CN111961067A - Azo-based dicarbole derivative and preparation method thereof - Google Patents
Azo-based dicarbole derivative and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an azo-based dicarbole derivative and a preparation method thereof, wherein the chemical structure of the azo-based dicarbole derivative is shown as (I), and the azo-based dicarbole derivative is obtained by carrying out suzuki coupling reaction on a 5-p-borate phenyl carbazole derivative and 4, 4' -diiodoazobenzene under the catalysis of tetrakis (triphenylphosphine) palladium. The compound has the advantages of simple preparation method, mild reaction conditions, simple and convenient operation and excellent optical performance, and can be used for solar cells, light storage materials, photodynamic therapy and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of an azo-based dicarbole derivative.
Background
The corrole compound is a novel porphyrin macrocyclic compound formed by conjugatively connecting four pyrroles. The N and C in the molecule are hybridized by sp2, and the rest p orbital is occupied by a single electron or a lone pair of electrons to form a large pi bond of 18 electrons. Compared with porphyrin, the corrole molecule lacks a 20-bit carbon atom, has a small inner cavity, can stabilize high-valence transition metal ions, has a lower oxidation potential, a higher fluorescence quantum yield, a larger Stokes shift and stronger red light absorption than porphyrin, is an important multifunctional compound, and particularly, in recent years, the corrole compound is used as a cancer detection reagent and a photosensitizer for photodynamic therapy (PDT). The photochromic switch of fluorescence emission is a reliable foundation for preparing an optical molecular memory device, and the reasonable adjustment of a chromophoric group and a photosensitive group in a material is a key for successfully developing the fluorescent molecular memory device, wherein the important point is that the fluorescence emission cannot interfere with the photochromic process. The corrole derivative is an ideal material in the aspect of molecular switch due to the large Stokes shift and excellent optical performance.
Azobenzene is a diazene derivative, two hydrogen atoms of the diazene are respectively replaced by two benzene rings, and trans-cis isomerization of the azobenzene is researched in many aspects. Azobenzene is converted from a thermodynamically stable trans form into a cis form under the irradiation of ultraviolet rays or visible light, the cis form can be changed into the trans form through illumination (generally different wavelengths relative to a forward process) or heating, and the reversible chemical process is accompanied by the change of color, refractive index, dielectric constant, dipole moment and the like, so that azobenzene has potential application in the fields of optical information storage, molecular switching, photochromic materials, liquid crystal materials, sensors, thin film transistors and the like. Based on the superior performances of the corrole and azobenzene, the azo-based dicarbole derivative is designed and synthesized, the corrole derivative is grafted at two ends of azobenzene, so that the azobenzene has both corrole property and photochromic performance of an azo compound, and the method is worthy of developing deeper and more effective research work in synthesis and application research, and has not been reported in the aspect.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide a preparation method of an azo-based dicarbole derivative.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the azo-based dicarbole derivative has the following structure:
the synthetic route of the azo-based dicarbole derivative provided by the invention is as follows:
the preparation process of the azo-based dicarbole derivative comprises the following steps:
under the protection of argon, dissolving a 5-p-borate phenyl corrole derivative and 4, 4' -diiodoazobenzene in tetrahydrofuran, adding a mixed solution of anhydrous sodium carbonate and water and methanol in a certain proportion into a reactor, finally adding a catalyst of tetrakis (triphenylphosphine) palladium, reacting at 75-85 ℃ for 12-16 hours, cooling to room temperature after the reaction is finished, adding a saturated ammonium chloride solution, extracting and separating with dichloromethane, evaporating an organic solvent to dryness, and separating and purifying by silica gel column chromatography to obtain the azo-based dicarbole derivative (I).
In the reaction, the mass ratio of the 5-p-borate phenyl corrole derivative to the 4, 4' -diiodoazobenzene is 2.0-2.5: 1;
in the above reaction, tetrakis (triphenylphosphine) palladium (Pd (PPh) is used as a catalyst3)4) The using amount of the catalyst is 10-20% of the amount of the reactant raw material substances;
in the reaction, the volume ratio of the methanol to the water is 1: 1-2.
