reaction formula:
wherein n is selected from 0, 1 or 2.R is a halogen atom, and may include: F. cl, br, I, etc.;
R 3 is-H or X - is an anion and may include Cl-、Br-、I-、NO3 -、ClO4 -、CH3COO-、CH3SO3 - or CF 3SO3 -, and the like.
Wherein, in some more specific embodiments, the specific synthetic steps of the asymmetric near infrared organic fluorescent probe are as follows:
(1) Synthesis of probe backbone a: stirring concentrated sulfuric acid to constant temperature under ice bath condition, slowly dripping cyclic ketone (cyclopentanone, cyclohexanone or cycloheptanone) into concentrated sulfuric acid, adding corresponding 2- (2-hydroxy-4-iodobenzoyl) benzoic acid, stirring uniformly, and heating at elevated temperature; after the reaction is finished, dripping the reaction liquid into ice water containing perchloric acid to generate precipitation; centrifuging to separate a precipitate; the precipitate was washed with ice water and dried and used directly in the subsequent reaction.
(2) Synthesis of intermediate C: firstly weighing a probe skeleton A and an aldehyde group-containing property regulating group B (namely the first intermediate with the aldehyde group at the tail end), stirring and dissolving with toluene and n-butanol solvent (volume ratio is 3:1), then under the protection of nitrogen, raising the temperature to a certain temperature for condensation reaction, and after the reaction is finished, performing rotary evaporation, column purification and drying to obtain a target product.
(3) Synthesis of styrene intermediate D of different lengths: a) The conjugate chain is prolonged by Heck reaction and 4-bromobenzaldehyde is coupled under the catalysis of palladium acetate and tri (2-tolyl) phosphine, and simultaneously, a styrene intermediate containing aldehyde group is obtained: firstly, drying a flask, then adding a styrene raw material, 4-bromobenzaldehyde, palladium acetate, tri (2-tolyl) phosphine, triethylamine and dried DMF into the flask, sealing and reacting for 18h at 110 ℃ under the protection of nitrogen atmosphere, and finally, steaming, purifying and drying. b) The structure of the para-position benzaldehyde is changed into a styrene structure through a Wittig reaction: under the conditions of room temperature and nitrogen protection, firstly, dry THF is used for dissolving methyl triphenylphosphine bromide, after full stirring, tertiary butyl methanol is slowly added dropwise, and the mixture is fully stirred again; dissolving the raw material with the benzaldehyde structure by using dry THF, slowly dripping the raw material into the solution, and reacting overnight; transferring to a flask, steaming, adding a large amount of petroleum ether, filtering, and collecting filtrate; and finally spin-drying the filtrate to obtain a corresponding styrene structure D.
Wherein, FIG. 2a, FIG. 2b, FIG. 2c, FIG. 2d are the 1H-NMR spectra of styrene and benzaldehyde chains of different lengths synthesized in an embodiment of the invention, respectively.
(4) Synthesis of asymmetric-structured organic probe molecules: intermediate D (i.e., the "second intermediate ending in a double bond" described above) is coupled with the iodine substitution site of intermediate C under the catalysis of palladium acetate with tris (2-tolyl) phosphine: firstly, drying a flask, then adding a styrene raw material, 4-bromobenzaldehyde, palladium acetate, tri (2-tolyl) phosphine, triethylamine and dried DMF into the flask, sealing and reacting for 18h at 110 ℃ under the protection of nitrogen, and finally, steaming, purifying and drying.
The invention provides a preparation method of an organic probe based on an asymmetric organic probe skeleton and easy to apply in multiple functions, which can be applied to near infrared fluorescence imaging and optical diagnosis by utilizing the characteristics of near infrared emission and multiple functions.
Another aspect of an embodiment of the present invention also provides an asymmetric near-infrared organic fluorescent probe prepared by the aforementioned synthesis method.
The asymmetric near-infrared organic fluorescent probe prepared by the invention greatly prolongs the length of a conjugated chain on the basis of a probe framework, so that the absorption and emission of probe molecules are subjected to red shift.
Another aspect of the embodiments of the present invention also provides an application of the asymmetric near infrared organic fluorescent probe in the field of materials for fluorescence imaging in the near infrared region or materials for optical diagnosis (such as materials for photodynamic therapy).
Furthermore, in the near infrared region, the phenomenon of autofluorescence and photon scattering in organisms is weak, so that the probe can fully exert the advantage of near infrared imaging and is used for biological imaging.
