Method for producing deuterated aromatic compounds and deuterated reaction composition

Abstract

The present specification relates to a method for producing deuterated aromatic compounds and a deuteration reaction composition.

Description

[Technical field]

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2020-0108192 filed with the Korean Intellectual Property Office on August 27, 2020, and Korean Patent Application No. 10-2020-0178795 filed with the Korean Intellectual Property Office on December 18, 2020, the entire contents of which are incorporated herein by reference.

[0002] The present specification relates to a method for producing deuterated aromatic compounds and a deuteration reaction composition. [Background technology]

[0003] Compounds containing deuterium are used for various purposes, such as as labeling compounds for investigating chemical reaction mechanisms or substance metabolism, as well as for medicines, insecticides, organic electroluminescence materials, and other purposes.

[0004] It is known that aromatic compounds are substituted with deuterium to improve the lifespan of organic light-emitting diode (OLED) materials. The principle of this effect is that the LUMO energy of the CD bond becomes lower than that of the CH bond when substituted with deuterium, improving the lifespan of OLED materials.

[0005] When carrying out a deuteration reaction on one or more aromatic compounds using existing heterogeneous catalytic reactions, a problem occurred in which by-products were continuously generated due to side reactions. This was due to the hydrogenation reaction generated by hydrogen gas, and in order to remove this, attempts were made to increase the purity through a post-reaction purification process, but it was difficult to achieve high purity because there was little difference in melting point and solubility from existing substances. To improve this, the reaction must be carried out at very high temperatures (approximately 220℃ or higher) in order to react without hydrogen gas, which can cause stability problems at certain stages. Summary of the Invention [Problem to be solved by the invention]

[0006] The present specification provides methods for producing deuterated aromatic compounds and deuteration reaction compositions. [Means for solving the problem]

[0007] The present specification provides a method for producing a deuterated aromatic compound, the method including a step of carrying out a deuteration reaction of the aromatic compound using a solution containing heavy water, an organic compound that can be hydrolyzed by the heavy water, an aromatic compound containing at least one hydrocarbon aromatic ring, and an organic solvent.

[0008] In the method for producing a deuterated aromatic compound of the present specification, the step of carrying out a deuteration reaction of the aromatic compound includes: The method includes the steps of: preparing a solution containing an aromatic compound containing at least one hydrocarbon aromatic ring, heavy water, an organic compound that can be hydrolyzed by the heavy water, and an organic solvent; and heating the deuteration reaction solution to cause a deuteration reaction of the aromatic compound to proceed.

[0009] In the method for producing a deuterated aromatic compound of the present specification, the organic compound that can be hydrolyzed by heavy water includes at least one compound represented by the following chemical formulas 1 to 4. [Chemical formula 1] R1-C(O)OC(O)-R2 [Chemical formula 2] R3-S(O 2 )OS(O 2 )-R4 [Chemical formula 3] R5-C(O)O-R6 [Chemical formula 4] R7-CONH-R8 In the above chemical formulas 1 to 4, R1 to R8 are the same or different and each independently represents a monovalent organic group that is unsubstituted or substituted with a halogen group.

[0010] In the method for producing a deuterated aromatic compound of the present specification, the organic compound that can be hydrolyzed by heavy water includes at least one of trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, methanesulfonic anhydride, methyl acetate, ethyl acetate, and dimethylacetamide.

[0011] The present specification also provides a deuteration reaction composition comprising an aromatic compound containing at least one hydrocarbon aromatic ring, heavy water, an organic compound that can be hydrolyzed by the heavy water, and an organic solvent.

[0012] In the method for producing a deuterated aromatic compound or the deuteration reaction composition of the present specification, the organic solvent is selected from the group consisting of a hydrocarbon chain substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an aliphatic hydrocarbon ring substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an aromatic hydrocarbon ring substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an alkene compound substituted or unsubstituted with a group selected from an alkyl group and a halogen group; a straight-chain or branched-chain hetero chain; a substituted or unsubstituted aliphatic hetero ring; and a substituted or unsubstituted aromatic hetero ring.

[0013] In the method for producing a deuterated aromatic compound or the deuteration reaction composition of the present specification, the organic solvent is selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decalin, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, dichlorobenzene, and 1,2,4-trichlorobenzene.

[0014] Further provided herein is a deuterated aromatic compound produced by the above-described method.

[0015] The deuterated aromatic compounds herein contain a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group.

[0016] In the deuterated aromatic compounds herein, the leaving group is selected from the group consisting of a halogen group and a boronic acid group.

[0017] In the present specification, the deuterated aromatic compound containing a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group is represented by any one of chemical formulas 7 to 10: [Chemical formula 7] [ka] [Chemical formula 8] [ka] [Chemical formula 9] [ka] [Chemical formula 10] [ka] In the above Chemical Formulas 7 to 10, at least one of A1 to A12 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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, which may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; at least one of B1 to B10 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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, which may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; at least one of Y1 to Y10 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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, which may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; At least one of Z1 to Z8 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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 may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring.

[0018] The present disclosure also provides an electrical device that includes a deuterated aromatic compound. Effect of the Invention

[0019] The manufacturing method according to the first embodiment of the present specification has the advantage that impurities due to hydrogen gas are not generated.

[0020] The manufacturing method according to the second embodiment of the present specification has an advantage that the deuterium substitution rate is high.

