Process for the preparation of deuterated aromatic compounds and deuterated reaction compositions

Abstract

The present specification relates to methods and deuterated reaction compositions for producing deuterated aromatic compounds.

Description

Technical Field

[0001] This application claims priority and benefit to Korean Patent Application Nos. 10-2020-0108192 and 10-2020-0178795, filed with the Korean Intellectual Property Office on August 27, 2020 and December 18, 2020, respectively, the entire contents of which are incorporated herein by reference.

[0002] This specification relates to methods for producing deuterated aromatic compounds and deuteration reaction compositions. Background Technology

[0003] Compounds containing deuterium are used for a variety of purposes. For example, compounds containing deuterium are frequently used not only as labeling compounds to explain the mechanisms of chemical reactions or to illustrate metabolism, but also in pharmaceuticals, pesticides, organic EL materials, and other purposes.

[0004] To improve the lifetime of organic light-emitting device (OLED) materials, deuterium substitution of aromatic compounds is known. The principle behind this effect is that the lifetime characteristics of OLED materials are improved when the LUMO energy of the CD bond is lower than that of the CH bond during deuterium substitution.

[0005] When using existing heterogeneous catalytic reactions to deuterate one or more aromatic compounds, there is a persistent problem of byproducts arising from side reactions. These byproducts are generated by hydrogenation reactions produced by hydrogen gas, and attempts have been made to improve purity through post-reaction purification processes to remove them, but achieving high purity is difficult because the materials do not differ from existing materials in terms of melting point and solubility. When attempting to mitigate this problem by carrying out the reaction without hydrogen gas, the reaction needs to be conducted at very high temperatures (approximately 220°C or higher), which could pose safety risks during the process. Summary of the Invention

[0006] Technical issues

[0007] This specification aims to provide methods for producing deuterated aromatic compounds and deuteration reaction compositions.

[0008] Technical solution

[0009] This specification provides a method for producing deuterated aromatic compounds, the method comprising: carrying out a deuteration reaction of the aromatic compound using a solution containing heavy water, an organic compound that can be hydrolyzed by heavy water, an aromatic compound containing one or more hydrocarbon aromatic rings, and an organic solvent.

[0010] In the method for producing deuterated aromatic compounds described in this specification, the deuteration reaction of the aromatic compounds includes:

[0011] The preparation of a solution comprising an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water, an organic compound that can be hydrolyzed by heavy water, and an organic solvent; and the deuteration of the aromatic compound by heating the solution used for the deuteration reaction.

[0012] In the method for producing deuterated aromatic compounds described in this specification, the organic compounds that can be hydrolyzed by heavy water include at least one compound of the following chemical formulas 1 to 4.

[0013] [Chemical Formula 1]

[0014] R1-C(O)OC(O)-R2

[0015] [Chemical Formula 2]

[0016] R3-S(O2)OS(O2)-R4

[0017] [Chemical Formula 3]

[0018] R5-C(O)O-R6

[0019] [Chemical Formula 4]

[0020] R7-CONH-R8

[0021] In chemical formulas 1 to 4, R1 to R8 may be the same or different from each other, and each is an unsubstituted or halogenated monovalent organic group.

[0022] In the method for producing deuterated aromatic compounds described in this specification, the organic compounds that can be hydrolyzed by heavy water include at least one of the following: trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, methanesulfonic anhydride, methyl acetate, ethyl acetate, and dimethylacetamide.

[0023] In addition, this specification provides deuteration reaction compositions comprising an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water, an organic compound that can be hydrolyzed by heavy water, and an organic solvent.

[0024] In the methods or deuteration reaction compositions for producing deuterated aromatic compounds described in this specification, the organic solvent is selected from unsubstituted or substituted chain hydrocarbons with groups selected from alkyl and halogen groups; unsubstituted or substituted aliphatic cyclic hydrocarbons with groups selected from alkyl and halogen groups; unsubstituted or substituted aromatic cyclic hydrocarbons with groups selected from alkyl and halogen groups; unsubstituted or substituted olefin compounds with groups selected from alkyl and halogen groups; straight-chain or branched heterochain hydrocarbons; substituted or unsubstituted aliphatic heterocyclic hydrocarbons; and substituted or unsubstituted aromatic heterocyclic hydrocarbons.

[0025] In the methods or deuteration reaction compositions for producing deuterated aromatic compounds described in this specification, the organic solvent is selected from cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dicyclohexane, etc. Alkane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decahydronaphthalene, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene.

[0026] In addition, this specification provides deuterated aromatic compounds prepared by the above method.

[0027] The deuterated aromatic compounds described in this specification contain substituents selected from leaving groups, hydroxyl groups, substituted or unsubstituted amine groups, and cyano groups.

[0028] In the deuterated aromatic compounds described in this specification, the leaving group may be selected from halogen groups and borate groups.

[0029] In the deuterated aromatic compounds described in this specification, the deuterated aromatic compounds containing substituents selected from leaving groups, hydroxyl groups, substituted or unsubstituted amino groups, and cyano groups can be any of the chemical formulas 7 to 10:

[0030] [Chemical Formula 7]

[0031]

[0032] [Chemical Formula 8]

[0033]

[0034] [Chemical Formula 9]

[0035]

[0036] [Chemical Formula 10]

[0037]

[0038] In chemical formulas 7 to 10,

[0039] At least one of A1 to A12 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings,

[0040] At least one of B1 to B10 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings,

[0041] At least one of Y1 to Y10 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or group that can be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings, and

[0042] At least one of Z1 to Z8 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings.

[0043] In addition, this specification provides electronic devices comprising the aforementioned deuterated aromatic compounds.

[0044] Beneficial effects

[0045] The production method according to the first exemplary embodiment of this specification has the advantage of not producing impurities due to hydrogen.

[0046] The production method according to the second exemplary embodiment of this specification has the advantage of a high deuterium substitution rate.

[0047] The production method according to the third exemplary embodiment of this specification has the advantage of obtaining compounds with high purity.

[0048] The production method according to the fourth exemplary embodiment of this specification enables the deuteration reaction to be carried out at lower pressure.

[0049] The production method according to the fifth exemplary embodiment of this specification enables the deuteration reaction to be carried out at a lower temperature. Detailed Implementation

[0050] This instruction manual will be described in detail below.

[0051] This specification provides a method for producing deuterated aromatic compounds, the method comprising: carrying out a deuteration reaction of the aromatic compound using a solution containing heavy water, an organic compound that can be hydrolyzed by heavy water, an aromatic compound containing one or more hydrocarbon aromatic rings, and an organic solvent.

[0052] The method for producing deuterated aromatic compounds described in this specification is characterized by the absence of a hydrogen supply step.

[0053] In related technologies, hydrogen is supplied to activate a metal catalyst (which is a heterogeneous catalyst added to produce deuterated aromatic compounds). When the deuteration reaction is carried out by supplying hydrogen, the hydrogen undergoes a hydrogenation reaction, and byproducts are thus generated through side reactions.

[0054] To remove the generated byproducts, a purification process is required after the reaction to improve the purity. However, even after the purification process described above, the byproducts do not differ from the target material in terms of melting point and solubility, making it difficult to produce high-purity deuterated aromatic compounds.

[0055] The method for producing deuterated aromatic compounds described in this specification has the advantage of not producing impurities due to hydrogen gas, because it eliminates the need to supply metal catalysts and hydrogen gas for activating metal catalysts by using organic compounds that can be hydrolyzed by heavy water instead of heterogeneous metal catalysts.

