CN115028562B - Polysulfide aromatic compound, preparation method and application thereof - Google Patents

Polysulfide aromatic compound, preparation method and application thereof Download PDF

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CN115028562B
CN115028562B CN202210601359.9A CN202210601359A CN115028562B CN 115028562 B CN115028562 B CN 115028562B CN 202210601359 A CN202210601359 A CN 202210601359A CN 115028562 B CN115028562 B CN 115028562B
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polysulfide
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benzene
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CN115028562A (en
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李旭萍
卢建军
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Taiyuan University of Technology
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    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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    • C07D209/04—Indoles; Hydrogenated indoles
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Abstract

The invention provides a polysulfide aromatic compound, a preparation method and application thereof, and relates to the technical field of luminescent materials. The polysulfide aromatic compound provided by the invention is a centrosymmetric compound which takes polysulfide benzene as a core and has different numbers of amide structure substituents. The preparation method comprises the following steps: the method comprises the steps of taking hexafluorobenzene as a raw material to perform a first-stage reaction to prepare central symmetry intermediates of p-benzoic acid substituted polysulfide benzene with different amounts, and then performing a second-stage reaction with substituent compounds to obtain the polysulfide aromatic compound. The polysulfide aromatic compound is applied to fluorescent imaging of a luminescent probe in a time resolution process. The polysulfide aromatic compound provided by the invention has long-life double-emission light under single molecule and aggregation state, and the preparation method provided by the invention has the advantages of cheap and easily available raw materials, simple synthesis and contribution to expansion production, and the polysulfide aromatic compound provided by the invention is applied to the field of luminescent probes, so that the imaging quality under various environments such as poor imaging conditions is effectively improved.

Description

Polysulfide aromatic compound, preparation method and application thereof
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a polysulfide aromatic compound, a preparation method and application thereof.
Background
Organic luminescent molecules have wide application in biological imaging. The time-resolved fluorescence imaging technology has great potential in the fields of biological imaging, detection, diagnosis and treatment integration and the like by setting a certain delay time between excitation light and long-life light emission so as to eliminate endogenous substances with short service life (generally nanosecond level) in a detection environment and background autofluorescence interference. Since the first report, time-resolved technology based on long-life detection has revolutionized the visual detection method (n.weibel, et al j.am.chem.soc.,2004,126,4888.).
Organic Thermal Activation Delayed Fluorescence (TADF) and Room Temperature Phosphorescence (RTP) molecules have long emission lifetimes and are free of heavy metal participation and free of toxic and side effects, and are therefore widely used in time-resolved fluorescence imaging (j.jin, et al, nat. Commun.,2020,11,842.). However, according to the restrictions of the Kasha rule, most molecules can only emit photons from the lowest excited state of a certain multiple state, so that most TADF or RTP molecules have a single emission wavelength, and when such single emission molecules are used as probes, once the emission intensity is weakened, the emission lifetime is hard to collect, and further, signal loss is caused, so that the imaging quality is reduced. Since the proposed theory of aggregation-induced emission (AIE) by the Tang Benzhong institution 2001 (i.e., some molecules emit poorly in solution and strongly in the aggregated or solid state) (j.luo, et al chem. Commun.,2001,1740.), some reports introduced molecules of AIE properties into time-resolved fluorescence imaging, which solved the problem of poor acquisition of lifetime signals due to the weakening of the emission intensity caused by aggregation of conventional molecules. However, in some complex microenvironments (such as cells, biological tissues, etc.), the comprehensive factors of temperature, polarity, pH, viscosity, etc. of the local area weaken the emission intensity, and although increasing the probe concentration can improve the emission intensity to a certain extent, the detection environment can be interfered, so that partial imaging is blurred or missing, and therefore, on the basis of the AIE property, a photophysical strategy with universality is created from the molecular level to cope with the challenging problem, and the development of a time-resolved probe is more scientifically significant. Compared with single-emission molecules, the probe with two emission wavelengths on the monolayer surface has self-correction potential, can provide two channels for biological imaging, and can effectively enhance emission signals through superposition, so that the imaging result is more real and reliable.
In combination with the research background, a single molecule with AIE performance and presenting TADF-RTP dual emission is developed, which not only has two long-life emissions independent of probe concentration, but also has certain complementarity of the life signals of the two emissions, can effectively enhance imaging quality, and can be used as a powerful candidate of a time resolution probe.
In view of this, the present invention has been made.
Disclosure of Invention
The invention provides a polysulfide aromatic compound, a preparation method and application thereof, which are used for solving the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polysulfide aromatic compound is a centrosymmetric compound which takes polysulfide benzene as a core and has different numbers of amide structure substituents.
Optionally, the polysulfide aromatic compound comprises any one or more of compounds I, ii, iii, iv, v, and vi:
compound I:
compound II:
compound iii:
compound IV:
compound V:
compound VI:
wherein R is one or more of benzene, carbazole, indole, indoline, phenothiazine and phenoxazine.
Optionally, the R is benzene or indole.
A process for the preparation of said polysulfide aromatic compound comprising:
the method comprises the steps of taking hexafluorobenzene as a raw material to perform a first-stage reaction to prepare central symmetry intermediates of p-benzoic acid substituted polysulfide benzene with different amounts, and then performing a second-stage reaction with substituent compounds to obtain the polysulfide aromatic compound.