Further, the asymmetric near-infrared organic fluorescent probe is applied to near-infrared region fluorescent imaging.
Furthermore, compared with the traditional organic fluorescent dye in the ultraviolet-visible wavelength range, the novel near infrared asymmetric organic fluorescent probe can remarkably reduce the scattering and absorption of photons in organisms and the interference of biological autofluorescence, and has potential application value in the field of biological diagnosis and treatment.
The technical solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The implementation conditions used in the following examples may be further adjusted according to actual needs, and the implementation conditions not specified are generally those in routine experiments.
Example 1:
Dissolving probe frameworks A 1 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 1; the flask was dried, then intermediate C 1 (0.1 mmol), the responding group D 1 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 140 ℃ for 12h under nitrogen protection, finally a black powder (denoted Dye 1) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 829.85. The ultraviolet absorption spectra before and after synthesis of the probe skeleton A are shown in FIG. 1.
Example 2:
Dissolving probe frameworks A 2 (0.5 mmol) and B 1 (1.0 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (2:1), heating to 100 ℃ under the protection of nitrogen, reacting for about 3 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 2; the flask was dried, then intermediate C 2 (0.1 mmol), responding group D 1 (0.2 mmol), palladium acetate (0.0002 mmol), triethylamine (0.2 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 13h under nitrogen protection, finally a black powder (denoted Dye 2) was obtained by rotary evaporation, purification, drying, and the characterization data were as follows: HRMS (m+) = 843.88.
Example 3:
Dissolving probe frameworks A 3 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (1:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 3; the flask was dried, then intermediate C 1 (0.1 mmol), the responding group D 1 (0.1 mmol), palladium acetate (0.0002 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 130 ℃ for 14h under nitrogen protection, finally a black powder (denoted Dye 3) was obtained by rotary evaporation, purification, drying, and the characterization data were as follows: HRMS (m+) = 857.91.
Example 4:
Dissolving probe frameworks A 1 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 1; the flask was dried, then intermediate C 1 (0.1 mmol), the responding group D 2 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 120 ℃ for 15h under nitrogen protection, finally a black powder (denoted Dye 4) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 931.99.
Example 5:
Dissolving probe frameworks A 2 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 2; the flask was dried, then intermediate C 2 (0.1 mmol), the responding group D 2 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 16h under nitrogen protection, finally a black powder (denoted Dye 5) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 946.02.
Example 6:
Dissolving probe frameworks A 3 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 3; the flask was dried, then intermediate C 3 (0.1 mmol), the responding group D 2 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110deg.C under nitrogen protection for 17h, finally a black powder (indicated as Dye 6) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 960.04.
Example 7:
Dissolving probe frameworks A 1 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 4; the flask was dried, then intermediate C 4 (0.1 mmol), the responding group D 3 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 7) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 803.81.
Example 8:
Dissolving probe frameworks A 2 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 5; the flask was dried, then intermediate C 5 (0.1 mmol), the responding group D 3 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 8) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 817.84.
Example 9:
Dissolving probe frameworks A 3 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 6; the flask was dried, then intermediate C 6 (0.1 mmol), the responding group D 3 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 9) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 831.87.
Example 10:
Dissolving probe frameworks A 1 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 4; the flask was dried, then intermediate C 4 (0.1 mmol), the responding group D 4 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 10) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 905.95.
Example 11:
Dissolving probe frameworks A 2 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 5; the flask was dried, then intermediate C 5 (0.1 mmol), the responding group D 4 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 11) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 919.98.
Example 12:
Dissolving probe frameworks A 3 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 6; the flask was dried, then intermediate C 6 (0.1 mmol), the responding group D 4 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 12) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 934.00.
Example 13:
Dissolving probe frameworks A 1 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 7; the flask was dried, then intermediate C 7 (0.1 mmol), the responding group D 3 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 13) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 822.40.
Example 14:
Dissolving probe frameworks A 2 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 8; the flask was dried, then intermediate C 8 (0.1 mmol), the responding group D 3 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 14) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 836.33.
Example 15:
Dissolving probe frameworks A 3 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 9; the flask was dried, then intermediate C 9 (0.1 mmol), the responding group D 3 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 15) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 850.35.
Example 16:
Dissolving probe frameworks A 1 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 7; the flask was dried, then intermediate C 7 (0.1 mmol), the responding group D 4 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 16) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 924.44.
