CN112876406A - Deuterated carbazole compound, preparation method thereof, photoelectric material and medicine - Google Patents
Deuterated carbazole compound, preparation method thereof, photoelectric material and medicine Download PDFInfo
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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Abstract
The application discloses a deuterated carbazole compound, a preparation method thereof and a photoelectric material, wherein the deuterated carbazole compound takes cheap deuterium as a deuterated raw material, and hydrogen and deuterium exchange reaction is directly carried out on the structure of the carbazole compound, so that the problems of complicated synthesis process and high cost of the deuterated carbazole compound are solved, and meanwhile, 1, 4-dioxane is taken as a solvent, expensive deuterated reagents are not used as the solvent, cheap fluorine-containing acid is taken as a catalyst, the expensive catalyst is not used, and the deuterated carbazole compound is cheap, efficient and pollution-free and can be suitable for industrial production.
Description
Technical Field
The application relates to the field of organic chemical synthesis, in particular to a deuterated carbazole compound and a preparation method thereof, a photoelectric material and a medicament.
Background
Because deuterium atoms replace hydrogen atoms in biological molecules or material molecules, the physical, chemical and biological properties of the original molecules can be obviously changed. Therefore, deuterated compounds are widely used in the fields of pharmaceutical science, material science, bioscience, nuclear science, food science, and organic matter identification.
In the field of medicine design, after hydrogen in medicine molecules is replaced by deuterium, the metabolic stability of the medicine molecules can be improved under the condition of not changing the targeting property of the medicine molecules. Therefore, the deuterium technology is considered as a shortcut for developing new drugs, and is favored by various large pharmaceutical companies. In 2017, the first example deuterium-substituted drug ausedo worldwide obtained approval from the U.S. Food and Drug Administration (FDA) for marketing. In the field of materials, the deuterated materials have lower internal energy compared with non-deuterated materials, and C-D bonds and C-H bonds have obviously smaller stretching vibration and bending vibration, so that the stability and the service life of the deuterated materials are remarkably improved due to the factors.
Carbazole compounds have been widely used in medicines, pesticides, dyes, photoelectric materials, and synthetic resins as common materials in organic chemistry.
In medicine, carbazochrome and non-steroidal drug carprofen are used as antibacterial drugs; ellipticine, pyrrolocarbazole derivatives, carbazole amide compounds, etc. have inhibitory effect on tumor cells; the novel carbazole drug midostaurin can be used for treating Acute Myeloid Leukemia (AML) positive for FLT3 mutation. In the photoelectric material, because a carbazole skeleton unit contains a larger pi electron conjugated system, the carbazole skeleton unit has strong electron transfer capacity and a condensed ring rigid skeleton structure, and thus, carbazole derivatives are widely used for constructing fluorescent molecular probes, sensors, light-emitting diodes and organic light-emitting electronic devices, and are widely used for constructing bipolar blue light materials in OLEDs.
Currently, in a synthesis method of a deuterated carbazole compound, a final product can be obtained through multiple synthesis steps. The synthesis method of the deuterated carbazole compound has various methods, and is illustrated by the following examples:
firstly, synthesizing a deuterated intermediate, and then carrying out reactions such as dehydrocyclization, coupling and the like to obtain deuterated carbazole; and secondly, adding a group on the deuterated aniline through other reaction methods to obtain the deuterated carbazole compound.
Second, in 2015, Chiharu Suzuki et al performed N-C coupling using deuterated o-aminobiphenyl as a raw material and an iridium catalyst to obtain deuterated carbazole.
Third, 2016, Wen Lixian et al used Pd (OAc)2、Cu(OAc)2As a catalyst, deuterated diphenylamine is used as a raw material to synthesize deuterated carbazole.
However, all three of the above methods must be synthesized through multiple steps, and deuteration does not occur in the last step, which greatly increases the cost of synthesizing deuterated carbazoles.