Optionally, the first stage reaction comprises:
carrying out a first reaction on hexafluorobenzene and p-mercaptophenethyl ester in the presence of a first solvent and potassium carbonate to obtain a compound 1, and then carrying out hydrolysis and acidification under alkaline conditions to obtain a compound 2;
or,
carrying out a second reaction on hexafluorobenzene and sodium thiophenolate in the presence of a second solvent to obtain a compound 3, then reacting with p-mercaptophenethyl ester to obtain a compound 4, and then hydrolyzing and acidifying under alkaline conditions to obtain a compound 5;
the structural formula of the compound 1 is as follows:
the structural formula of the compound 2 is as follows:
the structural formula of the compound 3 is as follows:
the structural formula of the compound 4 is as follows:
the structural formula of the compound 5 is as follows:
optionally, the first solvent is N, N dimethylformamide, and the second solvent is 1, 3-dimethyl-2-imidazolidinone.
Optionally, the substituent compound includes: R-NH 2 Or (b)Wherein R is any one of benzene, carbazole, indole, indoline, phenothiazine and phenoxazine.
Optionally, the substituent compound is aniline or
Optionally, theThe synthesis of (2) comprises: adding 5-nitroindole, p-chlorophenyl phenyl sulfone and potassium carbonate into N-methyl pyrrolidone, reacting for 3-6 hours at 120-160 ℃, and reacting the reaction product with stannous chloride dihydrate to obtain the +.>
Optionally, the solvent of the second-stage reaction comprises DMF, the reaction temperature is between room temperature and 60 ℃, and the reaction time is between 24 and 40 hours;
2- (7-azabenzotriazol) -N, N, N ', N' -tetramethylurea hexafluorophosphate and N, N-diisopropylethylamine were also added during the second stage reaction.
The application of the polysulfide aromatic compound is applied to fluorescent imaging of a luminescent probe in a time resolution process.
The invention has the beneficial effects that:
the polysulfide aromatic compound provided by the invention takes a polysulfide benzene structure as a core, and different numbers of amide structures are centrosymmetric compounds formed by branches, and has the characteristics of dual long-life emission of heat activation delayed fluorescence and room-temperature phosphorescence and aggregation-induced luminescence, and has long-life dual-emission light in a single molecule and an aggregation state. The long-life emission can shield the self-background fluorescence interference, the dual-phase luminescence can enable the dual-phase luminescence to be independent of the probe concentration for imaging, and most importantly, the dual-emission property can provide a dual-channel imaging mode, and the superimposed long-life signal greatly improves the imaging quality, so that the negative effects caused by the self-background fluorescence, signal deletion and probe concentration fluctuation in the biological imaging process are effectively reduced, and the imaging quality is comprehensively improved.
The central symmetry intermediates of the p-benzoic acid substituted polysulfide benzene with different numbers are prepared by taking hexafluorobenzene as a raw material, then the central symmetry intermediates are reacted with substituent compounds to obtain polysulfide aromatic compounds, and the central symmetry compounds with the polysulfide benzene as the center and different numbers of amide structures as branches are prepared.
The central symmetry polysulfide aromatic compound which takes polysulfide benzene as the center and takes different numbers of amide structures as branches is used as a novel time-resolved luminescence probe, and has double-phase long-life double emission in a solvent, so that two emitted wavelengths can be used as detection channels, and the service life is used as detection signals, thereby improving imaging quality, solving imaging problems in certain complex microenvironments and having important value in related industries.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic diagram of a luminescent probe according to the present invention.
FIG. 2 is a graph showing fluorescence emission patterns of 50. Mu. Mol/L of Compound A-4 prepared in example 1 in a mixed solvent of tetrahydrofuran and water in various ratios.
FIG. 3 is a graph showing fluorescence emission patterns of the compound A-4 prepared in example 1 in tetrahydrofuran of different concentrations.
FIG. 4 is a graph showing the decay lifetime of a tetrahydrofuran solution of Compound A-4 at a concentration of 50. Mu. Mol/L obtained in example 1 at various temperatures.
FIG. 5 is a fluorescence emission spectrum of the compound A-1 having a concentration of 1. Mu. Mol/L obtained in example 2 dissolved in organic solvents of different polarities.
FIG. 6 is a graph showing fluorescence emission patterns of the compound A-1 produced in example 2 in tetrahydrofuran of different concentrations.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
First, the present invention is explained in its entirety, specifically as follows:
the invention provides a polysulfide aromatic compound which is a centrosymmetric compound taking polysulfide benzene as a core and having different numbers of amide structure substituents.
Two light-emitting units exist in the structure of the compound, wherein the polythiobenzene core is a first light-emitting unit and is used for providing phosphorescence emission at room temperature in molecules due to heavy atom effect and conformational limitation; the peripheral group is a second light-emitting unit, and the excited state is regulated and controlled through the bridging group to provide heat activation in the molecule and delay fluorescence emission. And both light emitting units (or between the light emitting units and the bridging group) have a non-planar twisted structure to exhibit an aggregation-induced emission effect. Therefore, the compound with the structure has the characteristics of dual long-life emission of heat activation delay fluorescence and room-temperature phosphorescence and aggregation-induced luminescence, and has long-life dual-emission light in a single molecule and an aggregation state, so that the negative effects caused by self-background fluorescence, signal deletion and probe concentration fluctuation in the biological imaging process can be effectively reduced, and the imaging quality is improved.