The invention has the beneficial effects that:
compared with the prior art, the preparation method of the azo-based dicarbole derivative has the following advantages: (1) the azobenzene bridged bis-borate carbazole derivative is used for obtaining an azo-based bis-carbazole derivative, and can be used for photodynamic therapy and optical storage materials; (2) the method has the advantages of simple synthetic route, mild reaction conditions, good reaction selectivity, simple separation method and universality, and can be popularized and applied to the synthesis of a binary system of the azo-group bridged corrole derivative.
Drawings
FIG. 1 is a high resolution mass spectrum of azo-based dicarbole derivative (I);
FIG. 2 is a UV-VIS absorption spectrum of example 1 of the present invention;
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
ESI MASS and UV-Vis spectroscopy were used to characterize the structure of the compounds and to study the photophysical properties of the compounds. The detection instrument is as follows: the U.S. Thermo electric CORPORATION mass spectrometry workstation, Shimadzu UV-3100 model UV-visible spectrophotometer (scan range 400-800 nm, 2nm light path slit).
Example 1
Adding 5-p-borate phenyl carbazole derivative (0.22mmol) and 4, 4-diiodoazobenzene (0.09mmol) into a reactor, dissolving in tetrahydrofuran (8mL), weighing anhydrous sodium carbonate (1.57mmol), adding water and methanol (2mL/2mL) in proportion, adding tetrakis (triphenylphosphine) palladium (0.02mmol) into the reaction under the condition of argon, heating to reflux, reacting for 12h, extracting an organic phase with dichloromethane after the reaction is finished, washing with a saturated ammonium chloride aqueous solution, drying the organic layer with anhydrous sodium sulfate, decompressing, spin-drying the solvent, and separating and purifying by silica gel column chromatography with dichloromethane-petroleum ether as an eluent to obtain the azo-based dicarbole derivative (I) with the yield of 40%.1H NMR(CDCl3，400MHz，ppm)9.14-9.13(d，J＝3.2Hz，4H)， 8.82-8.74(m，8H)，8.59(s，4H)，8.33-8.31(d，J＝7.6Hz，4H)，8.25-8.23(d，J＝8Hz，4H)， 8.13-8.11(d，J＝7.2Hz，8H).
Example 2
Adding 5-p-borate phenyl carbazole derivative (0.18mmol) and 4, 4-diiodoazobenzene (0.09mmol) into a reactor, dissolving in tetrahydrofuran (8mL), weighing anhydrous sodium carbonate (1.57mmol), adding water and methanol (2mL/1mL) in proportion, adding tetrakis (triphenylphosphine) palladium (0.02mmol) into the reaction under the condition of argon, heating to reflux, reacting for 16h, extracting an organic phase with dichloromethane after the reaction is finished, washing with a saturated ammonium chloride aqueous solution, drying the organic layer with anhydrous sodium sulfate, decompressing, drying the solvent, and separating and purifying by silica gel column chromatography with dichloromethane-petroleum ether as an eluent to obtain the azo-based dicarbole derivative (I) with the yield of 37%.
Example 3
Adding 5-p-borate phenyl carbazole derivative (0.20mmol) and 4, 4-diiodoazobenzene (0.09mmol) into a reactor, dissolving in tetrahydrofuran (8mL), weighing anhydrous sodium carbonate (1.57mmol), adding water and methanol (2mL/2mL) in proportion, adding tetrakis (triphenylphosphine) palladium (0.04mmol) into the reaction under the condition of argon, heating to reflux, reacting for 14h, extracting an organic phase with dichloromethane after the reaction is finished, washing with a saturated ammonium chloride aqueous solution, drying the organic layer with anhydrous sodium sulfate, decompressing, drying the solvent, and separating and purifying by silica gel column chromatography with dichloromethane-petroleum ether as an eluent to obtain the azo-based dicarbole derivative (I) with the yield of 45%.