[0056] Meanwhile, when a metal catalyst is used during the deuteration reaction, the metal catalyst reacts with the reactive groups (i.e., halogen groups, amino groups, hydroxyl groups, cyano groups, etc.) of the compound to be deuterated, so that in the deuteration reaction using a metal catalyst, the compound to be deuterated is limited to compounds that do not have reactive groups that can react with the metal catalyst or have reactive groups with low reactivity.

[0057] Since the method for producing deuterated aromatic compounds described in this specification uses an organic compound that can be hydrolyzed by heavy water instead of a heterogeneous metal catalyst, compounds having reactive groups such as halogen groups, amino groups, hydroxyl groups, and cyano groups can also be selected as the compounds to be deuterated. Specifically, after the compound, which is an intermediate having reactive groups such as halogen groups, amino groups, hydroxyl groups, and cyano groups, is deuterated, a reaction can be carried out to replace the reactive groups with other aromatic substituents.

[0058] The production method according to this specification has the advantage of a high deuterium substitution rate.

[0059] The production method according to this specification has the advantage of yielding compounds with high purity.

[0060] The production method according to this specification enables the deuteration reaction to be carried out under relatively low pressure.

[0061] The production method according to this specification enables the deuteration reaction to be carried out at a relatively low temperature.

[0062] The method for producing deuterated aromatic compounds described in this specification includes: preparing a solution comprising an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water (D2O), an organic compound that can be hydrolyzed by heavy water, and an organic solvent.

[0063] A solution comprising an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water (D2O), an organic compound that can be hydrolyzed by heavy water, and an organic solvent can be prepared by introducing the solution comprising the aromatic compound containing one or more hydrocarbon aromatic rings, heavy water (D2O), an organic compound that can be hydrolyzed by heavy water, and an organic solvent into a reactor, or by introducing the aromatic compound containing one or more hydrocarbon aromatic rings, heavy water (D2O), an organic compound that can be hydrolyzed by heavy water, and an organic solvent into the reactor separately.

[0064] In one exemplary embodiment of this specification, there are no particular limitations on the organic compounds that can be hydrolyzed by heavy water, as long as the organic compound has a reactive group that can be hydrolyzed by heavy water, and the organic compound may include at least one compound of, for example, the following chemical formulas 1 to 4.

[0065] [Chemical Formula 1]

[0066] R1-C(O)OC(O)-R2

[0067] [Chemical Formula 2]

[0068] R3-S(O2)OS(O2)-R4

[0069] [Chemical Formula 3]

[0070] R5-C(O)O-R6

[0071] [Chemical Formula 4]

[0072] R7-CONH-R8

[0073] In chemical formulas 1 to 4, R1 to R8 may be the same or different from each other, and each is an unsubstituted or halogenated monovalent organic group.

[0074] In one exemplary embodiment of this specification, R1 and R2 may be the same substituent.

[0075] In one exemplary embodiment of this specification, R3 and R4 may be the same substituent.

[0076] In one exemplary embodiment of this specification, R5 and R6 may be the same substituent.

[0077] In one exemplary embodiment of this specification, R7 and R8 may be the same substituent.

[0078] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be an unsubstituted or halogenated alkyl group; or an unsubstituted or halogenated aryl group.

[0079] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be an alkyl group having 1 to 30 carbon atoms that is unsubstituted or substituted with a halogen group; or an aryl group having 6 to 50 carbon atoms that is unsubstituted or substituted with a halogen group.

[0080] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be an alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with a halogen group; or an aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with a halogen group.

[0081] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be an alkyl group having 1 to 10 carbon atoms that is either unsubstituted or substituted with a halogen group.

[0082] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be an alkyl group having 1 to 5 carbon atoms that is either unsubstituted or substituted with a halogen group.

[0083] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be a substituent of the following chemical formula 5 or 6 independently.

[0084] [Chemical Formula 5]

[0085] -(CH2) l (CF2) m (CF3) n (CH3) l-n

[0086] [Chemical Formula 6]

[0087] -C(H) a ((CH2) l (CF2) mCF3) 3-a

[0088] In chemical formulas 5 and 6, l and m are each integers from 0 to 10, and n and a are each 0 or 1.

[0089] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be a substituent of chemical formula 5 independently.

[0090] In one exemplary embodiment of this specification, R1 to R8 may be the same as or different from each other, and may each be independently -CF3, -CH2CH3 or -CH3.

[0091] In the method for producing deuterated aromatic compounds described in this specification, the organic compounds that can be hydrolyzed by heavy water include at least one of the following: trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, methanesulfonic anhydride, methyl acetate, ethyl acetate, and dimethylacetamide.

[0092] In one exemplary embodiment of this specification, the organic compound that can be hydrolyzed by heavy water may include trifluoromethanesulfonic anhydride.

[0093] In one exemplary embodiment of this specification, the organic compound that can be hydrolyzed by heavy water may include trifluoroacetic anhydride.

[0094] In one exemplary embodiment of this specification, the organic compound that can be hydrolyzed by heavy water may include acetic anhydride.

[0095] In one exemplary embodiment of this specification, the organic compound that can be hydrolyzed by heavy water may include methanesulfonic anhydride.

[0096] In one exemplary embodiment of this specification, the organic compounds that can be hydrolyzed by heavy water may include trifluoromethanesulfonic anhydride and trifluoroacetic anhydride.

[0097] In one exemplary embodiment of this specification, the organic compounds that can be hydrolyzed by heavy water may include trifluoromethanesulfonic anhydride and acetic anhydride.

[0098] In one exemplary embodiment of this specification, the organic compounds that can be hydrolyzed by heavy water may include methanesulfonic anhydride and trifluoroacetic anhydride.

[0099] In one exemplary embodiment of this specification, the organic compounds that can be hydrolyzed by heavy water may include methanesulfonic anhydride and acetic anhydride.

[0100] In one exemplary embodiment of this specification, the organic compound that can be hydrolyzed by heavy water may include at least one of a compound of formula 1 and a compound of formula 2. When at least one of a compound of formula 1 and a compound of formula 2 is introduced into heavy water, hydrolysis by heavy water readily occurs even at room temperature.

[0101] In one exemplary embodiment of this specification, the organic compound that can be hydrolyzed by heavy water includes at least one of compounds of formula 1 and formula 2, and may also include at least one of compounds of formula 3 and formula 4. When the organic compound that can be hydrolyzed by heavy water includes at least one of compounds of formula 1 and formula 2, the temperature generated due to the hydrolysis reaction (which is an exothermic reaction) can be controlled by adding at least one of compounds of formula 3 and formula 4, which have a relatively slow hydrolysis reaction.

[0102] In one exemplary embodiment of this specification, when the organic compound that can be hydrolyzed by heavy water includes at least one of compounds of formula 3 and formula 4, the organic compound may also include at least one of compounds of formula 1 and formula 2. The hydrolysis reaction can be accelerated by adding compounds of formula 1 and formula 2, in which the hydrolysis reaction is relatively easy to occur.

[0103] In one exemplary embodiment of this specification, the organic compound that can be hydrolyzed by heavy water includes at least one of trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, and methanesulfonic anhydride, and may also include at least one of methyl acetate, ethyl acetate, and dimethylacetamide.

[0104] In one exemplary embodiment of this specification, in an organic compound that can be hydrolyzed by heavy water, the weight ratio of at least one of the compounds of formula 3 and formula 4 to at least one of the compounds of formula 1 and formula 2 can be 100:0 to 0:100, 99:1 to 0:100, 90:10 to 0:100, 80:20 to 0:100, 70:30 to 0:100, 60:40 to 0:100, 50:50 to 0:100, 40:60 to 0:100, 30:70 to 0:100, 20:80 to 0:100, or 10:90 to 0:100.