In an alternative embodiment, the polysulfide aromatic compound comprises any one or more of compounds I, ii, iii, iv, v, and vi:
compound I:
compound II:
compound iii:
compound IV:
compound V:
compound VI:
wherein R is one or more of benzene, carbazole, indole, indoline, phenothiazine and phenoxazine;
optionally, the R is benzene or indole.
The heterocyclic functional groups of N, O, S and like atoms generally have good electron donating ability and are often used as donor units to build donor-acceptor structures with other acceptor units (diphenyl sulfone). In particular to heterocyclic indole containing N atoms, which has low toxicity, low cost, easy availability, wide biological activity and easy functional modification, and is commonly used for constructing biological probes. In addition, as the most basic conjugated structural unit, the benzene ring structure is easily modified.
When R is benzene, the polysulfide aromatic compound can be one or more of A-1, A-2 and A-3;
A-1：
A-2：
A-3：
when R is indole, the polysulfide aromatic compound can be one or more of A-4, A-5 and A-6;
A-4：
A-5：
A-6：
a process for the preparation of said polysulfide aromatic compound comprising:
the method comprises the steps of taking hexafluorobenzene as a raw material to perform a first-stage reaction to prepare central symmetry intermediates of p-benzoic acid substituted polysulfide benzene with different amounts, and then performing a second-stage reaction with substituent compounds to obtain the polysulfide aromatic compound.
In an alternative embodiment, the first stage reaction comprises:
carrying out a first reaction on hexafluorobenzene and p-mercaptophenethyl ester in the presence of a first solvent and potassium carbonate to obtain a compound 1, and then carrying out hydrolysis and acidification under alkaline conditions to obtain a compound 2;
or,
carrying out a second reaction on hexafluorobenzene and sodium thiophenolate in the presence of a second solvent to obtain a compound 3, then reacting with p-mercaptophenethyl ester to obtain a compound 4, and then hydrolyzing and acidifying under alkaline conditions to obtain a compound 5;
the structural formula of the compound 1 is as follows:
the structural formula of the compound 2 is as follows:
the structural formula of the compound 3 is as follows:
the structural formula of the compound 4 is as follows:
the structural formula of the compound 5 is as follows:
in an alternative embodiment, the first solvent is N, N dimethylformamide and the second solvent is 1, 3-dimethyl-2-imidazolidinone.
In an alternative embodiment, the substituent compound comprises: R-NH 2 Or (b)Wherein R is any one of benzene, carbazole, indole, indoline, phenothiazine and phenoxazine. />
In an alternative embodiment, the substituent compound is aniline or
In an alternative embodiment, theThe synthesis of (2) comprises: adding 5-nitroindole, p-chlorophenyl phenyl sulfone and potassium carbonate into N-methyl pyrrolidone, reacting for 3-6 hours at 120-160 ℃, and reacting the reaction product with stannous chloride dihydrate to obtain the +.>
In an alternative embodiment, the solvent of the second stage reaction comprises DMF, the reaction temperature is from room temperature to 60 ℃, and the reaction time is from 24 to 40 hours;
2- (7-azabenzotriazol) -N, N, N ', N' -tetramethylurea hexafluorophosphate and N, N-diisopropylethylamine were also added during the second stage reaction.
Preparation of Compound A-1:
first stage reaction: under the protection of nitrogen, taking dry N, N dimethylformamide as a reaction solvent, adding a certain amount of hexafluorobenzene, p-mercaptophenethyl ester and anhydrous potassium carbonate, and reacting for 24-40 hours at room temperature to 60 ℃ (the reaction temperature can be exemplified by any value between 25 ℃, 28 ℃, 30 ℃,35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃ and the reaction time can be any value between 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours and 40 hours), so as to obtain yellow solid which is marked as a compound 1; dissolving compound 1 in an appropriate amount of tetrahydrofuran, adding an appropriate amount of aqueous sodium hydroxide solution to the solution, stirring at room temperature for 18-24 hours (for example, stirring time can be any value between 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours and 24 hours), and then adding a dilute hydrochloric acid solution to make the solution acidic and precipitate out to obtain a central symmetry intermediate of p-benzoic acid substituted polysulfide benzene, which is denoted as compound 2;
the second stage reaction: dissolving the compound 2 and 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea Hexafluorophosphate (HATU) in a proper amount of DMF, stirring for 15min under the protection of nitrogen, adding a proper amount of substituent compound aniline and N, N-Diisopropylethylamine (DIPEA), stirring at room temperature to 60 ℃ for 24-40h (the temperature can be any value between 25 ℃, 28 ℃, 30 ℃,35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃ for 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h and 40h, for an exemplary time, and the stirring time can be any value between 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h and 40 h), and dripping into 200ml of ice water to collect precipitate to obtain the compound shown as the compound I, wherein R is benzene, and the compound A-1 is recorded.