Example 17:
Dissolving probe frameworks A 2 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 8; the flask was dried, then intermediate C 8 (0.1 mmol), the responding group D 4 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 17) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 938.46.
Example 18:
Dissolving probe frameworks A 3 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 9; the flask was dried, then intermediate C 9 (0.1 mmol), the responding group D 4 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 18) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 952.49.
Example 19:
Dissolving probe frameworks A 1 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 1; the flask was dried, then intermediate C 1 (0.1 mmol), the responding group D 5 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 19) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 730.20.
Example 20:
Dissolving probe frameworks A 2 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 2; the flask was dried, then intermediate C 2 (0.1 mmol), the responding group D 5 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 20) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 744.23.
Example 21:
Dissolving probe frameworks A 3 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 3; the flask was dried, then intermediate C 3 (0.1 mmol), the responding group D 5 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 21) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 758.26.
Example 22:
Dissolving probe frameworks A 1 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 1; the flask was dried, then intermediate C 1 (0.1 mmol), the responding group D 6 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 22) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 832.34.
Example 23:
Dissolving probe frameworks A 2 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 2; the flask was dried, then intermediate C 2 (0.1 mmol), the responding group D 6 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 23) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 846.37.
Example 24:
Dissolving probe frameworks A 3 (0.5 mmol) and B 1 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 3; the flask was dried, then intermediate C 3 (0.1 mmol), the responding group D 6 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 24) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 860.39.
Example 25:
Dissolving probe frameworks A 1 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 10; the flask was dried, then intermediate C 10 (0.1 mmol), the responding group D 7 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 25) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 694.72.
Example 26:
Dissolving probe frameworks A 2 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 11; the flask was dried, then intermediate C 11 (0.1 mmol), the responding group D 7 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 26) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 708.75.
Example 27:
Dissolving probe frameworks A 3 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 12; the flask was dried, then intermediate C 12 (0.1 mmol), the responding group D 7 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 27) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 722.78.
Example 28:
Dissolving probe frameworks A 1 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 10; the flask was dried, then intermediate C 10 (0.1 mmol), the responding group D 8 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 28) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 796.86.
Example 29:
Dissolving probe frameworks A 2 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 11; the flask was dried, then intermediate C 11 (0.1 mmol), the responding group D 8 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 29) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 810.89.
Example 30:
Dissolving probe frameworks A 3 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 12; the flask was dried, then intermediate C 12 (0.1 mmol), the responding group D 8 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 30) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 824.91.
Example 31:
Dissolving probe frameworks A 1 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 13; the flask was dried, then intermediate C 13 (0.1 mmol), the responding group D 9 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 31) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 592.59.
Example 32:
Dissolving probe frameworks A 2 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 14; the flask was dried, then intermediate C 14 (0.1 mmol), the responding group D 9 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 32) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 606.61.
Example 33:
Dissolving probe frameworks A 3 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 15; the flask was dried, then intermediate C 15 (0.1 mmol), the responding group D 9 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 33) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 620.64.
Example 34:
Dissolving probe frameworks A 1 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 13; the flask was dried, then intermediate C 13 (0.1 mmol), the responding group D 10 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 34) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 694.72.
Example 35:
Dissolving probe frameworks A 2 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 14; the flask was dried, then intermediate C 14 (0.1 mmol), the responding group D 10 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 35) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 708.75.
Example 36:
Dissolving probe frameworks A 3 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 15; the flask was dried, then intermediate C 15 (0.1 mmol), the responding group D 10 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 36) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 722.78.
Example 37:
Dissolving probe frameworks A 1 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 13; the flask was dried, then intermediate C 13 (0.1 mmol), the responding group D 11 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 37) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 767.07.
Example 38:
Dissolving probe frameworks A 2 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 14; the flask was dried, then intermediate C 14 (0.1 mmol), the responding group D 11 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 38) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 781.12.
Example 39:
Dissolving probe frameworks A 3 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 15; the flask was dried, then intermediate C 15 (0.1 mmol), the responding group D 11 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 39) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 795.13.
Example 40:
Dissolving probe frameworks A 1 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 13; the flask was dried, then intermediate C 13 (0.1 mmol), the responding group D 12 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 40) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 869.21.
Example 41:
Dissolving probe frameworks A 2 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 14; the flask was dried, then intermediate C 14 (0.1 mmol), the responding group D 12 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 41) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 883.23.