[0105] According to one exemplary embodiment of this specification, the content of organic compounds that can be hydrolyzed by heavy water can be 1 mol% or more and 100 mol% or less, based on the molar amount of heavy water. Specifically, according to one exemplary embodiment of this specification, the content of organic compounds that can be hydrolyzed by heavy water is no greater than the molar equivalent of heavy water and is adjusted according to the target material. In this case, there is the advantage of increasing the affinity between immiscible aromatic compounds and heavy water and enhancing deuterium substitution reactivity.

[0106] According to an exemplary embodiment of this specification, based on the weight of the aromatic compound containing one or more hydrocarbon aromatic rings, as described below, the content of the organic solvent can be 1 to 40 times, specifically 3 to 15 times, the content of the aromatic compound. In this case, the temperature of the entire process can be controlled and the reaction time can be shortened.

[0107] In the method for producing deuterated aromatic compounds described in this specification, the deuteration reaction of the aromatic compounds includes:

[0108] Preparation of a solution comprising an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water, an organic compound that can be hydrolyzed by heavy water, and an organic solvent; and

[0109] The deuteration reaction of aromatic compounds is carried out by heating the solution.

[0110] According to one exemplary embodiment of this specification, the content of aromatic compounds can be 3 times or more and 100 times or less, based on the molar number of organic compounds that can be hydrolyzed. In this case, there is an advantage that deuterium can be effectively replaced from organic compounds that can be hydrolyzed by heavy water.

[0111] According to one exemplary embodiment of this specification, the content of heavy water can be 0.1 times or more and 30 times or less the weight of the aromatic compound. In this case, there is an advantage that deuterium can be effectively displaced from the heavy water.

[0112] According to one exemplary embodiment of this specification, the solution used for the deuteration reaction may contain an additional deuterium source. This additional deuterium source may be a deuterated aromatic solvent, such as benzene-d6, toluene-d8, etc.

[0113] According to one exemplary embodiment of this specification, the content of the additional deuterium source can be 0.1 times or more and 30 times or less the weight of the aromatic compound. In this case, there is the advantage of enhancing reactivity and reducing heat generation during the reaction.

[0114] In the method for producing deuterated aromatic compounds described in this specification, the solution used for the deuteration reaction also contains an organic solvent. There are no particular limitations on the organic solvent, as long as it can dissolve the aromatic compound, and the organic solvent can be selected according to the aromatic compound used.

[0115] In one exemplary embodiment of this specification, a reaction can also be carried out in one phase using an organic solvent miscible with heavy water, and the phase can be separated into two phases at the interface by using an organic solvent immiscible with heavy water as the organic solvent for the deuteration reaction.

[0116] Specifically, in the case of a single-phase reaction, an excess of the organic compound needs to be hydrolyzed to maintain a suitable concentration of the fully hydrolyzed organic compound. In the case of a two-phase reaction, however, the amount of hydrolyzable organic compound can be reduced to maintain a suitable concentration of the hydrolyzable organic compound. Thus, in the case of a two-phase reaction, the amount of hydrolyzable organic compound can be reduced, which can lead to an increase in the purity of the deuterium substitution rate.

[0117] When aromatic compounds contain a high amount of hydrogen, excess heavy water is required to increase the deuteration rate. However, when the deuteration reaction occurs in one phase, the solubility of the aromatic compound deteriorates due to the excess heavy water, making it highly likely that the reactants will precipitate during, before, or after the reaction. In contrast, when the deuteration reaction occurs in two phases, the aromatic compound dissolves in the organic solvent, and the heavy water and hydrolyzed organic compound coexist as they are separated into aqueous layers. This allows for increased deuteration rates of the aromatic compound during the reaction without precipitation problems, even with the use of excess heavy water, in the two-phase case.

[0118] When no organic solvent is used, if a certain concentration or more of deuterium-containing hydrolyzed organic compounds are produced by the hydrolysis reaction of hydrolyzable organic compounds, the deuterium-containing hydrolyzed organic compounds cause heavy water and aromatic compounds, which are the target materials, to mix with each other, making it very likely that a deuterium substitution reaction will occur.

[0119] However, since the organic compounds hydrolyzed by heavy water are themselves superacids, an increase in the concentration of hydrolyzed organic compounds tends to cause side reactions, thereby reducing purity. Furthermore, in terms of stability, handling solutions containing large amounts of hydrolyzed organic compounds during post-reaction processing can also be dangerous.

[0120] In contrast, when using organic solvents, the amount of organic compounds that can be hydrolyzed by heavy water can be reduced by about 30% to 90% compared to deuteration reactions without organic solvents, resulting in improved purity and stability.

[0121] When no organic solvent is used, the concentration of deuterated trifluoromethanesulfonic acid, formed by the hydrolysis of trifluoromethanesulfonic anhydride (an organic compound that can be hydrolyzed by heavy water), increases, making it very likely that a deuteration substitution reaction will occur.

[0122] However, since trifluoromethanesulfonic acid is a superacid, increasing its concentration tends to cause side reactions, thereby reducing its purity. Furthermore, handling solutions containing large amounts of trifluoromethanesulfonic acid during post-reaction processing can be dangerous in terms of stability.

[0123] In contrast, when organic solvents are used together, the amount of trifluoromethanesulfonic anhydride used can be reduced by about 30% to 90% compared to existing quantities, which allows for improved purity and stability.

[0124] In the method for producing deuterated aromatic compounds described in this specification, the organic solvent is selected from unsubstituted or substituted chain hydrocarbons with groups selected from alkyl and halogen groups; unsubstituted or substituted aliphatic cyclic hydrocarbons with groups selected from alkyl and halogen groups; unsubstituted or substituted aromatic cyclic hydrocarbons with groups selected from alkyl and halogen groups; unsubstituted or substituted olefin compounds with groups selected from alkyl and halogen groups; straight-chain or branched heterochain hydrocarbons; substituted or unsubstituted aliphatic heterocyclic hydrocarbons; and substituted or unsubstituted aromatic heterocyclic hydrocarbons.

[0125] In one exemplary embodiment of this specification, the organic solvent is selected from unsubstituted or halogen-substituted alkyl groups; unsubstituted or alkyl-substituted monocyclic or polycyclic cycloalkyl groups; unsubstituted or alkyl-substituted benzene rings; substituted or unsubstituted alkyl acetates; alkyl ketones; alkyl sulfoxides; lactones having 4 to 10 carbon atoms; alkylamides; diols having 4 to 10 carbon atoms; and diols. Alkane; alkyl ether; unsubstituted or alkoxylated acetic acid.

[0126] In the method for producing deuterated aromatic compounds described in this specification, the organic solvent is selected from cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dicyclohexane, etc. Alkane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decahydronaphthalene, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene.

[0127] When the organic solvent content is too high, the deuterium substitution rate decreases; conversely, when the organic solvent content is too low, the reactants cannot dissolve well, and therefore the deuterium substitution rate decreases. Preferably, the mass ratio of organic solvent can be from 2 to 40 times, specifically from 3 to 16 times, based on the mass of the aromatic compound.

[0128] According to an exemplary embodiment of this specification, the solution is characterized by the fact that it does not contain a metal catalyst and can be replaced by an organic compound obtained by hydrolysis of heavy water. Thus, problems arising from the addition of a metal catalyst, such as the need to supply hydrogen, the need to remove impurities caused by hydrogen, and the need to provide process equipment capable of maintaining and withstanding high reaction temperatures and pressures, are resolved.