Alternatively, in the second stage reaction, compound 2 and HATU are first dissolved in DMF, stirred under nitrogen, and then the substituent compound aniline is added, and the molar mass ratio of compound 2, HATU and aniline is 0.9-1.1mmol:5.4-6.6mmol:8.1-9.9mmol (exemplary molar mass ratios of Compound 2, HATU and aniline may be 0.9mmol:5.4mmol:8.1mmol, 1.0mmol:5.5mmol:8.2mmol, 1.1mmol:5.7mmol:8.3mmol, 0.9mmol:5.6mmol:8.4mmol, 0.9mmol:5.8mmol:8.6mmol, 1.0mmol:5.9mmol:9.0mmol, 1.1mmol:6.5mmol:9.3mmol, 1.1mmol:6.3mmol:8.5mmol, 1.1mmol:6.1mmol:8.7mmol, 1.1mmol:6.0mmol:9.2mmol, 1.0mmol:6.6mmol:9.9mmol, 1.0mmol: 6.9 mmol:9.9mmol and 0.9mmol: 9.8 mmol), and any of the reaction mixture is dried in water and the aqueous solution is collected after completion of any of the reaction mixture of the two, and the aqueous solution is dried to obtain a large precipitate of acetone solution.
The synthetic route is as follows:
preparation of Compounds A-2, A-3:
first stage reaction: under the protection of nitrogen, 1, 3-dimethyl-2-imidazolone is taken as a solvent, a certain amount of sodium thiophenol and hexafluorobenzene are added, and stirring reaction is carried out for 72 hours at 40 ℃ to obtain a compound 3; reacting a certain amount of compound 3, p-mercaptophenethyl ester and anhydrous potassium carbonate with dry N, N dimethylformamide as a reaction solvent at room temperature to 60 ℃ for 24-40h under the protection of nitrogen (the reaction temperature can be exemplified by any value between 25 ℃, 28 ℃, 30 ℃,35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃ and the reaction time can be any value between 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h and 40 h), to obtain yellow solid which is recorded as compound 4; dissolving compound 4 in an appropriate amount of tetrahydrofuran, adding an appropriate amount of aqueous sodium hydroxide solution to the solution, stirring at room temperature for 18-24 hours (for example, stirring time may be any value between 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours and 24 hours), then adding a dilute hydrochloric acid solution to make the solution acidic and precipitate out, denoted as compound 5;
the second stage reaction: dissolving the compound 5 and 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea Hexafluorophosphate (HATU) in a proper amount of DMF, stirring for 15min under the protection of nitrogen, adding a proper amount of substituent compound aniline and N, N-Diisopropylethylamine (DIPEA), stirring at room temperature to 60 ℃ for 24-40h (the temperature can be any value between 25 ℃, 28 ℃, 30 ℃,35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃ for 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h and 40h, for an exemplary time, and the stirring time can be any value between 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h and 40 h), and dripping into 200ml of ice water to collect precipitate to obtain a compound with R being benzene as shown in a compound II, namely a compound A-2;
alternatively, in the second stage reaction for preparing the compound A-2, the compound 5 and the HATU are dissolved in DMF, stirred under nitrogen, and then the substituent compound aniline is added, and the molar mass ratio of the compound 5 to the HATU to the aniline is 0.9-1.1mmol:3.6-4.4mmol:5.4-6.6mmol (exemplary molar mass ratios of compound 5, HATU and aniline may be 0.9mmol:4.4mmol:5.4mmol, 1.0mmol:3.6mmol:5.8mmol, 1.1mmol:4.4mmol:6.6mmol, 0.9mmol:3.6mmol:5.4mmol, 0.9mmol:3.8mmol:6.1mmol, 1.0mmol:4.0mmol:6.0mmol, 1.1mmol:4.0mmol:6.3mmol, 1.1mmol:3.8mmol:6.5mmol, 1.1mmol:4.1mmol:5.5mmol, 1.1mmol:3.9mmol:5.9mmol, 1.0mmol:3.7mmol:6.4mmol, 1.0mmol:4.2mmol:5.6mmol, 0.9mmol:4.3mmol:5.7mmol and 0.9mmol: 4.9 mmol) of any of the aqueous solution is collected by washing the reaction mixture with water to obtain a large amount of acetone solution after completion of the reaction mixture.
This step also yields a compound of formula III, herein designated compound A-3, wherein R is benzene;
alternatively, in the second stage reaction for preparing the compound A-3, the compound 5 and the HATU are dissolved in DMF, stirred under nitrogen, and then the substituent compound aniline is added, and the molar mass ratio of the compound 5 to the HATU to the aniline is 0.9-1.1mmol:1.8-2.2mmol:2.7-3.3mmol (exemplary molar mass ratio of compound 5, HATU and aniline may be any of 0.9mmol:1.8mmol:3.3mmol, 1.0mmol:1.9mmol:3.2mmol, 1.1mmol:2.0mmol:3.1mmol, 0.9mmol:2.1mmol:3.0mmol, 0.9mmol:2.2mmol:2.7mmol, 1.0mmol:2.0mmol:2.9mmol, 1.1mmol:1.9mmol:2.8mmol, 1.1mmol:1.8mmol:3.3mmol, 1.1mmol:2.1mmol: 3.9 mmol) and after the reaction has ended, the reaction solution is dropped into cold water to collect the precipitate, which is washed with a large amount of water, ethanol, acetone to purify compound A-3.