In order to simplify the synthesis steps, in the prior art, deuterium exchange is directly performed on carbazole compounds to prepare deuterated carbazoles, so that the synthesis steps of deuterated carbazole compounds are reduced. However, this method requires a large amount of expensive Pt catalyst and reacts at a high temperature of about 200 ℃, which greatly increases the synthesis cost and is not favorable for industrial production, and this method has poor group compatibility and a narrow range of substrates that can be prepared.
Disclosure of Invention
The invention aims to provide a deuterated carbazole compound, a preparation method thereof, a photoelectric material and a medicament, and aims to solve the technical problems of complex synthetic process, high production cost and poor group compatibility of the conventional deuterated carbazole compound.
In order to achieve the purpose, the invention provides a deuterated carbazole compound, which comprises the following raw material components of the carbazole compound, a fluoric acid catalyst, deuterium water and a 1, 4-dioxane solvent; wherein the carbazole-based compound: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
Further, the molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group.
Further, the carbazole-based compound is any one of carbazole, 3, 6-di-tert-butylcarbazole, 9-methylcarbazole, 2-methoxycarbazole, 2-chlorocarbazole, 9-phenylcarbazole, 3, 6-diphenylcarbazole, 9-isopropylcarbazole, 9-butylcarbazole, and 2-bromocarbazole.
Further, the fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
In order to achieve the above object, the present invention further provides a preparation method of a deuterated carbazole compound, comprising the following steps:
obtaining carbazole compounds, a fluoric acid catalyst, deuterium water and a 1, 4-dioxane solvent which are raw material components, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the mol ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10);
adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution;
heating the mixed solution;
after the mixed solution is completely reacted, adding a saturated ammonium chloride solution into the reactor for quenching;
and adding a dichloromethane solvent into the reactor, extracting, combining organic phases, and performing rotary evaporation and concentration to obtain the deuterated carbazole compound.
Further, in the step of performing the heating treatment on the mixed solution, the mixed solution is subjected to the heating treatment at the temperature of 100-120 ℃ for 11-13 hours, so that the mixed solution is fully reacted.
Further, in the step of adding a saturated ammonium chloride solution, 99 to 101ml of the saturated ammonium chloride solution is added to the reactor.
Further, in the step of adding a dichloromethane solvent, 99 to 101ml of the dichloromethane solvent is added to the reactor.
In order to achieve the above object, the present invention also provides a photovoltaic material, including the deuterated carbazole-based compound described above.
In order to achieve the above objects, the present invention also provides a medicament comprising the deuterated carbazole-based compound as described above.
The invention has the technical effects that the deuterium substituted carbazole compound takes cheap deuterium water as a deuterium substituted raw material, and the deuterium exchange reaction is directly carried out on the structure of the carbazole compound, so that the problems of complicated synthesis process and high cost of the deuterium substituted carbazole compound are solved, and meanwhile, the method takes 1, 4-dioxane as a solvent, avoids using expensive deuterium substituted reagent as the solvent, takes cheap fluoric acid as a catalyst, avoids using expensive catalyst, is cheap, efficient and pollution-free, and can be suitable for industrial production.
Drawings
The technical solution and other advantages of the present application will become apparent from the detailed description of the embodiments of the present application with reference to the accompanying drawings.
FIG. 1 is a nuclear magnetic diagram of a deuterated carbazole described in example 1 of the present application;
FIG. 2 is a nuclear magnetic diagram of deuterated 3, 6-di-tert-butylcarbazole described in example 2 herein;
FIG. 3 is a nuclear magnetic diagram of deuterated 9-methylcarbazole described in example 3 herein;
FIG. 4 is a nuclear magnetic diagram of deuterated 9-phenylcarbazole described in example 4 herein;
FIG. 5 is a nuclear magnetic diagram of deuterated 3, 6-diphenylcarbazole described in example 5 herein;
FIG. 6 is a nuclear magnetic diagram of deuterated 9-butylcarbazole described in example 6 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments. Additionally, in the description of the present application, various embodiments of the invention may exist in a range of versions; it is to be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges such as, for example, from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range such as, for example, 1, 2, 3, 4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the indicated range.