[0129] According to one exemplary embodiment of this specification, the deuteration reaction of an aromatic compound can be carried out by heating the solution.

[0130] The deuteration reaction of aromatic compounds by heating the reactor can be carried out at a temperature of 160°C or lower, 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 90°C or lower, or 80°C or higher, specifically, heating the solution at a temperature of 80°C or higher and 140°C or lower.

[0131] When the reactor is heated to 80°C or lower, the deuteration rate of aromatic compounds may slow down, resulting in a potentially low deuteration rate in the final compound. Furthermore, heating the reactor to 160°C or higher may generate a large amount of undesirable byproducts.

[0132] In this case, the deuterium reaction time is 1 hour or longer after the temperature has fully increased. Specifically, after the temperature of the deuterium reaction has fully increased, the deuterium reaction time can be 1 hour or longer and 24 hours or less, preferably 2 hours or longer and 18 hours or less.

[0133] The method for producing deuterated aromatic compounds described in this specification also includes obtaining the deuterated aromatic compound after deuteration. The method of obtaining the compound can be carried out by methods known in the art, and there are no particular limitations.

[0134] The higher the deuteration substitution rate of the obtained deuterated aromatic compound, the better the deuteration substitution rate. Specifically, the deuteration substitution rate of the obtained deuterated aromatic compound can be 50% or more, 60% or more, 70% or more, 80% or more, 85% or more, 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 100%.

[0135] The higher the purity of the obtained deuterated aromatic compound, the better the purity. Specifically, the purity of the obtained deuterated aromatic compound can be 90% or greater, 91% or greater, 92% or greater, 93% or greater, 94% or greater, 95% or greater, 96% or greater, 97% or greater, 98% or greater, 99% or greater, or 100%.

[0136] In one exemplary embodiment of this specification, the aromatic compound is an aromatic compound comprising one or more hydrocarbon aromatic rings, and specifically, an aromatic compound comprising 1 to 30 hydrocarbon aromatic rings. In this context, having one or more hydrocarbon aromatic rings means having one or more hydrocarbon aromatic rings that are monocyclic, polycyclic, or combinations thereof, or having one or more hydrocarbon aromatic rings as basic units (e.g., benzene rings). For example, an anthracene ring means one hydrocarbon aromatic ring, or it may mean three benzene rings linked together based on benzene rings as basic units.

[0137] According to one exemplary embodiment of this specification, the content of aromatic compounds may be 3% by weight or more and 50% by weight or less, based on the total weight of the solvent.

[0138] In one exemplary embodiment of this specification, the aromatic hydrocarbon ring can be a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon ring. For example, the aromatic hydrocarbon ring can be a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted benzo[a]phenanthrene ring, a substituted or unsubstituted phenanthrene ring, etc.

[0139] In this specification, an aromatic compound comprising a hydrocarbon aromatic ring means that the aromatic ring forming the main chain is a hydrocarbon ring, and the substituted hydrogens in the main chain can be replaced by other substituents, and in this case, the type of substituent is not particularly limited. In one exemplary embodiment of this specification, the aromatic compound may be an anthracene-based compound.

[0140] In one exemplary embodiment of this specification, the aromatic compound may be benzene; toluene; naphthalene; naphthylamine; etc.

[0141] In one exemplary embodiment of this specification, the aromatic compound may be an anthracene-based compound, and specifically, may be substituted or unsubstituted anthracene.

[0142] In one exemplary embodiment of this specification, the aromatic compound participating in the deuteration reaction may include a compound represented by the following chemical formula A. Through the deuteration reaction, at least one hydrogen atom in the selected compound is substituted with deuterium.

[0143] [Chemical Formula A]

[0144]

[0145] In chemical formula A,

[0146] L21 to L23 may be the same as or different from each other, and each is independently a direct bond; or a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.

[0147] R21 to R27 may be the same as or different from each other, and each is independently hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted silyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

[0148] Ar21 to Ar23 may be identical or different from each other, and each is independently a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and

[0149] a is 0 or 1.

[0150] In one exemplary embodiment of this specification, the aromatic compound participating in the deuteration reaction can be any of the following chemical formulas 7 to 10. Through the deuteration reaction, at least one hydrogen atom in the selected compound is substituted with deuterium.

[0151] [Chemical Formula 7]

[0152]

[0153] [Chemical Formula 8]

[0154]

[0155] [Chemical Formula 9]

[0156]

[0157] [Chemical Formula 10]

[0158]

[0159] In chemical formulas 7 to 10,

[0160] A1 to A12 are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings.

[0161] B1 through B10 are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings.

[0162] Y1 to Y10 are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings, and

[0163] Z1 to Z8 are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings.

[0164] Examples of substituents in this specification will be described below, but are not limited thereto.

[0165] The term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent, and there are no restrictions on the position to be substituted, as long as the position is where the hydrogen atom is substituted (i.e., the position where the substituent can be substituted), and when two or more are substituted, the two or more substituents can be the same as or different from each other.

[0166] In this specification, the term "substituted or unsubstituted" means substituted with one or more substituents selected from: halogen groups; cyano; nitro; hydroxyl; amino; silyl; boron; alkoxy; alkyl; cycloalkyl; aryl; and heterocyclic groups, substituted with two or more substituents linked together from the substituents exemplified above, or without substituents. For example, "substituents linked together with two or more substituents" can be biphenyl. That is, biphenyl can also be aryl and can be interpreted as substituents linked together with two phenyl groups.

[0167] In this specification, "adjacent" groups can mean a substituent that substitutes an atom directly bonded to an atom substituted with the corresponding substituent, a substituent positioned spatially closest to the corresponding substituent, or another substituent that substitutes an atom substituted with the corresponding substituent. For example, two substituents substituted at the ortho position on a benzene ring and two substituents substituted on the same carbon atom in an aliphatic ring can be interpreted as "adjacent" groups. Furthermore, substituents bonded to two consecutive carbons in an aliphatic ring (a total of four) can be interpreted as "adjacent" groups.

[0168] In this specification, "adjacent groups bond to each other to form a hydrocarbon ring" in the context of substituents means that the substituent bonds to adjacent groups to form a substituted or unsubstituted hydrocarbon ring.

[0169] In this specification, "a five- or six-membered ring formed by bonding adjacent groups" means a ring containing substituents that participate in cyclization that is five- or six-membered. It may include additional rings fused with the ring containing substituents that participate in cyclization.

[0170] Examples of halogen groups in this specification include fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0171] In this specification, silyl groups can be of the chemical formula -SiY a Y b Y c It indicates that Y a Y b and Y c Each can be hydrogen; substituted or unsubstituted alkyl; or substituted or unsubstituted aryl. Specific examples of silyl groups include, but are not limited to, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, etc.

[0172] In this specification, the boron group can be represented by the chemical formula -BY d Y e It indicates that Y d and Y e Each group can be hydrogen; substituted or unsubstituted alkyl; or substituted or unsubstituted aryl. Specific examples of boron groups include, but are not limited to, trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, phenylboryl, etc.

[0173] In this specification, the alkyl group can be straight-chain or branched, and its number of carbon atoms is not particularly limited, but is preferably from 1 to 60. According to one exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to yet another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, pentyl, n-pentyl, hexyl, n-hexyl, heptyl, n-heptyl, octyl, n-octyl, etc.

[0174] In this specification, the alkoxy group can be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, etc.