The synthetic route of the compound A-2 is as follows:
the synthetic route of the compound A-3 is as follows:
/>
preparation of Compound A-4:
preparation of the substituent compound: adding appropriate amount of 5-nitroindole, p-chlorophenyl phenyl sulfone and potassium carbonate under nitrogen protection, reacting at 120-160deg.C for 3-6 hr (it is understood that the reaction temperature can be any value between 120deg.C, 130deg.C, 140 deg.C, 150deg.C and 160deg.C, and the reaction time can be any value between 3 hr, 3.5 hr, 4 hr, 4.5 hr, 5 hr, 5.5 hr and 6 hr) to obtain the compoundUnder nitrogen protection, the compound +.>Dispersing in ethanol, adding appropriate amount of stannous chloride dihydrate, and reacting under reflux for 18-24 hr (it is understood that the reaction time can be any value between 18 hr, 19 hr, 20 hr, 21 hr, 22 hr, 23 hr and 24 hr) to obtain its reduction product, i.e. substituent compound->
First stage reaction: the same as in the first stage reaction in the preparation of compound A-1;
the second stage reaction: the first stage reaction product compound 2 and 2- (7-azabenzotriazol) -N, N, N ', N' -tetramethylurea Hexafluorophosphate (HATU) were dissolved in an appropriate amount of DMF and stirred under nitrogen for 15min before adding an appropriate amount of substituent compoundAnd N, N-Diisopropylethylamine (DIPEA), at room temperature to 60℃for 24-40 hours (it will be appreciated that the temperature here may be 25 ℃, 28 ℃, 30 ℃,35 ℃,40 °,Any value between 45 ℃, 50 ℃, 55 ℃ and 60 ℃, stirring for any value between 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours and 40 hours), and then dripping 200ml of ice water to collect precipitate, thus obtaining a compound with R being indole as shown in a compound IV, which is marked as a compound A-4;
alternatively, in the second stage of the reaction when preparing compound A-4, compound 2 and HATU are first dissolved in DMF and stirred under nitrogen, then the substituent compound is addedAnd Compound 2, HATU and substituent Compound +>The molar mass ratio of (2) is 0.9-1.1mmol:5.4-6.6mmol:8.1-9.9mmol (exemplary, compound 2, HATU and substituent Compounds +.>The molar mass ratio of (3) may be any of 0.9mmol:5.4mmol:8.1mmol, 1.0mmol:5.5mmol:8.2mmol, 1.1mmol:5.7mmol:8.3mmol, 0.9mmol:5.6mmol:8.4mmol, 0.9mmol:5.8mmol, 1.0mmol:5.9mmol, 1.1mmol:6.5mmol:9.3mmol, 1.1mmol:6.3mmol:8.5mmol, 1.1mmol:6.1mmol:8.7mmol, 1.1mmol:6.0mmol:9.2mmol, 1.0mmol:6.6mmol:9.9mmol, 1.0mmol: 6.9 mmol:9.7mmol, 0.9mmol: 6.8 mmol and 0.9mmol:6.2 mmol) and after the reaction has ended, the reaction liquid is dropped into cold water, and the product is washed with acetone to obtain a large amount of water, which is washed with acetone.
The synthetic route of the compound A-4 is as follows:
preparation of Compounds A-5, A-6:
preparation of the substituent compound: preparing a substituent compound in the same compound A-4;
first stage reaction: the same as the first stage reactions in the preparation of the compounds A-2, A-3, respectively;
the second stage reaction: dissolving the first-stage reaction product, namely the compound 5, and 2- (7-azabenzotriazol) -N, N, N ', N' -tetramethylurea Hexafluorophosphate (HATU) in a proper amount of DMF, stirring for 15min under the protection of nitrogen, and then adding a proper amount of substituent compoundAnd N, N-Diisopropylethylamine (DIPEA), stirring at room temperature to 60 ℃ for 24-40 hours (it is understood that the temperature herein may be any value between 25 ℃, 28 ℃, 30 ℃,35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃ and the stirring time may be any value between 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours and 40 hours), and then dropping into 200ml of ice water to collect precipitate, thereby obtaining the compounds of which R is indole as shown in a compound V and a compound VI, respectively, which are referred to herein as a compound A-5 and a compound A-6, respectively;
alternatively, in the second stage of the reaction when preparing compound A-5, compound 5 and HATU are first dissolved in DMF and stirred under nitrogen, then the substituent compound is addedAnd Compound 5, HATU and substituent Compound +>The molar mass ratio of (2) is 0.9-1.1mmol:3.6-4.4mmol:5.4-6.6mmol (exemplary, compound 5, HATU and substituent Compounds +.>The molar mass ratio of (C) may be 0.9mmol:4.4mmol:5.4mmol, 1.0mmol:3.6mmol:5.8mmol, 1.1mmol:4.4mmol:6.6mmol, 0.9mmol:3.6mmol:5.4mmol, 0.9mmol:3.8mmol:6.1mmol, 1.0mmol:4.0mmol:6.0mmol, 1.1mmol:4.0mmol:6.3mmol, 1.1mmol:3.8mmol:6.5mmol, 1.1mmol:4.1mmol:5.5mmol, 1.1mmol:3.9mmol:5.9mmol, 1.0mmol:3.7mmol:6.4mmol, 1.0mmol:4.2mmol:5.6mmol, 0.9mmol:4.3mmol:5.7mmol, and any value between 0.9mmol:4.0mmol:6.2 mmol); after the reaction is finished, dripping the reaction liquid into cold water to collect precipitate, and washing and purifying the precipitate with a large amount of water, ethanol and acetone to obtain a compound A-5;
alternatively, in the second stage of the reaction, compound 5 and HATU are dissolved in DMF and stirred under nitrogen before adding the substituent compound to the reaction mixtureAnd Compound 5, HATU and substituent Compound +>The molar mass ratio of (2) is 0.9-1.1mmol:1.8-2.2mmol:2.7-3.3mmol (exemplary, compound 5, HATU and substituent Compounds +.>The molar mass ratio of (3) may be any of 0.9mmol:1.8mmol:3.3mmol, 1.0mmol:1.9mmol:3.2mmol, 1.1mmol:2.0mmol:3.1mmol, 0.9mmol:2.1mmol:3.0mmol, 0.9mmol:2.2mmol:2.7mmol, 1.0mmol: 2.9mmol, 1.1mmol:1.9mmol:2.8mmol, 1.1mmol:1.8mmol:3.3mmol, 1.1mmol:2.1mmol:3.0mmol, and 1.1mmol:1.9 mmol) after the reaction has ended, the reaction liquid is poured into cold water to collect a precipitate, and the precipitate is washed with a large amount of water, ethanol, acetone to purify the compound A-6.