Example 42:
Dissolving probe frameworks A 3 (0.5 mmol) and B 5 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 15; the flask was dried, then intermediate C 15 (0.1 mmol), the responding group D 12 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 42) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 897.26.
Example 43:
Dissolving probe frameworks A 1 (0.5 mmol) and B 6 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 16; the flask was dried, then intermediate C 16 (0.1 mmol), the responding group D 7 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 43) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 869.21.
Example 44:
Dissolving probe frameworks A 2 (0.5 mmol) and B 6 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 17; the flask was dried, then intermediate C 17 (0.1 mmol), the responding group D 7 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 44) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 883.23.
Example 45:
Dissolving probe frameworks A 3 (0.5 mmol) and B 6 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 18; the flask was dried, then intermediate C 18 (0.1 mmol), the responding group D 7 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 45) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 897.26.
Example 46:
Dissolving probe frameworks A 1 (0.5 mmol) and B 6 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 16; the flask was dried, then intermediate C 16 (0.1 mmol), the responding group D 8 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 46) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 971.34.
Example 47:
Dissolving probe frameworks A 2 (0.5 mmol) and B 6 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 17; the flask was dried, then intermediate C 17 (0.1 mmol), responding group D 8 (0.1 mmol), palladium acetate, triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally black powder (denoted Dye 47) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 985.37.
Example 48:
Dissolving probe frameworks A 3 (0.5 mmol) and B 6 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 18; the flask was dried, then intermediate C 18 (0.1 mmol), the responding group D 8 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 48) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 999.40.
Example 49:
Dissolving probe frameworks A 1 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 7; the flask was dried, then intermediate C 7 (0.1 mmol), the responding group D 13 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 49) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 846.29.
Example 50:
Dissolving probe frameworks A 2 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 8; the flask was dried, then intermediate C 8 (0.1 mmol), the responding group D 13 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 50) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 860.32.
Example 51:
Dissolving probe frameworks A 3 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 9; the flask was dried, then intermediate C 9 (0.1 mmol), the responding group D 13 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 51) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 874.34.
Example 52:
Dissolving probe frameworks A 1 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 7; the flask was dried, then intermediate C 7 (0.1 mmol), the responding group D 14 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 52) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 948.42.
Example 53:
Dissolving probe frameworks A 2 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 8; the flask was dried, then intermediate C 8 (0.1 mmol), the responding group D 14 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 53) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 962.45.
Example 54:
Dissolving probe frameworks A 3 (0.5 mmol) and B 3 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 9; the flask was dried, then intermediate C 9 (0.1 mmol), the responding group D 14 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 54) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 976.48.
Example 55:
Dissolving probe frameworks A 1 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 19; the flask was dried, then intermediate C 19 (0.1 mmol), the responding group D 5 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 55) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 846.29.
Example 56:
Dissolving probe frameworks A 2 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 20; the flask was dried, then intermediate C 20 (0.1 mmol), the responding group D 5 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 56) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 860.32.
Example 57:
Dissolving probe frameworks A 3 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 21; the flask was dried, then intermediate C 21 (0.1 mmol), the responding group D 5 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 57) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 874.34.
Example 58:
Dissolving probe frameworks A 1 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 19; the flask was dried, then intermediate C 19 (0.1 mmol), the responding group D 6 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 58) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 948.42.
Example 59:
Dissolving probe frameworks A 2 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 20; the flask was dried, then intermediate C 20 (0.1 mmol), the responding group D 6 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 59) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 962.45.
Example 60:
Dissolving probe frameworks A 3 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 21; the flask was dried, then intermediate C 21 (0.1 mmol), the responding group D 6 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 60) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 976.48.
Example 61:
Dissolving probe frameworks A 1 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 19; the flask was dried, then intermediate C 19 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 61) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 788.93.
Example 62:
Dissolving probe frameworks A 2 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 20; the flask was dried, then intermediate C 20 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 62) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 802.96.
Example 63:
Dissolving probe frameworks A 3 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 21; the flask was dried, then intermediate C 21 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 63) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 816.99.
Example 64:
Dissolving probe frameworks A 1 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 19; the flask was dried, then intermediate C 19 (0.1 mmol), the responding group D 16 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 64) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 891.07.
Example 65:
Dissolving probe frameworks A 2 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 20; the flask was dried, then intermediate C 20 (0.1 mmol), the responding group D 16 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 65) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 905.10.