[0175] The substituents comprising alkyl, alkoxy, and other alkyl moieties described in this specification include both linear and branched forms.

[0176] In this specification, cycloalkyl groups are not particularly limited, but preferably have 3 to 60 carbon atoms, and according to one exemplary embodiment, the number of carbon atoms in a cycloalkyl group is 3 to 30. According to another exemplary embodiment, the number of carbon atoms in a cycloalkyl group is 3 to 20. According to yet another exemplary embodiment, the number of carbon atoms in a cycloalkyl group is 3 to 6. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0177] In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and can be monocyclic or polycyclic aryl. According to one exemplary embodiment, the aryl group has 6 to 39 carbon atoms. According to another exemplary embodiment, the aryl group has 6 to 30 carbon atoms. Examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, tetraphenyl, etc. Examples of polycyclic aryl groups include naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, triphenylene, etc. It includes, but is not limited to, methyl, fluorene, triphenylene, etc.

[0178] In this specification, the fluorene group may be substituted, and two substituents may bond together to form a spirocyclic structure.

[0179] When the fluorenyl group is substituted, the fluorenyl group can be a spirofluorenyl group, for example... And substituted fluorene groups, for example (9,9-dimethylfluorenyl) and (9,9-Diphenylfluorenyl). However, the substituents are not limited to this.

[0180] In this specification, a heterocyclic group is a cyclic group containing one or more of N, O, P, S, Si, and Se as heteroatoms, and its number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to one exemplary embodiment, the number of carbon atoms in the heterocyclic group is 2 to 36. Examples of heterocyclic groups include, but are not limited to, pyridinyl, pyrroloyl, pyrimidinyl, quinolinyl, pyridazinyl, furanyl, thiopheneyl, imidazoyl, pyrazolyl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl, benzocarbazoleyl, benzonaphthofuranyl, benzonaphthothiopheneyl, indobenzocarbazoleyl, indolocarbazoleyl, etc.

[0181] In this specification, the above description of heterocyclic groups can be applied to heteroaryl groups, except that heteroaryl groups are aromatic.

[0182] In this specification, the amino group may be selected from -NH2; alkylamino; N-alkylarylamino; arylamino; N-arylheteroarylamino; N-alkylheteroarylamino; and heteroarylamino, and there is no particular limitation on the number of carbon atoms thereon, but it is preferably 1 to 30. Specific examples of amino groups include, but are not limited to, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, anthraceneamino, 9-methyl-anthraylamino, diphenylamino, N-phenylnaphthylamino, xylylamino, N-phenyltolylamino, triphenylamino, N-phenylbiphenylamino, N-phenylnaphthylamino, N-biphenylnaphthylamino, N-naphthylfluorenylamino, N-phenylphenanthreneamino, N-biphenylphenanthreneamino, N-phenylfluorenylamino, N-phenyltriphenylamino, N-phenanthrenefluorenylamino, and N-biphenylfluorenylamino.

[0183] In this specification, N-alkylarylamine means that the N of the amine group is replaced by an alkyl or aryl amine group.

[0184] In this specification, N-arylheteroarylamine means that the N of the amine group is replaced by an aryl or heteroaryl amine group.

[0185] In this specification, N-alkylheteroarylamine means that the N of the amine group is replaced by an alkyl or heteroaryl amine group.

[0186] In this specification, the alkyl, aryl, and heteroaryl groups in alkylamino, N-alkylarylamino, arylamino, N-arylheteroarylamino, N-alkylheteroarylamino, and heteroarylamino are each identical to the alkyl, aryl, and heteroaryl groups described above.

[0187] In one exemplary embodiment of this specification, the aromatic compound may be any of the following structures.

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] The method for producing deuterated aromatic compounds described in this specification may also include replacing the internal air of the reactor with nitrogen or an inert gas.

[0204] This specification provides deuteration reaction compositions comprising an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water, an organic compound that can be hydrolyzed by heavy water, and an organic solvent.

[0205] For the deuteration reaction composition, the description of the solution in the above production method can be referenced.

[0206] This specification provides information on deuterated aromatic compounds produced by the above method.

[0207] In one exemplary embodiment of this specification, a deuterated aromatic compound means an aromatic compound that has been substituted with at least one or more deuterium atoms.

[0208] In one exemplary embodiment of this specification, the deuterated aromatic compound comprises a substituent selected from leaving groups, hydroxyl groups, substituted or unsubstituted amino groups, and cyano groups. In this specification, a compound containing a leaving group can be an intermediate of the final organic synthesis compound, and a leaving group refers to a reactive group that leaves based on the final compound, or a reactive group that is chemically modified by bonding to other reactants. Therefore, the type of leaving group and the position of its bonding are determined by the organic synthesis method and the position of the substituents in the final compound.

[0209] In the deuterated aromatic compounds described in this specification, the leaving group may be selected from halogen groups and borate groups.

[0210] In the deuterated aromatic compounds described in this specification, the deuterated aromatic compounds containing substituents selected from leaving groups, hydroxyl groups, substituted or unsubstituted amino groups, and cyano groups can be any compound of chemical formulas 7 to 10:

[0211] [Chemical Formula 7]

[0212]

[0213] [Chemical Formula 8]

[0214]

[0215] [Chemical Formula 9]

[0216]

[0217] [Chemical Formula 10]

[0218]

[0219] In chemical formulas 7 to 10,

[0220] At least one of A1 to A12 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings,

[0221] At least one of B1 to B10 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings,

[0222] At least one of Y1 to Y10 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or group that can be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings, and

[0223] At least one of Z1 to Z8 is deuterium, at least one is a substituent selected from leaving group, hydroxyl group, substituted or unsubstituted amino group, and cyano group, and the remainder are each independently hydrogen; leaving group; hydroxyl group; substituted or unsubstituted amino group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form substituted or unsubstituted hydrocarbon rings.

[0224] The compounds of chemical formulas 7 to 10 each have a substituent selected from leaving groups, hydroxyl groups, substituted or unsubstituted amino groups, and cyano groups.

[0225] A deuterated aromatic compound comprising a substituent selected from leaving groups, hydroxyl groups, substituted or unsubstituted amino groups, and cyano groups is a compound with any of the following structures, each of which is substituted with one or more deuterium groups.

[0226]

[0227]

[0228] Theoretically, the lifetime characteristics are most ideally improved when all hydrogens in a deuterated compound are replaced by deuterium, i.e., when the deuteration substitution rate is 100%. However, there are problems such as the need for extreme conditions due to steric hindrance and the destruction of the compound before deuteration due to side reactions. In practice, it is difficult to obtain a compound with all hydrogens at a 100% deuteration substitution rate, and even when a near 100% deuteration substitution rate is obtained, the efficiency is not good compared to the input, considering process time, cost, etc.

[0229] In this specification, since deuterated compounds produced by deuteration reactions and having one or more deuterates are produced as compositions having two or more isotopes with different molecular weights depending on the number of deuterates substituted, the position of the deuterium substitution in the structure will be omitted.

[0230] In compounds having the structure described above, at least one of the positions represented by hydrogen or in which the position where the hydrogen substitution is omitted can be replaced by deuterium.

[0231] This specification provides electronic devices that contain the aforementioned deuterated aromatic compounds.

[0232] This specification provides a method for manufacturing electronic devices, the method comprising: manufacturing electronic devices using the above-described deuterated aromatic compounds.

[0233] For electronic devices and methods for manufacturing electronic devices, descriptions of the compositions may be cited, and repeated descriptions will be omitted.