[0021] The manufacturing method according to the third embodiment of the present specification has an advantage that the purity of the obtained compound is high.

[0022] The production method according to the fourth embodiment of the present specification allows the deuteration reaction to be carried out at a lower pressure.

[0023] The production method according to the fifth embodiment of the present specification enables the deuteration reaction to be carried out at a lower temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The present specification will be explained in detail below.

[0025] The present specification provides a method for producing a deuterated aromatic compound, the method including a step of carrying out a deuteration reaction of the aromatic compound using a solution containing heavy water, an organic compound that can be hydrolyzed by the heavy water, an aromatic compound containing at least one hydrocarbon aromatic ring, and an organic solvent.

[0026] The method for producing a deuterated aromatic compound according to the present invention is characterized by the absence of a hydrogen supply step.

[0027] Conventionally, hydrogen gas was supplied to activate the metal catalyst, which is a heterogeneous catalyst added to produce deuterated aromatic compounds. When hydrogen is supplied to proceed with the deuteration reaction, the hydrogen gas advances the hydrogenation reaction, and by-products are generated due to side reactions.

[0028] In order to remove the by-products that are generated, a purification process is required to increase the purity. However, even after this purification step, the by-products are not different from the target material in terms of melting point or solubility, making it difficult to produce a high-purity compound.

[0029] The method for producing a deuterated aromatic compound according to the present invention has an advantage that an organic compound that can be hydrolyzed by heavy water is used instead of a metal catalyst, which is a heterogeneous catalyst, and therefore it is not necessary to supply a metal catalyst and hydrogen gas for activating the metal catalyst, and therefore no impurities due to hydrogen gas are generated.

[0030] On the other hand, when a metal catalyst is used in a deuteration reaction, the metal catalyst reacts with reactive groups of the compound to be deuterized, such as a halogen group, an amine group, a hydroxyl group, a cyano group, etc., and therefore, in the deuteration reaction using a metal catalyst, the compound to be deuterized is limited to a compound that does not have a reactive group capable of reacting with the metal catalyst or has a reactive group with low reactivity.

[0031] In the method for producing a deuterated aromatic compound according to the present specification, an organic compound capable of being hydrolyzed by heavy water is used instead of a metal catalyst, which is a heterogeneous catalyst, and therefore a compound having a reactive group such as a halogen group, an amine group, a hydroxyl group, a cyano group, etc. can also be selected as a compound to be deuterated. Specifically, after deuteration of an intermediate compound having a reactive group such as a halogen group, an amine group, a hydroxyl group, a cyano group, etc., a reaction for substituting an aromatic substituent on the reactive group can be carried out.

[0032] The manufacturing method according to the present specification has the advantage of a high deuterium substitution rate.

[0033] The preparation method according to the present invention has the advantage that the obtained compound has a high purity.

[0034] The production method according to the present specification allows the deuteration reaction to be carried out at a lower pressure.

[0035] The production method according to the present specification enables the deuteration reaction to be carried out at a lower temperature.

[0036] The method for producing a deuterated aromatic compound herein comprises the steps of: preparing an aromatic compound containing one or more hydrocarbon aromatic rings; 2 O) preparing a solution containing an organic compound capable of being hydrolyzed by heavy water and an organic solvent.

[0037] The aromatic compound containing at least one hydrocarbon aromatic ring, heavy water (D 2 The step of preparing a solution containing an aromatic compound having at least one hydrocarbon aromatic ring, heavy water (D O), an organic compound capable of being hydrolyzed by heavy water, and an organic solvent is carried out by preparing a solution containing an aromatic compound having at least one hydrocarbon aromatic ring, heavy water (D O), an organic compound capable of being hydrolyzed by heavy water, and an organic solvent in a reactor. 2 O), a solution containing an organic compound that can be hydrolyzed by the heavy water and an organic solvent, or an aromatic compound containing one or more hydrocarbon aromatic rings, heavy water (D 2 O) The organic compound capable of being hydrolyzed by heavy water and the organic solvent may be separately charged into a reactor to prepare a solution.

[0038] In one embodiment of the present specification, the organic compound hydrolyzable by heavy water is not particularly limited as long as it has a reactive group decomposable by heavy water, and may include, for example, at least one compound represented by the following chemical formulas 1 to 4. [Chemical formula 1] R1-C(O)OC(O)-R2 [Chemical formula 2] R3-S(O 2 )OS(O 2 )-R4 [Chemical formula 3] R5-C(O)O-R6 [Chemical formula 4] R7-CONH-R8 In the above chemical formulas 1 to 4, R1 to R8 are the same or different and each independently represents a monovalent organic group that is unsubstituted or substituted with a halogen group.

[0039] In one embodiment of the present specification, R1 and R2 may be the same substituents.

[0040] In one embodiment of the present specification, R3 and R4 may be the same substituents.

[0041] In one embodiment of the present specification, R5 and R6 may be the same substituents.

[0042] In one embodiment of the present specification, R7 and R8 may be the same substituents.

[0043] In one embodiment of the present specification, R1 to R8 are the same or different, and each may independently be an alkyl group substituted or unsubstituted with a halogen group; or an aryl group substituted or unsubstituted with a halogen group.

[0044] In one embodiment of the present specification, R1 to R8 may be the same or different, and each may independently be an alkyl group having 1 to 30 carbon atoms and substituted or unsubstituted with a halogen group; or an aryl group having 6 to 50 carbon atoms and substituted or unsubstituted with a halogen group.