Example 66:
Dissolving probe frameworks A 3 (0.5 mmol) and B 7 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 21; the flask was dried, then intermediate C 21 (0.1 mmol), the responding group D 16 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 66) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 919.12.
Example 67:
Dissolving probe frameworks A 1 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 22; the flask was dried, then intermediate C 22 (0.1 mmol), the responding group D 13 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 67) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 788.93.
Example 68:
Dissolving probe frameworks A 2 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 23; the flask was dried, then intermediate C 23 (0.1 mmol), the responding group D 13 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 68) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 802.96.
Example 69:
Dissolving probe frameworks A 3 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 24; the flask was dried, then intermediate C 24 (0.1 mmol), the responding group D 13 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 69) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 816.99.
Example 70:
Dissolving probe frameworks A 1 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 22; the flask was dried, then intermediate C 22 (0.1 mmol), the responding group D 14 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 70) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 891.07.
Example 71:
Dissolving probe frameworks A 2 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 23; the flask was dried, then intermediate C 23 (0.1 mmol), the responding group D 14 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 71) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 905.10.
Example 72:
Dissolving probe frameworks A 3 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 24; the flask was dried, then intermediate C 24 (0.1 mmol), the responding group D 14 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 72) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 919.12.
Example 73:
Dissolving probe frameworks A 1 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 22; the flask was dried, then intermediate C 22 (0.1 mmol), the responding group D 17 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 73) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 797.96.
Example 74:
Dissolving probe frameworks A 2 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 23; the flask was dried, then intermediate C 23 (0.1 mmol), the responding group D 17 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 74) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 811.99.
Example 75:
Dissolving probe frameworks A 3 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 24; the flask was dried, then intermediate C 24 (0.1 mmol), the responding group D 17 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 75) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 826.01.
Example 76:
Dissolving probe frameworks A 1 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 22; the flask was dried, then intermediate C 22 (0.1 mmol), the responding group D 18 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 76) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 900.10.
Example 77:
Dissolving probe frameworks A 2 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 23; the flask was dried, then intermediate C 23 (0.1 mmol), the responding group D 18 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 77) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 914.12.
Example 78:
Dissolving probe frameworks A 3 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 24; the flask was dried, then intermediate C 24 (0.1 mmol), the responding group D 18 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 78) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 928.15.
Example 79:
Dissolving probe frameworks A 1 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 25; the flask was dried, then intermediate C 25 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 79) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 797.96.
Example 80:
Dissolving probe frameworks A 2 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 26; the flask was dried, then intermediate C 26 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 80) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 811.99.
Example 81:
Dissolving probe frameworks A 3 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 27; the flask was dried, then intermediate C 27 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 81) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 826.01.
Example 82:
Dissolving probe frameworks A 1 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 25; the flask was dried, then intermediate C 25 (0.1 mmol), the responding group D 16 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 1) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 900.10.
Example 83:
Dissolving probe frameworks A 2 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 26; the flask was dried, then intermediate C 26 (0.1 mmol), the responding group D 16 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 83) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 914.12.
Example 84:
Dissolving probe frameworks A 3 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 27; the flask was dried, then intermediate C 27 (0.1 mmol), the responding group D 16 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 84) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 928.15.
Example 85:
Dissolving probe frameworks A 1 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 25; the flask was dried, then intermediate C 25 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 85) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 8810.90.
Example 86:
Dissolving probe frameworks A 2 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 26; the flask was dried, then intermediate C 26 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 86) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 824.93.
Example 87:
Dissolving probe frameworks A 3 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 27; the flask was dried, then intermediate C 27 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 87) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 838.95.
Example 88:
Dissolving probe frameworks A 1 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 25; the flask was dried, then intermediate C 25 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 88) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 913.04.
Example 89:
Dissolving probe frameworks A 2 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 26; the flask was dried, then intermediate C 26 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 89) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 927.06.
Example 90:
Dissolving probe frameworks A 3 (0.5 mmol) and B 9 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 27; the flask was dried, then intermediate C 27 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 90) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 941.09.
Example 91:
Dissolving probe frameworks A 1 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 28; the flask was dried, then intermediate C 28 (0.1 mmol), the responding group D 17 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 91) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 810.90.
Example 91:
Dissolving probe frameworks A 2 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 29; the flask was dried, then intermediate C 29 (0.1 mmol), the responding group D 17 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 92) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 824.93.