[0234] There are no particular restrictions on electronic devices, as long as the aforementioned deuterated aromatic compounds can be used, and they can be, for example, organic light-emitting devices, organic phosphorescent devices, organic solar cells, organic photoconductors, organic transistors, etc.

[0235] The electronic device includes: a first electrode; a second electrode disposed facing the first electrode; and an organic material layer having one or more layers disposed between the first electrode and the second electrode, wherein one or more layers of the organic material layer may contain the aforementioned deuterated aromatic compound.

[0236] This specification provides organic light-emitting devices comprising the aforementioned deuterated aromatic compounds.

[0237] In one exemplary embodiment of this specification, the organic light-emitting device includes: a first electrode; a second electrode disposed facing the first electrode; and an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer contains the deuterated aromatic compound.

[0238] In one exemplary embodiment of this specification, the organic material layer includes a light-emitting layer containing the deuterated aromatic compound.

[0239] The organic material layer of the organic light-emitting device described in this specification can be a single-layer structure, but it can also be a multi-layer structure in which two or more organic material layers are stacked. For example, the organic material layer of this specification can consist of one to three layers. Furthermore, the organic light-emitting device of this specification can have a structure that includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer as organic material layers. However, the structure of the organic light-emitting device is not limited to this, and it can include fewer organic layers.

[0240] When an organic light-emitting device comprises multiple layers of organic materials, the organic material layers can be formed from the same material or different materials.

[0241] For example, the organic light-emitting device of this specification can be manufactured by sequentially stacking a positive electrode, an organic material layer, and a negative electrode on a substrate. In this case, the organic light-emitting device can be manufactured by depositing a metal, or a conductive metal oxide, or an alloy thereof, on the substrate using a physical vapor deposition (PVD) method such as sputtering or electron beam evaporation to form a positive electrode; forming an organic material layer on the positive electrode, comprising a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer; and then depositing a material that can be used as a negative electrode on the organic material layer. In addition to the above method, the organic light-emitting device can also be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate.

[0242] Furthermore, in the manufacture of organic light-emitting devices, the aforementioned deuterated aromatic compounds can be formed into organic material layers not only by vacuum deposition but also by solution application. Here, solution application refers to, but is not limited to, spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, and roll coating.

[0243] In one exemplary embodiment of this specification, the first electrode is a positive electrode and the second electrode is a negative electrode.

[0244] According to another exemplary embodiment, the first electrode is a negative electrode and the second electrode is a positive electrode.

[0245] In another exemplary embodiment, the organic light-emitting device can be a normal type organic light-emitting device in which a positive electrode, an organic material layer having one or more layers, and a negative electrode are sequentially stacked on a substrate.

[0246] In yet another exemplary embodiment, the organic light-emitting device can be an inverted organic light-emitting device in which a negative electrode, an organic material layer having one or more layers, and a positive electrode are sequentially stacked on a substrate.

[0247] In this specification, there are no particular limitations on the materials used for the negative electrode, the organic material layer, and the positive electrode, except that at least one layer of the organic material layer contains a deuterated aromatic compound, and materials known in the art can be used.

[0248] In this specification, even in electronic devices including organic phosphorescent devices, organic solar cells, organic photoconductors, organic transistors, etc., the aforementioned deuterated aromatic compounds can be used using principles similar to those applied to organic light-emitting devices. For example, an organic solar cell may have a structure including a negative electrode, a positive electrode, and a photoactive layer disposed between the negative and positive electrodes, and the photoactive layer may contain a selected deuterated compound.

[0249] Invention Embodiments

[0250] The present specification will be described in more detail below by way of examples. However, the following examples are provided for illustrative purposes only and are not intended to limit the scope of the specification.

[0251] [Example]

[0252] [Example 1]

[0253] 35 ml of heavy water (D₂O) and 30 ml of cyclohexane were placed in a flask, and 15 g of methanesulfonic anhydride and 5.0 g of 9-(naphthyl-1-yl)anthracene were slowly added dropwise. The reaction mixture was then allowed to react at 80 °C for 18 hours. After the reaction was complete, the temperature was lowered to room temperature (25 °C), and ethyl acetate was added. The mixture was then neutralized by adding potassium carbonate to bring the pH to 7 or 8. After separating only the organic layer and removing residual water by magnesium sulfate (MgSO₄), the residue was filtered, and the solvent was removed by using a rotary evaporator to obtain deuterium-substituted 9-(naphthyl-1-yl)anthracene.

[0254] [Example 2]

[0255] The deuterated 9-(naphth-1-yl)anthracene was obtained by changing the organic solvent to methylcyclohexane instead of cyclohexane using the same method as in Example 1.

[0256] [Example 3]

[0257] The same method was used as in Example 1, by changing the organic solvent to 1,4-didi Alkane was used to replace cyclohexane to obtain deuterated 9-(naphth-1-yl)anthracene.

[0258] [Example 4]

[0259] The deuterated 9-(naphth-1-yl)anthracene was obtained by changing the organic solvent to 1,2-dimethoxyethane instead of cyclohexane using the same method as in Example 1.

[0260] [Example 5]

[0261] The deuterated 9-(naphth-1-yl)anthracene was obtained by changing the organic solvent to decahydronaphthalene instead of cyclohexane using the same method as in Example 1.

[0262] [Example 6]

[0263] 35 ml of heavy water (D₂O) and 30 ml of toluene were placed in a flask, and 15 g of methanesulfonic anhydride and 5.0 g of 9-phenylanthracene were slowly added to the flask. The reaction mixture was then allowed to react at 80 °C for 18 hours. After the reaction was complete, the temperature was lowered to room temperature (25 °C), and ethyl acetate was added. The mixture was then neutralized by adding potassium carbonate to bring the pH to 7 or 8. After separating only the organic layer and removing residual water by magnesium sulfate (MgSO₄), the residue was filtered, and the solvent was removed by using a rotary evaporator to obtain deuterated 9-phenylanthracene.

[0264] [Example 7]

[0265] The deuterated 9-phenylanthracene was obtained by changing the organic solvent to xylene instead of toluene using the same method as in Example 6.

[0266] [Example 8]

[0267] The deuterated 9-phenylanthracene was obtained by changing the organic solvent to chlorobenzene instead of toluene using the same method as in Example 6.

[0268] [Example 9]

[0269] The deuterated 9-phenylanthracene was obtained by changing the organic solvent to 1,2-dichlorobenzene instead of toluene using the same method as in Example 6.

[0270] [Example 10]

[0271] The deuterated 9-phenylanthracene was obtained by changing the organic solvent to 1,2,4-trichlorobenzene instead of toluene using the same method as in Example 6.

[0272] [Example 11]

[0273] 35 ml of heavy water (D₂O) and 30 ml of 1,1,1-trichloroethane were placed in a flask, and 15 g of methanesulfonic anhydride and 5.0 g of 9-([1,1′-biphenyl]-4-yl)anthracene were slowly added dropwise. The reaction mixture was then allowed to react at 80 °C for 18 hours. After the reaction was complete, the temperature was lowered to room temperature (25 °C), and ethyl acetate was added. The mixture was then neutralized by adding potassium carbonate to bring the pH to 7 or 8. After separating only the organic layer and removing residual water by magnesium sulfate (MgSO₄), the residue was filtered, and the solvent was removed by using a rotary evaporator to obtain deuterium-substituted 9-([1,1′-biphenyl]-4-yl)anthracene.

[0274] [Example 12]

[0275] The deuterium-substituted 9-([1,1′-biphenyl]-4-yl)anthracene was obtained by changing the organic solvent to 1,1,2,2-tetrachloroethane instead of 1,1,1-trichloroethane using the same method as in Example 11.