Synthetic route for Compound A-5:
synthetic route for Compound A-6:
the application of the polysulfide aromatic compound is applied to fluorescent imaging of a luminescent probe in a time resolution process.
In the application process, the compounds I, II, III, IV, V and VI are dissolved in THF solution, heLa cells are hatched, a laser confocal microscope with a time resolution function is used for representing cell fluorescence imaging, and long-life signals under double channels are superimposed, so that the imaging quality is enhanced.
Example 1
The polysulfide aromatic compound is prepared by using the preparation method of the polysulfide aromatic compound, and is applied to a luminescent probe, and the performance of the polysulfide aromatic compound is tested. The principle schematic diagram of the luminous probe is shown in figure 1.
S1: compound 1Is synthesized by (a)
Ethyl p-mercaptobenzoate (1.68 g,18mmol,9 eq.), hexafluorobenzene (0.332 g,2mmol,1 eq.) and anhydrous potassium carbonate (2.48 g,18mmol,9 eq.) were added to a two-necked flask and protected with nitrogen, then dried DMF (20 ml) was injected via syringe, reacted at 60 ℃ for 40 hours, cooled and 200ml of water was added to produce a yellow precipitate, the solid was collected by filtration, and then repeatedly washed with a large amount of water, ethanol and acetone, and dried to give compound 1 in 55% yield. 1 H NMR(400MHz，DMSO-d6)δ(ppm):7.85(d，J＝8.1Hz，12H)，7.20(d，J＝8.1Hz，12H)，4.34(q，J＝7.1Hz，12H)，1.37(t，J＝7.1Hz，18H)。
S2: compound 2Is synthesized by (a)
Compound 1 (1.15 g,1.0 mmol) synthesized in S1 was dissolved in THF (20 mL), aqueous sodium hydroxide solution (2.0M, 10 mL) was added to the solution, stirred at room temperature for 18 hours, then dilute hydrochloric acid solution (1.0M, 200 mL) was added to make the solution acidic and precipitate out, and the solid was collected by filtration, followed by water, ethanol, ethyl acetate and propylene in this orderKetone washing gave a yellow powder in 60% yield. 1 H NMR(400MHz，DMSO-d6)δ(ppm):12.90(s，6H)，7.82-7.75(m，12H),7.17-7.10(m，12H)。
S3: compounds of formula (I)Is synthesized by (a)
5-nitroindole (1.62 g,10 mmol), 4-chlorodiphenylsulfone (2.53 g,10 mmol) and potassium carbonate (19.35 g,100 mmol) are added into a 100mL round bottom flask, NMP15mL is injected under the protection of nitrogen, the reaction is carried out for 8 hours at 140 ℃, the temperature is reduced to room temperature, the reaction solution is dripped into 200mL ice water to separate out precipitate, suction filtration is carried out, and the filter cake is repeatedly washed by water and petroleum ether to obtain pale yellow solidThe yield was 90%. 1 H NMR(400MHz，DMSO-d6)δ(ppm):8.68(s，1H)，8.19(d，J＝7.9Hz，2H),8.05(dd，J＝20.5，12.6Hz，4H),7.92(d，J＝7.9Hz，2H),7.81(d，J＝8.9Hz，1H)，7.71(dd，J＝18.9，7.4Hz，3H)，7.05(s，1H)。
S4: compounds of formula (I)Is synthesized by (a)
S3-synthesized compound was added to a 250ml round bottom flask(3.78 g,10 mmol) and 180mL of ethanol, followed by addition of stannous chloride dihydrate (22.56 g,100 mmol), reflux for 20 hours under nitrogen protection, natural cooling to room temperature, dropping the reaction solution into 200mL of ice water, adding saturated sodium hydroxide solution to adjust pH to neutrality, extracting with dichloromethane (100 mL. Times.3), combining organic layers, washing with saturated brine, and drying over anhydrous sodium sulfate. Concentrating under vacuum, and washing with ethanol to obtain yellow solid +.>The yield was 70%. 1 H NMR(400MHz，DMSO-d6)δ(ppm):8.11-8.04(m，2H)，8.05-7.98(m，2H),7.82-7.76(m，2H)，7.75-7.69(m，1H),7.66(dd，J＝8.3，6.5Hz，2H)，7.58(d，J＝3.4Hz，1H)，7.43(d，J＝8.7Hz，1H)，6.76(d，J＝2.1Hz，1H)，6.59(dd，J＝8.8，2.2Hz，1H)，6.50(d，J＝3.4Hz，1H)，4.79(s，2H)。
S5: compound A-4Is synthesized by (a)
Compound 2 (0.495 g,0.5 mmol) synthesized from S2 and HATU (1.14 g,3 mmol) were dissolved in 10ml DMF and stirred for 15min under nitrogen protection in a double-necked flask, then added to compound synthesized from S4(1.566 g,4.5 mmol) and 1ml of DIPEA were poured, stirred at 35℃for 40 hours, then dropped into 200ml of ice water to collect precipitate, and washed with water, ethanol, acetone and the like to obtain yellow powder A-4 in 63% yield. 1 H NMR(400MHz，DMSO-d6)δ(ppm):10.15(s，6H)，8.10-7.98(m，30H)，7.95(d，J＝8.2Hz，12H)，7.67(dq，J＝14.8，7.5Hz，30H)，7.55(d，J＝3.4Hz，6H)，7.43(t，J＝7.1Hz，12H)，7.24(d，J＝8.2Hz，12H)，6.58(d，J＝3.4Hz，6H)。