Example 93:
Dissolving probe frameworks A 3 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 30; the flask was dried, then intermediate C 30 (0.1 mmol), the responding group D 17 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 93) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 838.95.
Example 94:
Dissolving probe frameworks A 1 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 28; the flask was dried, then intermediate C 28 (0.1 mmol), the responding group D 18 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 94) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 913.04.
Example 95:
Dissolving probe frameworks A 2 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 29; the flask was dried, then intermediate C 29 (0.1 mmol), the responding group D 18 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 95) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 927.06.
Example 96:
Dissolving probe frameworks A 3 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 30; the flask was dried, then intermediate C 30 (0.1 mmol), the responding group D 18 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 96) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 941.09.
Example 97:
Dissolving probe frameworks A 1 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 28; the flask was dried, then intermediate C 28 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 97) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 852.89.
Example 98:
Dissolving probe frameworks A 2 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 29; the flask was dried, then intermediate C 29 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 98) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 866.92.
Example 99:
Dissolving probe frameworks A 3 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 30; the flask was dried, then intermediate C 30 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 99) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 880.94.
Example 100:
Dissolving probe frameworks A 1 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 28; the flask was dried, then intermediate C 28 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 100) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 955.03.
Example 101:
Dissolving probe frameworks A 2 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 29; the flask was dried, then intermediate C 29 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 101) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 969.05.
Example 102:
Dissolving probe frameworks A 3 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 30; the flask was dried, then intermediate C 30 (0.1 mmol), the responding group D 15 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 102) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 983.08.
Example 103:
Dissolving probe frameworks A 1 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 22; the flask was dried, then intermediate C 22 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 103) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 852.89.
Example 104:
Dissolving probe frameworks A 2 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 23; the flask was dried, then intermediate C 23 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 104) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 866.92.
Example 105:
Dissolving probe frameworks A 3 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 24; the flask was dried, then intermediate C 24 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 105) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 880.94.
Example 106:
Dissolving probe frameworks A 1 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 22; the flask was dried, then intermediate C 22 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 106) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 955.03.
Example 107:
Dissolving probe frameworks A 2 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 23; the flask was dried, then intermediate C 23 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 107) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 969.05.
Example 108:
Dissolving probe frameworks A 3 (0.5 mmol) and B 8 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 24; the flask was dried, then intermediate C 24 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 108) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 983.08.
Example 109:
Dissolving probe frameworks A 1 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 28; the flask was dried, then intermediate C 28 (0.1 mmol), the responding group D 21 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 109) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 933.87.
Example 110:
Dissolving probe frameworks A 2 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 29; the flask was dried, then intermediate C 29 (0.1 mmol), the responding group D 21 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 110) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 947.90.
Example 111:
Dissolving probe frameworks A 3 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 30; the flask was dried, then intermediate C 30 (0.1 mmol), the responding group D 21 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 111) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 961.92.
Example 112:
Dissolving probe frameworks A 1 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 28; the flask was dried, then intermediate C 28 (0.1 mmol), the responding group D 22 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 112) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1036.00.
Example 113:
Dissolving probe frameworks A 2 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 29; the flask was dried, then intermediate C 29 (0.1 mmol), the responding group D 22 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 113) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1050.03.
Example 114:
Dissolving probe frameworks A 3 (0.5 mmol) and B 10 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 30; the flask was dried, then intermediate C 30 (0.1 mmol), the responding group D 22 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 114) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1064.06.
Example 115:
dissolving probe frameworks A 1 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 31; the flask was dried, then intermediate C 31 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 115) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 933.87.
Example 116:
Dissolving probe frameworks A 2 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 32; the flask was dried, then intermediate C 32 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 116) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 947.90.
Example 117:
Dissolving probe frameworks A 3 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 33; the flask was dried, then intermediate C 33 (0.1 mmol), the responding group D 19 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 117) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 961.92.
Example 118:
Dissolving probe frameworks A 1 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 31; the flask was dried, then intermediate C 31 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 118) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1036.00.
Example 119:
Dissolving probe frameworks A 2 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 32; the flask was dried, then intermediate C 32 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 119) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1050.03.
Example 120:
Dissolving probe frameworks A 3 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 33; the flask was dried, then intermediate C 33 (0.1 mmol), the responding group D 20 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 120) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1064.06.
Example 121:
Dissolving probe frameworks A 1 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 31; the flask was dried, then intermediate C 31 (0.1 mmol), the responding group D 9 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 121) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 878.83.