Example 1:
the embodiment provides a deuterated carbazole compound, which comprises components of a carbazole compound, a hydrofluoric acid catalyst, deuterium water and a 1, 4-dioxane solvent; wherein the carbazole-based compound: the fluoric acid catalyst: the deuterium water: the mol ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1): 20-40): 5-10)
Specifically, the molecular structural formula of the carbazole compound is as follows:
wherein, R1 is any one of hydrogen, methyl, vinyl and phenyl; and R2 and R3 are any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In this embodiment, the carbazole-based compound is carbazole.
The deuterium oxide is high deuterium oxide, and the deuterium substitution rate is 99.99%.
The concentration of the fluoric acid catalyst is anhydrous fluoric acid which is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
Therefore, the embodiment of the present application provides a deuterated carbazole compound, which uses cheap deuterium as a deuterated raw material, uses 1, 4-dioxane as a solvent, avoids using an expensive deuterated reagent as a solvent, uses cheap fluorine-containing acid as a catalyst, avoids using an expensive catalyst, improves and reduces production cost, and is suitable for large-scale production.
This embodiment also provides an optoelectronic material comprising the deuterated carbazole described above. The photoelectric material can be used for constructing fluorescent molecular probes, sensors, light-emitting diodes, organic light-emitting electronic devices and the like.
This example also provides a medicament comprising a deuterated carbazole as described above. The deuterated carbazole compound can improve the metabolic stability of drug molecules and can be widely applied to medicines.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S11) -S15).
S11) preparing and obtaining raw material components, including a carbazole compound, a fluoric acid catalyst, deuterium water and a 1, 4-dioxane solvent, wherein the carbazole compound: hydrofluoric acid catalyst: deuterium oxide: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the embodiments of the present application, the carbazole-based compound is carbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S12) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, 0.1mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the carbazole, and 5mol of the 1, 4-dioxane solvent are added into a 10mL reactor. In the examples of the present application, the reactor includes, but is not limited to, a reaction flask.
S13) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S14), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the saturated ammonium chloride solution, preferably 100ml of the saturated ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S15) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely deuterated carbazole, is obtained after treatment for 3 min. Wherein, the deuterated carbazole has 168mg, the yield is 95.4%, the deuteration rate is 95%, and the analytical purity is 99%.
As shown in fig. 1, fig. 1 is a nuclear magnetic diagram of deuterated carbazole described in example 1 of the present application. The aspects of nuclear magnetic spectrum appearance, signals, noise and the like of the deuterated carbazole can reflect that the deuterated carbazole has extremely high purity, no other organic impurities are generated in the preparation process, the step of purifying the product by column chromatography is omitted, and the production cost can be effectively reduced.
The embodiment provides a preparation method of a deuterated carbazole compound, which is characterized in that cheap deuterium water is used as a deuterated raw material, and hydrogen and deuterium exchange reaction is directly carried out on the structure of the carbazole compound, so that the problems of complicated synthesis process and high cost of the deuterated carbazole compound are solved, and meanwhile, 1, 4-dioxane is used as a solvent, an expensive deuterated reagent is not used as the solvent, cheap fluorine-containing acid is used as a catalyst, an expensive catalyst is not used, and the preparation method is cheap, efficient and pollution-free and is suitable for industrial production.
Example 2
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 3, 6-di-tert-butylcarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S21) -S25).
S21), obtaining carbazole compounds, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the embodiment of the application, the carbazole-based compound is 3, 6-di-tert-butyl carbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S22) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.08mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium oxide, 1mmol of the 3, 6-di-tert-butylcarbazole, and 5.2mol of the 1, 4-dioxane solvent are added. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S23) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S24), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S25) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely deuterated 3, 6-di-tert-butylcarbazole, is obtained after treatment for 3 min. Wherein, the deuterated 3, 6-di-tert-butylcarbazole is 271mg, the yield is 95%, the deuteration rate is 91%, and the analytical purity is 99%.