Performance test:
the compound A-4 synthesized by S5 is prepared into a mixed solution of tetrahydrofuran and water, and the water proportion is 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90% in sequence, and the concentration is 50 mu mol/L. 2mL of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and the fluorescence emission spectrum, lambda ex =315 nm, the result is shown in fig. 2.
As can be seen from fig. 2, the compound a-4 exhibits dual emission from the single molecular state to the aggregation state, and the second emission peak gradually increases and the first emission peak gradually decreases as the water content increases.
The compound A-4 obtained in the step S5 is prepared into tetrahydrofuran solutions with different concentrations, and the concentrations are 10, 20, 50, 100 and 1000 mu mol/L in sequence. Respectively dissolving 2mlThe solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and its fluorescence emission spectrum, lambda ex =315 nm, the result is shown in fig. 3.
As can be seen from fig. 3, the tetrahydrofuran solutions of the compound a-4 all exhibit dual emission within a certain concentration range, and the second emission peak gradually increases and the first emission peak gradually decreases as the concentration of the solution increases.
Compound A-4 obtained in S5 was prepared as a tetrahydrofuran solution having a concentration of 50. Mu. Mol/L. 2ml of the solution was added to a 1 cm. Times.1 cm. Times.4 cm cuvette with plug, and its decay lives, lambda. At different temperatures were tested ex =315 nm, the result is shown in fig. 4. Wherein fig. 4A and 4B are decay lifetimes at the first and second emission peaks, respectively.
As can be seen from fig. 4A, in a certain temperature range, the decay lifetime of the solution shows an increasing trend with the rise of temperature; as can be seen from fig. 4B, the decay lifetime of the solution showed a decreasing trend with increasing temperature over a certain temperature range.
Example 2
The polysulfide aromatic compound is prepared by using the preparation method of the polysulfide aromatic compound, and is applied to a luminescent probe, and the performance of the polysulfide aromatic compound is tested. The principle schematic diagram of the luminous probe is shown in figure 1.
S1: compound 1Is synthesized by (a)
Ethyl p-mercaptobenzoate (1.68 g,18mmol,9 eq.), hexafluorobenzene (0.332 g,2mmol,1 eq.) and anhydrous potassium carbonate (2.48 g,18mmol,9 eq.) were added to a two-necked flask and protected with nitrogen, then dried DMF (20 ml) was injected via syringe, reacted at 60 ℃ for 40 hours, cooled and 200ml of water was added to produce a yellow precipitate, the solid was collected by filtration, and then repeatedly washed with a large amount of water, ethanol and acetone, and dried to give compound 1 in 55% yield. 1 H NMR(400MHz，DMSO-d6)δ(ppm):7.85(d，J＝8.1Hz，12H)，7.20(d，J＝8.1Hz，12H)，4.34(q，J＝7.1Hz，12H)，1.37(t，J＝7.1Hz，18H)。
S2: compound 2Is synthesized by (a)
Compound 1 (1.15 g,1.0 mmol) synthesized in S1 was dissolved in THF (20 mL), aqueous sodium hydroxide solution (2.0M, 10 mL) was added to the solution, stirred at room temperature for 18 hours, then dilute hydrochloric acid solution (1.0M, 200 mL) was added to make the solution acidic and precipitate out, and the solid was collected by filtration, washed with water, ethanol, ethyl acetate and acetone in this order to obtain yellow powder in 60% yield. 1 H NMR(400MHz，DMSO-d6)δ(ppm):12.90(s，6H)，7.82-7.75(m，12H),7.17-7.10(m，12H)。
S3: compound A-1Is synthesized by (a)
Compound 2 (0.495 g,0.5 mmol) synthesized by S2 and HATU (1.14 g,3 mmol) were dissolved in 10ml of DMF and stirred under nitrogen protection in a double-necked flask for 15min, then aniline (0.4191 g,4.5 mmol) was added and 1ml of DIPEA was injected, stirred at 35℃for 40h, then added dropwise to 200ml of ice water to collect precipitate, and the precipitate was washed with water, ethanol, acetone and the like to give yellow powder A-1 in 69% yield. 1H NMR (400 MHz, DMSO-d 6) delta (ppm): 10.18 (s, 6H), 7.91 (d, J=8.2 Hz, 12H), 7.71 (d, J=8.0 Hz, 12H), 7.29 (t, J=7.7 Hz, 12H), 7.24 (d, J=8.2 Hz, 12H), 7.09 (t, J=7.4 Hz, 6H).