Example 122:
Dissolving probe frameworks A 2 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 32; the flask was dried, then intermediate C 32 (0.1 mmol), the responding group D 9 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 122) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 892.86.
Example 123:
Dissolving probe frameworks A 3 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 33; the flask was dried, then intermediate C 33 (0.1 mmol), the responding group D 9 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 123) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 906.89.
Example 124:
Dissolving probe frameworks A 1 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 31; the flask was dried, then intermediate C 31 (0.1 mmol), the responding group D 10 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 124) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 980.97.
Example 125:
Dissolving probe frameworks A 2 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 32; the flask was dried, then intermediate C 32 (0.1 mmol), the responding group D 10 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 125) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 995.00.
Example 126:
Dissolving probe frameworks A 3 (0.5 mmol) and B 11 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 33; the flask was dried, then intermediate C 33 (0.1 mmol), the responding group D 10 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 126) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1009.02.
Example 127:
Dissolving probe frameworks A 1 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 10; the flask was dried, then intermediate C 10 (0.1 mmol), the responding group D 21 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 127) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 878.83.
Example 128:
Dissolving probe frameworks A 2 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 11; the flask was dried, then intermediate C 11 (0.1 mmol), the responding group D 21 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 128) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 892.86.
Example 129:
Dissolving probe frameworks A 3 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 12; the flask was dried, then intermediate C 12 (0.1 mmol), the responding group D 21 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 129) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 906.89.
Example 130:
Dissolving probe frameworks A 1 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 10; the flask was dried, then intermediate C 10 (0.1 mmol), the responding group D 22 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 130) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 980.97.
Example 131:
Dissolving probe frameworks A 2 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 11; the flask was dried, then intermediate C 11 (0.1 mmol), the responding group D 22 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 131) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 995.00.
Example 132:
Dissolving probe frameworks A 3 (0.5 mmol) and B 4 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 12; the flask was dried, then intermediate C 12 (0.1 mmol), the responding group D 22 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 132) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1009.02.
Example 133:
Dissolving probe frameworks A 1 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 4; the flask was dried, then intermediate C 4 (0.1 mmol), the responding group D 23 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 133) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 949.36.
Example 134:
Dissolving probe frameworks A 2 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 5; the flask was dried, then intermediate C 5 (0.1 mmol), the responding group D 23 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 134) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 963.39.
Example 135:
Dissolving probe frameworks A 3 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 6; the flask was dried, then intermediate C 6 (0.1 mmol), the responding group D 23 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 135) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 977.42.
Example 136:
Dissolving probe frameworks A 1 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 4; the flask was dried, then intermediate C 4 (0.1 mmol), the responding group D 24 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 136) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1051.50.
Example 137:
dissolving probe frameworks A 2 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 5; the flask was dried, then intermediate C 5 (0.1 mmol), the responding group D 24 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 137) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1065.53.
Example 138:
dissolving probe frameworks A 3 (0.5 mmol) and B 2 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 6; the flask was dried, then intermediate C 6 (0.1 mmol), the responding group D 24 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 138) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1079.55.
Example 139:
Dissolving probe frameworks A 1 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 34; the flask was dried, then intermediate C 34 (0.1 mmol), the responding group D 1 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 139) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1051.50.
Example 140:
Dissolving probe frameworks A 2 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 35; the flask was dried, then intermediate C 35 (0.1 mmol), the responding group D 1 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 140) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1065.53.
Example 141:
Dissolving probe frameworks A 3 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 36; the flask was dried, then intermediate C 36 (0.1 mmol), the responding group D 1 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 141) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1079.55.
Example 142:
Dissolving probe frameworks A 1 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 34; the flask was dried, then intermediate C 34 (0.1 mmol), the responding group D 2 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 142) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1153.64.
Example 143:
Dissolving probe frameworks A 2 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 35; the flask was dried, then intermediate C 35 (0.1 mmol), the responding group D 2 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 143) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1167.66.
Example 144:
Dissolving probe frameworks A 3 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 36; the flask was dried, then intermediate C 36 (0.1 mmol), the responding group D 2 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 144) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 1181.69.
Example 145:
Dissolving probe frameworks A 1 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 34; the flask was dried, then intermediate C 34 (0.1 mmol), the responding group D 25 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 145) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 802.43.