[0045] In one embodiment of the present specification, R1 to R8 may be the same or different, and each may independently be an alkyl group having 1 to 10 carbon atoms and substituted or unsubstituted with a halogen group; or an aryl group having 6 to 20 carbon atoms and substituted or unsubstituted with a halogen group.

[0046] In one embodiment of the present specification, R1 to R8 may be the same or different, and each may independently be an alkyl group having 1 to 10 carbon atoms, which may be unsubstituted or substituted with a halogen group.

[0047] In one embodiment of the present specification, R1 to R8 may be the same or different, and each may independently be an alkyl group having 1 to 5 carbon atoms, which may be unsubstituted or substituted with a halogen group.

[0048] In one embodiment of the present specification, R1 to R8 may be the same or different, and each independently may be a substituent of the following Chemical Formula 5 or Chemical Formula 6. [Chemical formula 5] -(CH 2 ) l (CF 2 ) m (CF 3 ) n (CH 3 ) 1-n [Chemical formula 6] -C(H) a ((CH 2 ) l (CF 2 ) m CF 3 ) 3-a In the above chemical formulas 5 and 6, l and m are each an integer of 0 to 10, and n and a are each 0 or 1.

[0049] In one embodiment of the present specification, R1 to R8 may be the same or different, and each independently may be a substituent of Chemical Formula 5.

[0050] In one embodiment of the present specification, R1 to R8 are the same or different, and each independently represents -CF 3 ,-CH 2 CH 3 or -CH 3 may be also possible.

[0051] In the method for producing a deuterated aromatic compound of the present specification, the organic compound that can be hydrolyzed by heavy water includes at least one of trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, methanesulfonic anhydride, methyl acetate, ethyl acetate, and dimethylacetamide.

[0052] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include trifluorometanesulfonic anhydride.

[0053] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include trifluoroacetic anhydride.

[0054] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include acetic anhydride.

[0055] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include methanesulfonic anhydride.

[0056] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include trifluoromethansulfonic anhydride and trifluoroacetic anhydride.

[0057] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include trifluoromethanesulfonic anhydride and acetic anhydride.

[0058] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include trifluoromethansulfonic anhydride and trifluoroacetic anhydride.

[0059] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include trifluorometanesulfonic anhydride and acetic anhydride.

[0060] In one embodiment of the present specification, the organic compound that can be hydrolyzed by heavy water may include at least one of the compounds of Chemical Formula 1 and Chemical Formula 2. When at least one of the compounds of Chemical Formula 1 and Chemical Formula 2 is added to heavy water, hydrolysis with heavy water easily occurs even at room temperature.

[0061] In one embodiment of the present specification, the organic compound hydrolyzable by heavy water includes at least one of the compounds of Chemical Formula 1 and Chemical Formula 2, and may further include at least one of the compounds of Chemical Formula 3 and Chemical Formula 4. When the organic compound hydrolyzable by heavy water includes at least one of the compounds of Chemical Formula 1 and Chemical Formula 2, the temperature generated by the hydrolysis reaction, which is an exothermic reaction, can be controlled by adding at least one of the compounds of Chemical Formula 3 and Chemical Formula 4, which have a relatively slow hydrolysis reaction.

[0062] In one embodiment of the present specification, when the organic compound hydrolyzable by heavy water includes at least one of the compounds of Chemical Formula 3 and Chemical Formula 4, it may further include at least one of the compounds of Chemical Formula 1 and Chemical Formula 2. The hydrolysis reaction can be accelerated by adding the compounds of Chemical Formula 1 and Chemical Formula 2, which undergo a relatively easy hydrolysis reaction.

[0063] In one embodiment of the present specification, the organic compound hydrolyzable by heavy water includes at least one of trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, and methanesulfonic anhydride, and may further include at least one of methyl acetate, ethyl acetate, and dimethylacetamide.

[0064] In one embodiment of the present specification, in the organic compound hydrolyzable by heavy water, the weight ratio of at least one of the compounds of Chemical Formula 3 and Chemical Formula 4 to at least one of the compounds of Chemical Formula 1 and Chemical Formula 2 may 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.

[0065] According to one embodiment of the present specification, the content of the organic compound that can be hydrolyzed by heavy water may be 1 mol% or more and 100 mol% or less based on the moles of heavy water. Specifically, according to one embodiment of the present specification, the content of the organic compound that can be hydrolyzed by heavy water is equal to or less than the molar equivalent of heavy water and is adjusted according to the target material. In this case, it is possible to increase the affinity between the aromatic compound and heavy water, which are not mixed with each other, and there is an advantage in that the deuterium substitution reactivity is increased.

[0066] According to one embodiment of the present specification, the content of the organic solvent may be 1 to 40 times, specifically 3 to 15 times, the weight of the aromatic compound containing at least one hydrocarbon aromatic ring, which will be described later. In this case, the temperature of all steps can be controlled to shorten the reaction time.

[0067] In the method for producing a deuterated aromatic compound of the present specification, the step of carrying out a deuteration reaction of the aromatic compound includes: providing a solution containing an aromatic compound containing at least one hydrocarbon aromatic ring, heavy water, an organic compound hydrolyzable by said heavy water, and an organic solvent; and The method includes heating the solution to cause the deuteration reaction of the aromatic compound to proceed.