[0276] [Example 13]

[0277] The deuterium-substituted 9-([1,1′-biphenyl]-4-yl)anthracene was obtained by changing the organic solvent to 1,1,2,2-tetrachloroethylene instead of 1,1,1-trichloroethane using the same method as in Example 11.

[0278] [Example 14]

[0279] The deuterated 9-(naphth-1-yl)anthracene was obtained by changing the acid anhydride to trifluoroacetic anhydride instead of methanesulfonic anhydride using the same method as in Example 1.

[0280] [Example 15]

[0281] The deuterated 9-(naphth-1-yl)anthracene was obtained by changing the acid anhydride to acetic anhydride instead of methanesulfonic anhydride using the same method as in Example 1.

[0282] [Example 16]

[0283] The deuterated 9-(naphth-1-yl)anthracene was obtained by changing the acid anhydride to trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride using the same method as in Example 1.

[0284] [Comparative Example 1]

[0285] In this comparative example, the non-deuterated compound BH-A was used.

[0286]

[0287] [Example 17]

[0288] 30 ml of heavy water (D₂O) and 30 ml of cyclohexane were placed in a flask, and 50 g of methanesulfonic anhydride and 5.0 g of compound BH-A were slowly added dropwise. The reaction mixture was then allowed to react at 80 °C for 18 hours. After the reaction was complete, the temperature was lowered to room temperature (25 °C), and ethyl acetate was added. The mixture was then neutralized by adding potassium carbonate to bring the pH to 7 or 8. After separating only the organic layer and removing residual water by magnesium sulfate (MgSO₄), the residue was filtered, and the solvent was removed by using a rotary evaporator to obtain the deuterium-substituted compound BH-A.

[0289] [Example 18]

[0290] The deuterated 9-bromoanthracene was obtained by changing the reactant to 9-(naphth-1-yl)anthracene using the same method as in Example 1.

[0291] [Comparative Example 2]

[0292] 1 g of 9-(naphthyl-1-yl)anthracene, 15 ml of heavy water (D₂O), 0.5 g of 10% Pt / C, and 10 ml of toluene solvent were placed in a high-pressure reactor, and the reactor interior was sealed by covering the reactor head. A hydrogen-containing gas was blown into the reactants at a rate of 3 to 5 minutes per minute with stirring. The atmosphere in the reactor was then maintained as a gaseous atmosphere, and the reaction was carried out at 130 °C for 24 hours. After the reaction was complete, the temperature was lowered, the catalyst was removed by filtration, the heavy water was removed using MgSO₄, and the solvent was removed by rotary evaporation to obtain deuterium-substituted 9-(naphthyl-1-yl)anthracene.

[0293] [Comparative Example 3]

[0294] The deuterium substitution reaction was carried out using the same method as in Comparative Example 2, by adding 9-bromoanthracene instead of 9-(naphth-1-yl)anthracene. As a result, deuterated 9-bromoanthracene was obtained, but it was determined that the deuterated anthracene had lost most of its bromine group.

[0295] [Experimental Example 1]

[0296] The purity, deuterium substitution rate, and proportion of hydrogenated compounds of Examples 1 to 18 and Comparative Examples 2 to 3 were measured, and the results are shown in Table 1 below.

[0297] Purity and the proportion of hydrogenated compounds were obtained by dissolving the fully reacted sample in a tetrahydrofuran solvent for HPLC and integrating the spectrum at 254 nm wavelength by HPLC. In this case, a solvent containing acetonitrile and tetrahydrofuran mixed in a 5:5 ratio and 1% formic acid, along with water, was used as the mobile phase solvent.

[0298] The preparation of a sample sample involves quantifying a fully deuterated sample and dissolving it in a solvent used for NMR measurement, and an internal standard sample involves quantifying any compound whose peak does not overlap with that of the compound before deuteration in the same amount as the sample sample and dissolving that compound in the same solvent used for NMR measurement. For both the prepared sample sample and the internal standard sample, [further details are needed]. 1 H-NMR yielded NMR measurements.

[0299] In the specified 1 When the H-NMR peaks are obtained, the relative integral values ​​of each position of the sample that has undergone complete deuteration reaction are obtained by setting the internal standard peak to 1.

[0300] When a sample that has undergone complete deuteration is substituted with deuterium at all positions, no hydrogen-related peaks will appear, and in this case, the deuteration substitution rate is determined to be 100%. Conversely, when hydrogen at all positions is not substituted with deuterium, peaks of unsubstituted hydrogen will appear.

[0301] Based on this result, in this experiment, the deuteration rate was obtained by subtracting the integral value of the peaks caused by unsubstituted hydrogen in the NMR spectrum of the sample from the integral value of the hydrogen-related peaks in the NMR spectrum of the unsubstituted deuterium internal standard sample. This value is an integral relative to each position, does not represent the corresponding peaks due to deuteration, and indicates the rate of deuteration substitution.

[0302] Then, it is used in the preparation 1 The substitution rate at each location of the sample is calculated using the weight of the sample, the weight of the internal standard, and the relative integral value used in H-NMR measurements.

[0303] [Table 1]

[0304]

[0305]

[0306]

[0307] Because the reaction is carried out under acidic conditions, Examples 1 to 18 can be conducted at atmospheric pressure without increasing the pressure during the reaction. In contrast, in Comparative Examples 2 and 3, deuterium substitution was carried out in a high-pressure reactor using a catalyst, but the deuterium substitution reaction only occurred when the reaction was carried out at atmospheric pressure or higher (i.e., at least 5 bar or higher). Furthermore, when the reaction is carried out in a high-pressure reactor, a side reaction occurs in which the double bonds of the aromatic ring are partially reduced, resulting in a decrease in purity. In addition, it is difficult to separate the resulting side reactants, and the yield is significantly reduced even during separation.

[0308] Examples 18 and Comparative Example 3 were experiments conducted with the target compounds having leaving groups. Although the starting materials differed, all target compounds each contained a leaving group (-Br). Comparative Example 3 was an experiment involving the substitution of deuterium under high pressure using a catalyst. These experiments determined whether the leaving group was well attached and did not detach after the deuteration substitution reaction. In Example 18, the leaving group was well attached even after the deuteration substitution reaction, while in Comparative Example 3, peaks were identified by HPLC-Mass analysis as a result of the detachment of anthracene from the bromine group, which is a leaving group.

[0309] [Experimental Example 2]

[0310] Comparison device example 1

[0311] A thin coating with a thickness of An indium tin oxide (ITO) glass substrate is immersed in distilled water containing dissolved detergent and subjected to ultrasonic cleaning. In this case, a Decon ultrasonic cleaner manufactured by Fischer Co. is used. TM CON705 was used as the cleaning agent, and distilled water filtered twice using a 0.22μm sterilizing filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice for 10 minutes each using distilled water. After washing with distilled water, the substrate was ultrasonically cleaned for 10 minutes each with isopropanol, acetone, and methanol, dried, and then transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum deposition machine.