Claims (6)
1. An azo-based dicarbole derivative is characterized in that the chemical structure is shown as (I):
2. a method for preparing an azo-based biscarbazole derivative of formula (I) according to claim 1, said method comprising: the method comprises the following steps of (1) carrying out suzuki coupling reaction on a 5-p-borate phenyl corrole derivative and 4, 4' -diiodoazobenzene under the catalysis of tetrakis (triphenylphosphine) palladium to obtain an azo-based bicarbole derivative shown in a formula (I), wherein the reaction formula of the process is as follows:
3. the method of claim 2, wherein the method comprises:
under the condition of argon protection, dissolving a 5-p-borate phenyl corrole derivative and 4, 4' -diiodoazobenzene in tetrahydrofuran, adding a mixed solution of anhydrous sodium carbonate and water and methanol in a certain proportion into a reactor, finally quickly adding a catalyst of tetrakis (triphenylphosphine) palladium, reacting at 75-85 ℃ for 12-16 hours, cooling to room temperature after the reaction is finished, adding a saturated ammonium chloride solution, extracting and separating with dichloromethane, evaporating an organic solvent to dryness, and then separating and purifying through silica gel column chromatography to obtain the azo-based dicarbole derivative (I).
4. The method according to claim 3, wherein the ratio of the amount of the 5-p-boronate phenylcarbazole derivative to the amount of the compound of formula 4, 4-diiodoazobenzene in the reaction is 2.0 to 2.5: 1.
5. The preparation method according to claim 3, wherein in the reaction, the amount of the catalyst tetrakis (triphenylphosphine) palladium is 10-20% of the amount of the reactant raw material.
6. The method according to claim 3, wherein the volume ratio of methanol to water in the reaction is 1: 1-2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605440A (en) * | 2022-03-28 | 2022-06-10 | 南京林业大学 | Preparation method of carbazolyl gallium carbazole derivative and application of carbazolyl gallium carbazole derivative in photodynamic antibiosis and antitumor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976249A (en) * | 2017-12-29 | 2018-12-11 | 南京林业大学 | A kind of three polyindenes click coughs up-preparation method of the star-like compound of fullerene |
| CN109096313A (en) * | 2018-09-04 | 2018-12-28 | 南京林业大学 | A kind of trimeric indenyl click coughs up-preparation method of porphyrin-fullerene star-like compound |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976249A (en) * | 2017-12-29 | 2018-12-11 | 南京林业大学 | A kind of three polyindenes click coughs up-preparation method of the star-like compound of fullerene |
| CN109096313A (en) * | 2018-09-04 | 2018-12-28 | 南京林业大学 | A kind of trimeric indenyl click coughs up-preparation method of porphyrin-fullerene star-like compound |
Non-Patent Citations (5)
| Title |
|---|
| MANOJ KUMAR SINGH，等: "A new Organopalladium compound containing four Iron (III) Porphyrins for the selective oxidation of alkanes/alkenes by t-BuOOH", 《J. CHEM. SCI.》 * |
| NIKOLAOS LIAROS，等: "NLO Response of Photoswitchable Azobenzene-Based Materials", 《CHEMPHYSCHEM》 * |
| SHINJI TSUCHIYA: "Intramolecular Electron Transfer of Diporphyrins Comprised of Electron-Deficient Porphyrin and Electron-Rich Porphyrin with Photocontrolled Isomerization", 《J. AM. CHEM. SOC.》 * |
| TAKASHI YAMAMURA，等: "Synthesis and photochemical properties of porphyrin-azobenzene triad", 《TETRAHEDRON LETTERS》 * |
| YUANYUAN CHE，等: "Bodipy−Corrole dyad with truxene bridge: Photophysical Properties and Application in Triplet−Triplet Annihilation upconversion", 《DYES AND PIGMENTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605440A (en) * | 2022-03-28 | 2022-06-10 | 南京林业大学 | Preparation method of carbazolyl gallium carbazole derivative and application of carbazolyl gallium carbazole derivative in photodynamic antibiosis and antitumor |
| CN114605440B (en) * | 2022-03-28 | 2024-01-05 | 启林生物(江阴)有限公司 | Preparation method of carbazolyl gallium carbole derivative and application of carbazolyl gallium carbole derivative in photodynamic antibiosis and antitumor |
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