[0068] According to one embodiment of the present specification, the content of the aromatic compound may be 3 to 100 times the molar amount of the hydrolyzable organic compound, which is advantageous in that deuterium can be efficiently substituted from the hydrolyzable organic compound by heavy water.

[0069] According to one embodiment of the present specification, the content of the heavy water may be 0.1 to 30 times the weight of the aromatic compound. In this case, there is an advantage that deuterium can be efficiently substituted from the heavy water.

[0070] According to one embodiment of the present specification, the deuteration reaction solution may include an additional deuterium source, which may be a deuterated aromatic solvent, such as benzene-d6, toluene-d8, etc.

[0071] According to one embodiment of the present specification, the content of the additional deuterium source may be 0.1 to 30 times the weight of the aromatic compound, which has the advantage of increasing reactivity and reducing heat generation during the reaction.

[0072] In the method for producing a deuterated aromatic compound of the present specification, the deuteration reaction solution further contains an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the aromatic compound, and may be selected according to the aromatic compound to be used.

[0073] In one embodiment according to the present specification, the organic solvent may be an organic solvent miscible with deuterium oxide to allow the reaction to proceed in one phase, or an organic solvent immiscible with deuterium oxide may be used to separate the organic solvent into two phases and allow the deuteration reaction to proceed at the interface.

[0074] Specifically, in the case of a one-phase reaction, an excessive amount of hydrolyzable organic compound is required to maintain an appropriate concentration of the totally hydrolyzed organic compound, but in the case of a two-phase reaction, it is possible to reduce the amount of hydrolyzable organic compound to maintain an appropriate concentration of the hydrolyzed organic compound. Through this, in the case of a two-phase reaction, the amount of hydrolyzed organic compound can be reduced, leading to an increase in the purity of the deuterium substitution rate.

[0075] When the number of hydrogen atoms in an aromatic compound is large, an excess of heavy water is required to increase the deuterium substitution rate, but if the deuteration reaction is carried out in one phase, the solubility of the aromatic compound decreases due to the excess heavy water, and there is a high possibility that the reactants will precipitate during or before and after the reaction. In contrast, if the deuteration reaction is carried out in two phase, the aromatic compound is dissolved in the organic solvent, and the heavy water and hydrolyzed organic compound are separated and exist in the aqueous solution layer, so in the two phase case, the deuterium substitution rate of the aromatic compound can be increased without the problem of precipitation during the reaction, even when an excess of heavy water is used.

[0076] In the case where no organic solvent is used, when a certain concentration of hydrolyzed organic compounds having deuterium is generated by the hydrolysis reaction of a hydrolyzable organic compound, the deuterium substitution reaction occurs successfully as the deuterium-containing hydrolyzed organic compounds mix with the heavy water and the aromatic compound, which is the target material, due to the hydrolysis reaction of the deuterium-containing hydrolyzed organic compounds.

[0077] However, since the organic compounds hydrolyzed by heavy water are themselves very strong acids, side reactions often occur due to the increase in the concentration of the hydrolyzed organic compounds, which can reduce the purity. Furthermore, handling a solution containing a large amount of hydrolyzed organic compounds during the work-up process after the reaction can be dangerous in terms of stability.

[0078] On the other hand, when an organic solvent is used, 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 increased purity and improved stability.

[0079] When no organic solvent is used, the concentration of deuterium-substituted trifluoromethanesulfonic acid formed by the hydrolysis of trifluoromethanesulfonic anhydride, which is added as an organic compound capable of being hydrolyzed by heavy water, increases, and the deuterium substitution reaction occurs frequently.

[0080] However, because trifluoromethanesulfonic acid itself is a very strong acid, increasing the concentration of trifluoromethanesulfonic acid can also lead to side reactions and reduce purity. Furthermore, handling a solution containing a large amount of trifluoromethanesulfonic acid during the work-up process after the reaction can be dangerous from the standpoint of stability.

[0081] Meanwhile, when an organic solvent is used together, the amount of trifluoromethanesulfonic anhydride used can be reduced by about 30 to 90% compared to conventional methods, and the purity and stability can be increased.

[0082] In the method for producing a deuterated aromatic compound of the present specification, the organic solvent is selected from the group consisting of a hydrocarbon chain substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an aliphatic hydrocarbon ring substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an aromatic hydrocarbon ring substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an alkene compound substituted or unsubstituted with a group selected from an alkyl group and a halogen group; a straight-chain or branched-chain hetero chain; a substituted or unsubstituted aliphatic hetero ring; and a substituted or unsubstituted aromatic hetero ring.

[0083] In one embodiment of the present specification, the organic solvent is selected from the group consisting of alkyl substituted or unsubstituted with a halogen group; cycloalkyl substituted or unsubstituted with an alkyl group and having a monocyclic or polycyclic ring; a benzene ring substituted or unsubstituted with an alkyl group; substituted or unsubstituted alkyl acetate; alkyl ketone; alkyl sulfoxide; lactone having 4 to 10 carbon atoms; alkyl amide; glycol having 4 to 10 carbon atoms; dioxane; alkyl ether; and acetic acid substituted or unsubstituted with an alkoxy group.

[0084] In the method for producing a deuterated aromatic compound of the present specification, the organic solvent is selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, decalin, hexane, heptane, toluene, xylene, mesitylene, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethylene, chlorobenzene, dichlorobenzene, and 1,2,4-trichlorobenzene.