As shown in fig. 2, fig. 2 is a nuclear magnetic diagram of deuterated 3, 6-di-tert-butylcarbazole described in example 2 of the present application. The aspects of nuclear magnetic spectrum appearance, signals, noise and the like of the deuterated 3, 6-di-tert-butylcarbazole can reflect that the deuterated carbazole has extremely high purity, no other organic impurities are generated in the preparation process, the step of purifying the product by column chromatography is omitted, and the production cost can be effectively reduced.
Example 3
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 9-methylcarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S31) -S35).
S31), obtaining carbazole compounds, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the examples of the present application, the carbazole-based compound is 9-methylcarbazole。
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S32) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.06mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the 9-methylcarbazole, and 5.2mol of the 1, 4-dioxane solvent are added. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S33) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S34), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S35) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely the deuterated 9-methylcarbazole, is obtained after treatment for 3 min. Wherein, the deuterated 9-methylcarbazole has the yield of 90 percent, the deuterated rate of 95 percent and the analytical purity of 99 percent, wherein 170mg of deuterated 9-methylcarbazole has the advantages of high yield, high purity of 99 percent, and good stability.
As shown in fig. 3, fig. 3 is a nuclear magnetic diagram of deuterated 9-methylcarbazole described in example 3 of the present application. The aspects of nuclear magnetic spectrum appearance, signals, noise and the like of the deuterated 9-methylcarbazole can reflect that the deuterated carbazole has extremely high purity, no other organic impurities are generated in the preparation process, the step of purifying the product by column chromatography is omitted, and the production cost can be effectively reduced.
Example 4
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 9-phenylcarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S41) -S45).
S41), obtaining carbazole compounds, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the examples of the present application, the carbazole-based compound is 9-phenylcarbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S42) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.086mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the 9-phenylcarbazole, and 7mol of the 1, 4-dioxane solvent are added. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S43) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S44), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S45) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely the deuterated 9-phenylcarbazole, is obtained after treatment for 3 min. Wherein the deuterated 9-phenylcarbazole is 229mg, the yield is 91%, the deuteration rate is 95%, and the analytical purity is 99%.
As shown in fig. 4, fig. 4 is a nuclear magnetic diagram of deuterated 9-phenylcarbazole described in example 4 of the present application. The aspects of nuclear magnetic spectrum appearance, signals, noise and the like of the deuterated 9-phenylcarbazole can reflect that the deuterated carbazole has extremely high purity, no other organic impurities are generated in the preparation process, the step of purifying the product by column chromatography is omitted, and the production cost can be effectively reduced.
Example 5
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 3, 6-diphenylcarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S51) -S55).
S51), obtaining carbazole compounds, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the examples of the present application, the carbazole-based compound is 3, 6-diphenylcarbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S52) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.1mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium oxide, 1mmol of the 3, 6-diphenylcarbazole, and 7.3mol of the 1, 4-dioxane solvent are added. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S53) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S54), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S55) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely deuterated 3, 6-diphenylcarbazole, is obtained after treatment for 3 min. Wherein 309mg of the deuterated 3, 6-diphenylcarbazole is obtained, the yield is 95%, the deuteration rate is 97%, and the analytical purity is 99%.
As shown in fig. 5, fig. 5 is a nuclear magnetic diagram of deuterated 3, 6-diphenylcarbazole described in example 5 of the present application. The aspects of nuclear magnetic spectrum appearance, signals, noise and the like of the deuterated 3, 6-diphenylcarbazole can reflect that the deuterated 3, 6-diphenylcarbazole has extremely high purity, no other organic impurities are generated in the preparation process, the step of purifying the product by column chromatography is omitted, and the production cost can be effectively reduced.