Performance test:
the compound A-1 synthesized by S3 is dissolved in organic solvents with different polarities, namely toluene, methylene dichloride, tetrahydrofuran, ethyl acetate, chloroform, acetonitrile, N dimethylformamide and dimethyl sulfoxide, and the concentration is 1 mu mol/L. 2mL of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and the fluorescence emission spectrum, lambda ex =330 nm, the result is shown in fig. 5.
As can be seen from fig. 5, the positions of the two emission peaks do not change much with the change in polarity, and the compound a-1 exhibits dual emission in these solvents.
The compound A-1 obtained in S3Tetrahydrofuran solutions with different concentrations are prepared, and the concentrations are 0.1, 0.5, 1, 5, 10, 50 and 100 mu mol/L in sequence. 2ml of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and its fluorescence emission spectrum, lambda.was measured ex =330 nm, the result is shown in fig. 6.
As can be seen from fig. 6, the tetrahydrofuran solution of the compound a-1 showed dual emission in a certain concentration range, and the proportion of the second emission peak significantly increased as the concentration of the solution increased.
As can be seen from examples 1-2, the polysulfide aromatic compound provided by the invention has two phases of long-life double emission, and when the polysulfide aromatic compound is applied to the field of fluorescence imaging, the two emitted wavelengths can be used as detection channels, the service life is used as detection signals, and the purpose of improving the imaging quality is realized. Meanwhile, the preparation method has the advantages of cheap and easily available raw materials and simple and controllable process. Therefore, the fluorescent material has important application value and wide application prospect in the field of luminescent materials.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (9)

1. The polysulfide aromatic compound is characterized by being a centrosymmetric compound which takes polysulfide benzene as a core and has different numbers of amide structure substituents;
the polysulfide aromatic compound is selected from any one or more of compounds I, II, III, IV, V and VI:
compound I:
；
compound II:
；
compound iii:
；
compound IV:
；
compound V:
；
compound VI:
；
wherein R is one or more of benzene, carbazole, indole, indoline, phenothiazine and phenoxazine.
2. The polysulfide aromatic compound of claim 1, wherein R is benzene or indole.
3. A method for producing the polysulfide aromatic compound as recited in claim 1 or 2, characterized by comprising:
performing a first-stage reaction on hexafluorobenzene serving as a raw material to prepare central symmetry intermediates of p-benzoic acid substituted polysulfide benzene with different amounts, and then performing a second-stage reaction on the central symmetry intermediates and substituent compounds to obtain the polysulfide aromatic compound;
the first stage reaction comprises:
carrying out a first reaction on hexafluorobenzene and p-mercaptophenethyl ester in the presence of a first solvent and potassium carbonate to obtain a compound 1, and then carrying out hydrolysis and acidification under alkaline conditions to obtain a compound 2;
or,
carrying out a second reaction on hexafluorobenzene and sodium thiophenolate in the presence of a second solvent to obtain a compound 3, then reacting with p-mercaptophenethyl ester to obtain a compound 4, and then hydrolyzing and acidifying under alkaline conditions to obtain a compound 5;
the structural formula of the compound 1 is as follows:
；
the structural formula of the compound 2 is as follows:
；
the structural formula of the compound 3 is as follows:
or->；
The structural formula of the compound 4 is as follows:
or->；
The structural formula of the compound 5 is as follows:
or->。
4. The method of claim 3, wherein the first solvent is N, N dimethylformamide and the second solvent is 1, 3-dimethyl-2-imidazolidinone.
5. A method of preparation according to claim 3, wherein the substituent compound is selected from the group consisting of: R-NH 2 Or (b)Wherein R is any one of benzene, carbazole, indole, indoline, phenothiazine and phenoxazine.
6. The process according to claim 3, wherein the substituent compound is aniline or。
7. The method of claim 6, wherein the steps ofThe synthesis of (2) comprises: adding 5-nitroindole, p-chlorophenyl phenyl sulfone and potassium carbonate into N-methyl pyrrolidone, reacting at 120-160 ℃ for 3-6h, and reacting the reaction product with stannous chloride dihydrate to obtain the productSaid->。
8. The process according to any one of claims 3 to 7, wherein the solvent of the second stage reaction comprises DMF at a reaction temperature of from room temperature to 60 ℃ for a reaction time of from 24 to 40 hours;
2- (7-azabenzotriazol) -N, N, N ', N' -tetramethylurea hexafluorophosphate and N, N-diisopropylethylamine were also added during the second stage reaction.
9. Use of a polysulfide aromatic compound according to any one of claims 1-2 for fluorescence imaging of luminescent probes during time-resolved for non-diagnostic therapeutic purposes.
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CN112341379A (en) * 2020-10-23 2021-02-09 复旦大学 Polyaryl thiopyridine cationic salt light-operated cell pyrophoric material and preparation method and application thereof
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