[0085] If the content of the organic solvent is too high, the deuterium substitution rate decreases, and conversely, if the content of the organic solvent is too low, the reactants do not dissolve well, so the deuterium substitution rate decreases. Preferably, the mass ratio of the organic solvent is 2 to 40 times, specifically 3 to 16 times, based on the mass of the aromatic compound.

[0086] According to one embodiment of the present specification, the solution does not contain a metal catalyst, and instead an organic compound that can be hydrolyzed by heavy water plays the role of the metal catalyst, thereby solving problems that arise when adding a metal catalyst, such as the need to supply hydrogen gas, the need to remove impurities caused by hydrogen gas, and the need to prepare stage equipment that can maintain and withstand high reaction temperatures and high pressures.

[0087] According to one embodiment of the present specification, the step of proceeding with deuteration of the aromatic compound may involve heating the solution to proceed with deuteration.

[0088] The step of heating the reactor to proceed with deuteration of the aromatic compound may be a step of heating the solution at a temperature of 160° C. or less, 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or more, specifically, a step of heating at a temperature of 80° C. or more and 140° C. or less.

[0089] When the reactor is heated at a temperature below 80° C., the deuteration reaction rate of the aromatic compound may be slow, and the deuterium substitution rate of the final compound may not be high. Also, when the reactor is heated sufficiently to above 160° C., the production of undesired side products may increase.

[0090] In this case, the deuterium reaction time is 1 hour or more after the completion of the temperature increase. Specifically, the deuterium reaction can be performed for 1 hour to 24 hours, preferably 2 hours to 18 hours, after the completion of the temperature increase.

[0091] The method for preparing a deuterated aromatic compound according to the present invention further includes, after the deuteration step, obtaining the deuterated aromatic compound. The method for obtaining the deuterated aromatic compound may be a method known in the art and is not particularly limited.

[0092] The higher the deuterium substitution rate of the obtained deuterated aromatic compound, the better. Specifically, the deuterium substitution rate of the obtained deuterated aromatic compound may 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%.

[0093] The higher the purity of the obtained deuterated aromatic compound, the better. Specifically, the purity of the obtained deuterated aromatic compound may be 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%.

[0094] In one embodiment of the present specification, the aromatic compound is an aromatic compound containing one or more hydrocarbon aromatic rings, specifically, an aromatic compound containing 1 to 30 hydrocarbon aromatic rings. At this time, the term "one or more hydrocarbon aromatic rings" means one or more monocyclic, polycyclic or combinations thereof, or one or more basic unit hydrocarbon aromatic rings (e.g., benzene rings). For example, an anthracene ring may mean one hydrocarbon aromatic ring, or may mean that three benzene rings are connected based on the basic unit benzene ring.

[0095] According to one embodiment of the present specification, the content of the aromatic compound may be 3 wt % or more and 50 wt % or less based on the total weight of the solvent.

[0096] In one embodiment of the present specification, the hydrocarbon aromatic ring may be a substituted or unsubstituted, monocyclic or polycyclic hydrocarbon aromatic ring.For example, the hydrocarbon aromatic ring may be a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted triphenylene ring, a substituted or unsubstituted phenanthrene ring, etc.

[0097] In the present specification, the aromatic compound containing a hydrocarbon aromatic ring means that the aromatic ring forming the backbone is a hydrocarbon ring, and the hydrogen substituted on the backbone may be substituted with another substituent, and the type of the substituent is not particularly limited. In one embodiment of the present specification, the aromatic compound may be an anthracene-based compound.

[0098] In one embodiment herein, the aromatic compound may be benzene; toluene; naphthalene; naphthylamine;

[0099] In one embodiment of the present specification, the aromatic compound may be an anthracene-based compound, specifically, substituted or unsubstituted anthracene.

[0100] In one embodiment of the present 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 of the selected compound is replaced with deuterium. [Chemical formula A] [ka] In the above chemical formula A, L21 to L23 are the same or different and each independently represents a direct bond; a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; R21 to R27 are the same or different and each independently represent a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; Ar21 to Ar23 are the same or different and each independently represents a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; a is 0 or 1.

[0101] In one embodiment of the present specification, the aromatic compound participating in the deuteration reaction may be any of the following formulas 7 to 10. Through the deuteration reaction, at least one hydrogen of the selected compound is replaced with deuterium. [Chemical formula 7] [ka] [Chemical formula 8] [ka] [Chemical formula 9] [ka] [Chemical formula 10] [ka] In the above Chemical Formulas 7 to 10, A1 to A12 each independently represent 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, which may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; B1 to B10 each independently represent 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 may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; Y1 to Y10 each independently represent 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 may combine with adjacent groups to form a substituted or unsubstituted hydrocarbon ring; Z1 to Z8 each independently represent 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 may combine with adjacent groups to form a substituted or unsubstituted hydrocarbon ring.

[0102] Examples of the substituents in this specification are described below, but are not limited to these.

[0103] The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position of the substitution is not limited as long as it is a position at which a hydrogen atom is substituted, i.e., a position at which a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

[0104] In this specification, the term "substituted or unsubstituted" means that it is substituted with one or more substituents selected from the group consisting of halogen group, cyano group, nitro group, hydroxy group, amine group, silyl group, boron group, alkoxy group, alkyl group, cycloalkyl group, aryl group, and heterocyclic group, or it is substituted with a substituent in which two or more of the above-mentioned exemplary substituents are linked, or it does not have any substituent. For example, the "substituent in which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are linked.