Example 6
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 9-butylcarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S61) -S65).
S61), obtaining carbazole compounds, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the examples of the present application, the carbazole-based compound is 9-butylcarbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S62) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.076mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the 9-butylcarbazole, and 6.6mol of the 1, 4-dioxane solvent were added. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S63) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S64), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S65) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely the deuterated 9-butylcarbazole, is obtained after treatment for 3 min. Wherein, the deuterated 9-butyl carbazole is 206mg, the yield is 95%, the deuterated rate is 95%, and the analytical purity is 99%.
As shown in fig. 6, fig. 6 is a nuclear magnetic diagram of deuterated 9-butylcarbazole described in example 6 of the present application. The aspects of nuclear magnetic spectrum appearance, signals, noise and the like of the deuterated 9-butyl carbazole can reflect that the deuterated 9-butyl carbazole has extremely high purity, no other organic impurities are generated in the preparation process, the step of purifying the product by column chromatography is omitted, and the production cost can be effectively reduced.
Example 7
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 2-bromocarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S71) -S75).
S71), obtaining carbazole compounds, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1In the hydrogen, methyl, vinyl, phenyl groupsEither one of them; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the examples of the present application, the carbazole-based compound is 2-bromocarbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S72) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.98mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the 2-bromocarbazole, and 9.5mol of the 1, 4-dioxane solvent are added. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S73) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S74), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S75) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely the deuterated 2-bromocarbazole, is obtained after treatment for 3 min. Wherein, the deuterated 2-bromocarbazole is 236mg, the yield is 93%, the deuteration rate is 97%, and the analytical purity is 99%.
Example 8
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 2-methoxy carbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S81) -S85).
S81) preparing and obtaining raw material components, including a carbazole compound, a fluoric acid catalyst, deuterium water and a 1, 4-dioxane solvent, wherein the carbazole compound: hydrofluoric acid catalyst: deuterium oxide: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the embodiments of the present application, the carbazole-based compound is 2-methoxycarbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S82) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.1mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the 2-methoxycarbazole, and 5.6mol of the 1, 4-dioxane solvent are added. In the examples of the present application, the reactor includes, but is not limited to, a reaction flask.
S83) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S84), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the saturated ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S85) adding a saturated dichloromethane solvent into the reactor, extracting, combining organic phases, and performing rotary evaporation and concentration to obtain the deuterated carbazole compound.
Specifically, 99 to 101ml of the saturated methylene chloride solvent, preferably 100ml of the methylene chloride solvent, is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely the deuterated 2-methoxy carbazole, is obtained after treatment for 3 min. Wherein, the deuterated 2-methoxy carbazole is 184mg, the yield is 90%, the deuteration rate is 96%, and the analytical purity is 99%.
Example 9
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 2-chlorocarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S91) -S95).
S91), obtaining carbazole compounds, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the examples of the present application, the carbazole-based compound is 2-chlorocarbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S92) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, to 10mL of the reactor, 0.078mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the 2-chlorocarbazole, and 8mol of the 1, 4-dioxane solvent are added. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S93) heat-treating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S94), adding saturated ammonium chloride solution into the reactor and quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the saturated ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S95) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, and a rotary evaporator is used for processing for 3min at the rotating speed of 120rpm, the temperature of 37 ℃ and the vacuum degree of 0.1MPa to obtain the deuterated carbazole compound (not shown in the figure). Wherein 187mg of deuterated 2-chlorocarbazole is obtained, the yield is 90%, the deuteration rate is 97%, and the analytical purity is 99%.
Example 10
The embodiment provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, which include most technical solutions of embodiment 1, and are different in that the carbazole compound is 9-isopropylcarbazole.
The embodiment of the application also provides a preparation method of the deuterated carbazole compound, which comprises the following steps of S101) to S105).