[0312] The following HT and PD were vacuum deposited at a weight ratio of 95:5 onto the thus prepared transparent ITO electrode to form a... The thickness is such that a hole injection layer is formed, and then HT material is vacuum deposited only to a thickness that forms a hole injection layer. The thickness is such that a hole transport layer is formed. A compound represented by EB is thermally vacuum deposited onto the hole transport layer to form a layer with... The thickness serves as an electron blocking layer. Subsequently, BH-A and a compound represented by BD (as follows) are vacuum-deposited at a weight ratio of 96:4 onto a substrate with... The thickness was used as the luminescent layer. Subsequently, ET and the compound represented by Liq were vacuum-deposited at a weight specific heat of 1:1 onto a substrate with... The thickness serves as an electron transport layer, and subsequently, the following compound, represented by Liq, is vacuum-deposited onto a substrate with... The thickness is thus formed into an electron-injected layer. Magnesium and silver are then deposited on the electron-injected layer at a weight ratio of 10:1 to form a layer with... The thickness and deposit aluminum to have The thickness is used to form the negative electrode, thereby manufacturing organic light-emitting devices.

[0313]

[0314] Device Example 1

[0315] An organic light-emitting device was manufactured in the same manner as in Comparative Device Example 1, except that in Comparative Device Example 1, the compound prepared in Example 17 (deuterium-substituted BH-A) was used instead of BH-A as the host compound of the light-emitting layer.

[0316] Comparator Examples 2 to 3

[0317] The organic light-emitting device was manufactured in the same manner as in Comparative Device Example 1, except that in Comparative Device Example 1, the compounds described in Table 2 were used instead of BH-A as the host compound of the light-emitting layer. Furthermore, the corresponding compounds for BH-B and BH-C in Table 2 are as follows.

[0318]

[0319] Voltage, efficiency, and lifetime (T95) were measured by applying current to organic light-emitting devices fabricated in previous experimental and comparative examples, and the results are shown in Table 2 below. In this case, voltage and efficiency were measured by applying 10 mA / cm². 2 The current density is measured, and T95 means 20 mA / cm². 2 The time it takes for the initial brightness to decrease to 95% at a given current density.

[0320] [Table 2]

[0321]

Claims

1. A method for producing a deuterated aromatic compound, the method comprising: a deuterium exchange reaction of an aromatic compound is performed using a solution containing heavy water, an organic compound capable of being hydrolyzed by the heavy water, an aromatic compound containing one or more hydrocarbon aromatic rings, and an organic solvent, wherein the aromatic compound is represented by Chemical Formula A or Chemical Formula 9: [Chemical Formula A] ， in Chemical Formula A, L21to L23are the same as or different from each other, and each is independently a direct bond; or a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group, R21to R27are the same as or different from each other, and each is independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, Ar21to Ar23are the same as or different from each other, and each is independently a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and a is 0 or 1, [Chemical Formula 9] ， in Chemical Formula 9, at least one of Y1to Y10is deuterium, at least one is a substituent selected from a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the others are each independently hydrogen; a leaving group; a hydroxyl group; a substituted or unsubstituted amine group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group, or can be bonded with an adjacent group to form a substituted or unsubstituted hydrocarbon ring, wherein the leaving group is selected from a halogen group and a boronic acid group, wherein the organic solvent is selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decaline, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene, wherein the organic solvent is selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decaline, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene, wherein the organic compound capable of being hydrolyzed by the heavy water includes at least one compound of Chemical Formulas 1 to 3: [Chemical Formula 1] ， [Chemical Formula 2] ， [Chemical Formula 3] ， in Chemical Formulas 1 to 3, R1to R6are the same as or different from each other, and each is independently an alkyl group unsubstituted or substituted with a halogen group; or an aryl group unsubstituted or substituted with a halogen group, and wherein the content of the organic solvent is 3 to 15 times the content of the aromatic compound, based on the weight of the aromatic compound, wherein the term "substituted or unsubstituted" means substituted with one or two or more substituents selected from a halogen group; a cyano group; a nitro group; a hydroxyl group; an amine group; an alkoxy group; an alkyl group; a cycloalkyl group; an aryl group; and a heterocyclic group, substituted with two or more substituents of the above substituents connected to each other, or not having a substituent, wherein, the number of carbon atoms of the alkyl group is 1 to 20; the number of carbon atoms of the alkoxy group is 1 to 20; the number of carbon atoms of the cycloalkyl group is 3 to 20; the number of carbon atoms of each of the aryl group and the arylene group is 6 to 30; the number of carbon atoms of each of the heterocyclic group, the heteroaryl group, and the heteroarylene group is 2 to 36; the amine group is selected from -NH2; an alkylamine group; an N-alkyl arylamine group; an arylamine group; an N-aryl heteroarylamine group; an N-alkyl heteroarylamine group; and a heteroarylamine group, and if containing a carbon atom, the number of carbon atoms thereof is 1 to 30.

2. The method according to claim 1, wherein the organic compound capable of being hydrolyzed by the heavy water includes at least one of triflic anhydride, trifluoroacetic anhydride, acetic anhydride, methanesulfonic anhydride, methyl acetate, ethyl acetate, and dimethylacetamide.

3. The method according to claim 1, wherein performing the deuterium exchange reaction of the aromatic compound comprises: preparing a solution containing an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent; and performing the deuterium exchange reaction of the aromatic compound by heating the solution.

4. The method according to claim 3, wherein the temperature at which the deuterium exchange reaction of the aromatic compound is performed by heating the solution is 80°C or higher and 140°C or lower.

5. A deuterium exchange reaction composition containing an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent, wherein the aromatic compound is represented by the following Chemical Formula A or Chemical Formula 9: [Chemical Formula A] in Chemical Formula A, ， L21to L23are the same as or different from each other, and each is independently a direct bond; or a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group, R21to R27are the same as or different from each other, and each is independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, Ar21to Ar23are the same as or different from each other, and each is independently a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and a is 0 or 1, [Chemical Formula 9] in Chemical Formula 9, ， at least one of Y1to Y10is deuterium, at least one is a substituent selected from a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the others are each independently hydrogen; a leaving group; a hydroxyl group; a substituted or unsubstituted amine group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group, or can be bonded with an adjacent group to form a substituted or unsubstituted hydrocarbon ring, wherein the leaving group is selected from a halogen group and a boronic acid group, wherein the organic compound capable of being hydrolyzed by the heavy water includes at least one compound of the following Chemical Formulas 1 to 3: wherein the organic solvent is selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decaline, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene, wherein the organic solvent is selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decaline, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene, [Chemical Formula 1] [Chemical Formula 2] ， [Chemical Formula 3] ， in Chemical Formulas 1 to 3, ， R1to R6are the same as or different from each other, and each is independently an alkyl group unsubstituted or substituted with a halogen group; or an aryl group unsubstituted or substituted with a halogen group, and wherein the content of the organic solvent is 3 to 15 times the content of the aromatic compound based on the weight of the aromatic compound, ​ wherein the term "substituted or unsubstituted" means substituted with one or two or more substituents selected from the group consisting of a halogen group; a cyano group; a nitro group; a hydroxyl group; an amine group; an alkoxy group; an alkyl group; a cycloalkyl group; an aryl group; and a heterocyclic group, a substituent substituted with two or more substituents among the above substituents, or no substituent, wherein, the number of carbon atoms of the alkyl group is 1 to 20; the number of carbon atoms of the alkoxy group is 1 to 20; the number of carbon atoms of the cycloalkyl group is 3 to 20; the number of carbon atoms of each of the aryl group and the arylene group is 6 to 30; the number of carbon atoms of each of the heterocyclic group, the heteroaryl group, and the heteroarylene group is 2 to 36; the amine group is selected from the group consisting of -NH2; an alkylamine group; an N-alkyl arylamine group; an arylamine group; an N-aryl heteroarylamine group; an N-alkyl heteroarylamine group; and a heteroarylamine group, and if containing a carbon atom, the number of carbon atoms thereof is 1 to 30.

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