[0105] In this specification, the term "adjacent" may refer to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. For example, two substituents substituted at the ortho position from a benzene ring and two substituents substituted on the same carbon in an aliphatic ring can be interpreted as "adjacent" groups to each other. In addition, substituents connected to two consecutive carbons in an aliphatic ring (a total of four) can also be interpreted as "adjacent" groups.

[0106] In this specification, the expression "adjacent groups are bonded to each other to form a hydrocarbon ring" among substituents means that adjacent groups are bonded to each other to form a substituted or unsubstituted hydrocarbon ring.

[0107] In the present specification, the term "a 5- or 6-membered ring formed by bonding adjacent groups" means that the ring including the substituents participating in the formation of the ring is 5- or 6-membered. It may include the ring including the substituents participating in the formation of the ring being condensed with an additional ring.

[0108] As used herein, examples of halogen groups include fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).

[0109] As used herein, a silyl group is -SiY a Y b Y c wherein Y is a cyclic alkyl group; a , Y b and Y c may be hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

[0110] As used herein, the boron group is represented by -BY d Y e wherein Y d and Y e may be hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Specific examples of the boron group include, but are not limited to, a trimethyl boron group, a triethyl boron group, a tert-butyl dimethyl boron group, a triphenyl boron group, and a phenyl boron group.

[0111] In this specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the alkyl group has 1 to 30 carbon atoms. According to another embodiment, the alkyl group has 1 to 20 carbon atoms. According to still another embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an n-pentyl group, a hexyl group, an n-hexyl group, a heptyl group, an n-heptyl group, an octyl group, and an n-octyl group.

[0112] In this specification, the alkoxy group may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferable that the number of carbon atoms is 1 to 20. Specifically, the alkoxy group may be, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, etc.

[0113] The alkyl groups, alkoxy groups and other substituents containing alkyl moieties described herein include both straight-chain and branched-chain forms.

[0114] In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to still another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0115] In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 39 carbon atoms. According to one embodiment, the aryl group has 6 to 30 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, a terphenyl group, or a quaterphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, or a triphenylenyl group, but is not limited thereto.

[0116] As used herein, the fluorene group may be substituted, and two substituents may be bonded together to form a spiro structure.

[0117] When the fluorene group is substituted, [ka] Spirofluorene groups such as [ka] (9,9-dimethylfluorene group), and [ka] (9,9-diphenylfluorene group) or a substituted fluorene group, but is not limited thereto.

[0118] In the present specification, the heterocyclic group is a ring group containing at least one of heteroatoms N, O, P, S, Si and Se, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to one embodiment, the number of carbon atoms of the heterocyclic group is 2 to 36. Examples of the heterocyclic group include, but are not limited to, a pyridine group, a pyrrole group, a pyrimidine group, a quinoline group, a pyridazine group, a furan group, a thiophene group, an imidazole group, a pyrazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a benzocarbazole group, a benzonaphthofuran group, a benzonaphthothiophene group, an indenocarbazole group, and an indolocarbazole group.

[0119] In this specification, the above explanation regarding the heterocyclic group may be applied to the heteroaryl group, except that the heteroaryl group is aromatic.

[0120] As used herein, an amine group is defined as -NH 2 It can be selected from the group consisting of: alkylamine groups; N-alkylarylamine groups; arylamine groups; N-arylheteroarylamine groups; N-alkylheteroarylamine groups, and heteroarylamine groups, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include, but are not limited to, a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, an N-phenylnaphthylamine group, a ditolylamine group, an N-phenyltolylamine group, a triphenylamine group, an N-phenylbiphenylamine group, an N-phenylnaphthylamine group, an N-biphenylnaphthylamine group, an N-naphthylfluorenylamine group, an N-phenylphenanthrenylamine group, an N-biphenylphenanthrenylamine group, an N-phenylfluorenylamine group, an N-phenylterphenylamine group, an N-phenanthrenylfluorenylamine group, and an N-biphenylfluorenylamine group.

[0121] As used herein, an N-alkylarylamine group refers to an amine group in which the N of the amine group is substituted with an alkyl group and an aryl group.

[0122] As used herein, an N-arylheteroarylamine group refers to an amine group in which the N of the amine group is substituted with an aryl group and a heteroaryl group.

[0123] As used herein, an N-alkylheteroarylamine group refers to an amine group in which the N of the amine group is substituted with an alkyl group and a heteroaryl group.

[0124] In this specification, the alkyl group, aryl group and heteroaryl group in the alkylamine group, N-alkylarylamine group, arylamine group, N-arylheteroarylamine group, N-alkylheteroarylamine group and heteroarylamine group are the same as the above-mentioned exemplified alkyl group, aryl group and heteroaryl group, respectively.

[0125] In one embodiment of the present specification, the aromatic compound may have any of the following structures: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] .

[0126] The method for producing a deuterated aromatic compound of the present invention may further include replacing the air inside the reactor with nitrogen or an inert gas.

[0127] The present specification provides a deuteration reaction composition including an aromatic compound containing at least one hydrocarbon aromatic ring, heavy water, an organic compound that can be hydrolyzed by the heavy water, and an organic solvent.

[0128] The deuteration reaction composition can be based on the description of the solution in the above-mentioned preparation method.