S101) obtaining carbazole compounds, a fluoric acid catalyst, deuterium water and a 1, 4-dioxane solvent, wherein the carbazole compounds: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
The molecular structural formula of the carbazole compound is as follows:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl; the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group. In the examples of the present application, the carbazole-based compound is 9-isopropylcarbazole.
The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
S102) adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution.
Specifically, 0.9mmol of the fluoric acid catalyst, 0.44g, 22mmol of the deuterium water, 1mmol of the 9-isopropylcarbazole, and 9mol of the 1, 4-dioxane solvent are added into a 10mL reactor. In the embodiments of the present application, the reaction solution includes, but is not limited to, a reaction flask.
S103) heating the mixed solution.
Specifically, the mixed solution is heated for 11-13 hours at the temperature of 100-120 ℃ so that the mixed solution is fully reacted.
S104) adding saturated ammonium chloride solution into the reactor for quenching after the mixed solution completely reacts.
Specifically, 99 to 101ml of the ammonium chloride solution, preferably 100ml of the ammonium chloride solution, is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.
S105) adding a dichloromethane solvent into the reactor, and obtaining the deuterated carbazole compound after extraction, organic phase combination and rotary evaporation concentration.
Specifically, 99 to 101ml of the dichloromethane solvent, preferably 100ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used for extraction for three to four times, organic phases extracted for several times are combined into a 250ml eggplant-shaped bottle, a rotary evaporator is used, the rotating speed is 120rpm, the temperature is 37 ℃, the vacuum degree is 0.1Mpa, and the deuterated carbazole compound, namely deuterated 9-isopropylcarbazole, is obtained after treatment for 3 min. Wherein, the deuterated 9-isopropylcarbazole is 206mg, the yield is 95%, the deuterated rate is 95%, and the analytical purity is 99%.
| Examples | Carbazole-based compound | Yield of deuterated carbazole compounds | Deuteration rate of deuterated carbazole compound |
| 1 | Carbazole | 95.40％ | 95％ |
| 2 | 3, 6-di-tert-butylcarbazole | 95％ | 91％ |
| 3 | 9-methylcarbazole | 90％ | 95％ |
| 4 | 9-phenylcarbazoles | 91％ | 95％ |
| 5 | 3, 6-diphenylcarbazole | 95％ | 97％ |
| 6 | 9-butylcarbazole | 95％ | 95％ |
| 7 | 2-bromocarbazole | 93％ | 97％ |
| 8 | 2-methoxy carbazole | 90％ | 96％ |
| 9 | 2-chlorocarbazole | 90％ | 97％ |
| 10 | 9-isopropylcarbazole | 95％ | 95％ |
Watch (1)
The above embodiments provide a deuterated carbazole compound, a preparation method thereof, and a photoelectric material, wherein deuterium water with low price is used as a deuterated raw material, and hydrogen and deuterium exchange reaction is directly performed on the structure of the carbazole compound. As shown in table (1), the substrate of the deuterated carbazole-based compound (carbazole-based compound) may be any one of carbazole, 3, 6-di-tert-butylcarbazole, 9-methylcarbazole, 2-methoxycarbazole, 2-chlorocarbazole, 9-phenylcarbazole, 3, 6-diphenylcarbazole, 9-isopropylcarbazole, 9-butylcarbazole, and 2-bromocarbazole.
As can be seen from the above table, when the substrate (carbazole compound) of the deuterated carbazole compound is any one of carbazole, 3, 6-di-tert-butylcarbazole, 9-methylcarbazole, 2-methoxycarbazole, 2-chlorocarbazole, 9-phenylcarbazole, 3, 6-diphenylcarbazole, 9-isopropylcarbazole, 9-butylcarbazole, and 2-bromocarbazole, the yield of the deuterated carbazole compound is 90% or more, and the deuteration ratio of the deuterated carbazole compound is 91% or more. Therefore, the embodiment of the application provides a preparation method of a deuterated carbazole compound, solves the technical problems of complex synthesis process, high production cost and poor group compatibility of the existing deuterated carbazole compound, and has high yield and high deuteration rate.