Example 146:
Dissolving probe frameworks A 2 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 35; the flask was dried, then intermediate C 35 (0.1 mmol), the responding group D 25 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 146) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 816.46.
Example 147:
Dissolving probe frameworks A 3 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 36; the flask was dried, then intermediate C 36 (0.1 mmol), the responding group D 25 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 147) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 830.48.
Example 148:
Dissolving probe frameworks A 1 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 34; the flask was dried, then intermediate C 34 (0.1 mmol), the responding group D 26 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 148) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 904.56.
Example 149:
Dissolving probe frameworks A 2 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 35; the flask was dried, then intermediate C 35 (0.1 mmol), the responding group D 26 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 149) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 918.59.
Example 150:
Dissolving probe frameworks A 3 (0.5 mmol) and B 12 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 36; the flask was dried, then intermediate C 36 (0.1 mmol), the responding group D 26 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 150) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 932.62.
Example 151:
Dissolving probe frameworks A 1 (0.5 mmol) and B 13 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 37; the flask was dried, then intermediate C 37 (0.1 mmol), the responding group D 23 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 151) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 802.43.
Example 152:
Dissolving probe frameworks A 2 (0.5 mmol) and B 13 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 38; the flask was dried, then intermediate C 38 (0.1 mmol), the responding group D 23 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 152) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 816.46.
Example 153:
Dissolving probe frameworks A 3 (0.5 mmol) and B 13 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 39; the flask was dried, then intermediate C 39 (0.1 mmol), the responding group D 23 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 153) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 830.48.
Example 154:
Dissolving probe frameworks A 1 (0.5 mmol) and B 13 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 37; the flask was dried, then intermediate C 37 (0.1 mmol), the responding group D 24 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 154) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 904.56.
Example 155:
Dissolving probe frameworks A 2 (0.5 mmol) and B 13 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 38; the flask was dried, then intermediate C 38 (0.1 mmol), the responding group D 24 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 155) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 918.59.
Example 156:
Dissolving probe frameworks A 3 (0.5 mmol) and B 13 (0.5 mmol) by using 20mL of a mixed solvent of toluene and n-butanol (3:1), heating to 90 ℃ under the protection of nitrogen, reacting for about 2 hours, separating, purifying and drying by using HPLC after the reaction is finished to obtain an intermediate C 39; the flask was dried, then intermediate C 39 (0.1 mmol), the responding group D 24 (0.1 mmol), palladium acetate (0.0001 mmol), triethylamine (0.1 mmol) and dried DMF were added to the flask, the reaction was sealed at 110 ℃ for 18h under nitrogen protection, finally a black powder (denoted Dye 156) was obtained by rotary evaporation, purification and drying, which was characterized as follows: HRMS (m+) = 932.62.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (5)
1. An asymmetric near-infrared organic fluorescent probe is characterized by having the following structural formula:
2. the method for synthesizing the asymmetric near infrared organic fluorescent probe according to claim 1, comprising:
providing a probe skeleton with a difunctional structure, wherein the probe skeleton has the structural formula:
providing a first intermediate terminating in an aldehyde group having the formula:
providing a second intermediate having a terminal double bond, the second intermediate having the structural formula:
In the atmosphere of anhydrous and inert gas, in the presence of toluene and n-butanol, carrying out condensation reaction on the probe skeleton and a first intermediate with an aldehyde group at the tail end, and then carrying out connection reaction on a mixed reaction system containing a reaction product, a second intermediate with a double bond at the tail end, a catalyst and an organic solvent to obtain an asymmetric near-infrared organic fluorescent probe;
The molar ratio of the probe skeleton to the first intermediate is 1:1, the molar ratio of the reaction product of the first intermediate to the second intermediate is 1:1, the molar ratio of the reaction product of the first intermediate to triethylamine is 1:1, the temperature of the condensation reaction is 90 ℃, and the time is 2 hours; the temperature of the connection reaction is 140 ℃ and the time is 12h.
3. The synthesis method according to claim 2, characterized in that: the catalyst is a combination of palladium acetate and triethylamine, and the molar ratio of the palladium acetate to the triethylamine is 1:1000.
4. The synthesis method according to claim 2, characterized in that: the organic solvent is DMF; the volume ratio of toluene to n-butanol is 3:1.
5. Use of the asymmetric near infrared organic fluorescent probe according to claim 1 for preparing a near infrared region fluorescent imaging material or an optical diagnostic material.
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