[0129] The present specification provides deuterated aromatic compounds produced by the above-mentioned methods.

[0130] In one embodiment of the present specification, the deuterated aromatic compound refers to an aromatic compound substituted with at least one deuterium.

[0131] In one embodiment of the present specification, the deuterated aromatic compound includes a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group. In the present specification, the compound including the leaving group may be an intermediate of a final compound in an organic synthesis, and the leaving group means a reactive group that is eliminated based on the final compound or is chemically changed by binding with another reactant. Thus, the type of the leaving group and the position at which the leaving group is bound are determined depending on the method of organic synthesis and the position of the substituent of the final compound.

[0132] In the deuterated aromatic compounds herein, the leaving group is selected from the group consisting of a halogen group and a boronic acid group.

[0133] In the present specification, the deuterated aromatic compound containing a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group is any one of compounds represented by chemical formulas 7 to 10: [Chemical formula 7] [ka] [Chemical formula 8] [ka] [Chemical formula 9] [ka] [Chemical formula 10] [ka] In the above Chemical Formulas 7 to 10, at least one of A1 to A12 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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, which may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; at least one of B1 to B10 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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, which may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; at least one of Y1 to Y10 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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, which may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; At least one of Z1 to Z8 is deuterium, at least one is a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group, and the remaining 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 may be bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring.

[0134] The compounds of the above formulas 7 to 10 each have a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group.

[0135] The deuterated aromatic compound containing a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group is a compound having any one of the following structures, each of which is substituted with one or more deuterium atoms: [ka] [ka]

[0136] Theoretically, if all hydrogen in a deuterated compound is replaced with deuterium, i.e., the deuterium replacement rate is 100%, the life characteristics will be most ideally improved. However, there are problems such as extreme conditions being required due to steric hindrance, or the compound being destroyed by a side reaction before being deuterized, so in reality it is difficult to obtain a 100% deuterium replacement rate for all hydrogen in a compound. Even if a deuterium replacement rate approaching 100% can be obtained, it is not efficient in terms of investment when the time and cost of each step are taken into consideration.

[0137] In this specification, a deuterated compound having one or more deuterium atoms produced by a deuteration reaction is produced from a composition having two or more isotopes whose molecular weights differ depending on the number of substituted deuterium atoms, and therefore the position where deuterium is substituted in the structure is omitted.

[0138] In the compound of the above structure, at least one of the positions where hydrogen is omitted and is represented or substituted by hydrogen may be substituted by deuterium.

[0139] The present specification provides an electronic device comprising the above-mentioned deuterated aromatic compound.

[0140] The present specification provides a method for producing an electronic device, comprising the step of producing an electronic device using the deuterated aromatic compound described above.

[0141] The electronic device and the method for producing the electronic device may refer to the description of the composition, and a duplicated description will be omitted.

[0142] The electronic device is not particularly limited as long as it is an element in which the above-mentioned deuterated aromatic compound can be used, and may be, for example, an organic light-emitting device, an organic phosphorescent device, an organic solar cell, an organic photoreceptor, an organic transistor, or the like.

[0143] The electronic element includes a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, and at least one of the organic layers may include the deuterated aromatic compound described above.

[0144] The present specification provides an organic light-emitting device that includes the deuterated aromatic compound described above.

[0145] In one embodiment of the present specification, the organic light-emitting element includes a first electrode; a second electrode provided opposite to the first electrode; and an organic layer provided between the first electrode and the second electrode, the organic layer including the deuterated aromatic compound.

[0146] In one embodiment of the present specification, the organic layer includes a light-emitting layer including the deuterated aromatic compound.

[0147] The organic layer of the organic light-emitting device of the present specification may have a single-layer structure, or may have a multi-layer structure in which two or more organic layers are laminated. For example, the organic layer of the present specification may be composed of one to three layers. In addition, the organic light-emitting device of the present specification may have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. as the organic layer. However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number of organic layers.

[0148] When the organic light emitting device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

[0149] For example, the organic light emitting device of the present invention may be fabricated by sequentially stacking an anode, an organic layer, and a cathode on a substrate. In this case, a metal or a conductive metal oxide or an alloy thereof may be deposited on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form an anode, and an organic layer including a hole injection layer, a hole transport layer, an emitting layer, and an electron transport layer may be formed thereon, and a material usable as a cathode may be deposited thereon. In addition to this method, an organic light emitting device may be fabricated by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.

[0150] In addition, the deuterated aromatic compound may be formed in the organic layer by a solution coating method as well as a vacuum deposition method during the preparation of the organic light emitting device, where the solution coating method refers to, but is not limited to, spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc.

[0151] In one embodiment herein, the first electrode is an anode and the second electrode is a cathode.

[0152] According to another embodiment, the first electrode is a cathode and the second electrode is an anode.

[0153] In another embodiment, the organic light emitting device may be a normal type organic light emitting device having an anode, one or more organic layers, and a cathode sequentially laminated on a substrate.

[0154] In another embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate.

[0155] In the present specification, the materials of the cathode, the organic layer, and the anode are not particularly limited except that at least one organic layer contains a deuterated aromatic compound, and materials known in the art may be used.