The embodiment of the application provides a deuterated carbazole compound, a preparation method thereof and a photoelectric material, wherein the deuterated carbazole compound takes cheap deuterium as a deuterated raw material, and hydrogen and deuterium exchange reaction is directly carried out on the structure of the carbazole compound, so that the problems of complicated synthesis process and high cost of the deuterated carbazole compound are solved, and meanwhile, the method takes 1, 4-dioxane as a solvent, avoids using an expensive deuterated reagent as a solvent, takes cheap fluorine-containing acid as a catalyst, avoids using an expensive catalyst, is cheap, efficient and pollution-free, and can be suitable for industrial production.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The deuterated carbazole compound, the preparation method thereof and the photoelectric material provided by the embodiment of the application are described in detail, a specific example is applied to illustrate the principle and the implementation mode of the application, and the description of the embodiment is only used for helping to understand the technical scheme and the core concept of the application; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.
Claims (10)
1. The deuterated carbazole compound is characterized by comprising the following raw material components: carbazole compounds, a fluoric acid catalyst, deuterium water and a 1, 4-dioxane solvent;
wherein the carbazole-based compound: the fluoric acid catalyst: the deuterium water: the molar ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10).
2. The deuterated carbazole compound according to claim 1, wherein the carbazole compound has a molecular structural formula:
wherein, R is1Is any one of hydrogen, methyl, vinyl and phenyl;
the R is2、R3Any one of ester group, cyano group, carbonyl group, hydroxyl group, alkoxy group, alkyl group, tert-butyl group, bromine, chlorine, fluorine, iodine, amide, amino group, borate ester, alkynyl group, alkenyl group, phenyl group and heterocyclic aryl group.
3. The deuterated carbazole-based compound according to claim 1, wherein the carbazole-based compound is any one of carbazole, 3, 6-di-tert-butylcarbazole, 9-methylcarbazole, 2-methoxycarbazole, 2-chlorocarbazole, 9-phenylcarbazole, 3, 6-diphenylcarbazole, 9-isopropylcarbazole, 9-butylcarbazole, and 2-bromocarbazole.
4. The deuterated carbazole-based compound according to claim 1,
the fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid and pentafluoropropionic acid.
5. A preparation method of a deuterated carbazole compound is characterized by comprising the following steps:
obtaining raw material components including a carbazole compound, a fluoric acid catalyst, deuterium oxide and a 1, 4-dioxane solvent, wherein the carbazole compound: the fluoric acid catalyst: the deuterium water: the mol ratio of the 1, 4-dioxane solvent is 1 (0.05-0.1) to (20-40) to (5-10);
adding the fluoric acid catalyst, the deuterium water, the carbazole compound and the 1, 4-dioxane solvent into a reactor to obtain a mixed solution;
heating the mixed solution;
after the mixed solution is completely reacted, adding a saturated ammonium chloride solution into the reactor for quenching;
and adding a dichloromethane solvent into the reactor, extracting, combining organic phases, and performing rotary evaporation and concentration to obtain the deuterated carbazole compound.
6. The method for preparing deuterated carbazole-based compound according to claim 5,
in the step of performing the heat treatment on the mixed solution,
and heating the mixed solution at the temperature of 100-120 ℃ for 11-13 hours to fully react the mixed solution.
7. The method of claim 5, wherein in the step of adding the saturated ammonium chloride solution, 99-101ml of the saturated ammonium chloride solution is added to the reactor.
8. The method of preparing a deuterated carbazole-based compound according to claim 5, wherein in the step of adding a dichloromethane solvent, 99 to 101ml of the dichloromethane solvent is added to the reactor.
9. An optoelectronic material comprising the deuterated carbazole-based compound according to any one of claims 1 to 4.
10. A medicament comprising the deuterated carbazole-based compound according to any one of claims 1 to 4.
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