[0156] In this specification, the above-mentioned deuterated aromatic compounds can be used in electronic devices such as organic phosphorescent devices, organic solar cells, organic photoconductors, organic transistors, etc., based on the same principles as those applied to organic light-emitting devices. For example, an organic solar cell has a structure including a cathode, an anode, and a photoactive layer provided between the cathode and the anode, and the photoactive layer may include the selected deuterated compound.

[0157] The present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrating the present invention and are not intended to limit the present invention.

[0158] [Example] [Example 1] Heavy water (D 2 35 ml of methanesulfonic anhydride and 30 ml of cyclohexane were placed in a flask, and 15 g of methanesulfonic anhydride and 5.0 g of 9-(naphthalene-1-yl)anthracene were slowly added dropwise to the flask. The mixture was then reacted 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. Potassium carbonate was then added to neutralize the mixture to a pH of 7-8. The organic layer was then separated and magnesium sulfate (MgSO 4) to remove residual moisture, then filtering and removing the solvent using a vacuum rotary evaporator to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0159] [Example 2] Using the same method as in Example 1, the organic solvent was changed from cyclohexane to methylcyclohexane to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0160] [Example 3] Using the same method as in Example 1, the organic solvent was changed from cyclohexane to 1,4-dioxane to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene. [Example 4] Using the same method as in Example 1, the organic solvent was changed from cyclohexane to 1,2-dimethoxyethane to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0161] [Example 5] Using the same method as in Example 1, the organic solvent was changed from cyclohexane to decalin to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0162] [Example 6] Heavy water (D 2Put 35 ml of methanesulfonic anhydride and 30 ml of toluene into the flask, then slowly add 15 g of methanesulfonic anhydride and 5.0 g of 9-phenylanthracene to the flask. Then, the reaction was carried out at 80°C for 18 hours. After the reaction was completed, the temperature was lowered to room temperature (25°C) and ethyl acetate was added. Then, potassium carbonate was added to neutralize the pH to 7-8. The organic layer was separated and magnesium sulfate (MgSO 4 After removing residual moisture using a vacuum rotary evaporator, the mixture was filtered and the solvent was removed using a vacuum rotary evaporator to obtain deuterium-substituted 9-phenylanthracene.

[0163] [Example 7] The same method as in Example 6 was used, except that the organic solvent was changed from toluene to xylene, thereby obtaining deuterium-substituted 9-phenylanthracene.

[0164] [Example 8] The same method as in Example 6 was used, except that the organic solvent was changed from toluene to chlorobenzene, to obtain deuterium-substituted 9-phenylanthracene.

[0165] [Example 9] The same method as in Example 6 was used, except that the organic solvent was changed from toluene to 1,2-dichlorobenzene, thereby obtaining deuterium-substituted 9-phenylanthracene.

[0166] [Example 10] The same method as in Example 6 was used, except that the organic solvent was changed from toluene to 1,2,4-trichlorobenzene, to obtain deuterium-substituted 9-phenylanthracene.

[0167] [Example 11] Heavy water (D 2 35 ml of 1,1,1-trichloroethane and 30 ml of 1,1,1-trichloroethane are placed in a flask, and 15 g of methanesulfonic anhydride and 5.0 g of 9-([1,1'-biphenyl]-4-yl)anthracene are slowly added dropwise. The mixture is then reacted at 80°C for 18 hours. After the reaction is complete, the temperature is lowered to room temperature (25°C) and ethyl acetate is added. Potassium carbonate is then added to neutralize the mixture to a pH of 7-8. The organic layer is separated and magnesium sulfate (MgSO 4 ) to remove residual moisture, then filtering and removing the solvent using a vacuum rotary evaporator to obtain deuterium-substituted 9-([1,1'-biphenyl]-4-yl)anthracene.

[0168] [Example 12] Using the same method as in Example 11, the organic solvent was changed from 1,1,1-trichloroethane to 1,1,2,2-tetrachloroethane, to obtain deuterium-substituted 9-([1,1'-biphenyl]-4-yl)anthracene.

[0169] [Example 13] Using the same method as in Example 11, the organic solvent was changed from 1,1,1-trichloroethane to 1,1,2,2-tetrachloroethylene, thereby obtaining deuterium-substituted 9-([1,1'-biphenyl]-4-yl)anthracene.

[0170] [Example 14] Using the same method as in Example 1, the anhydride was changed to trifluoroacetic anhydride instead of methanesulfonic anhydride to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0171] [Example 15] Using the same method as in Example 1, the anhydride was changed to acetic anhydride instead of methanesulfonic anhydride to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0172] [Example 16] Using the same method as in Example 1, the anhydride was changed to trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0173] [Comparative Example 1] This comparative example uses the non-deuterated compound, BH-A. [ka] (BH-A)

[0174] [Example 17] Heavy water (D 2 30 ml of methanesulfonic anhydride and 30 ml of cyclohexane are placed in a flask, and 50 g of methanesulfonic anhydride and 5.0 g of compound BH-A are slowly added dropwise. The reaction is then carried out at 80°C for 18 hours. After the reaction is complete, the temperature is lowered to room temperature (25°C) and ethyl acetate is added. Potassium carbonate is then added to neutralize the pH to 7-8. The organic layer is separated and magnesium sulfate (MgSO 4 ) to remove residual moisture, then filtered and the solvent was removed using a vacuum rotary evaporator to obtain deuterium-substituted compound BH-A.

[0175] [Example 18] Using the same method as in Example 1, the reactant was changed to 9-bromoanthracene instead of 9-(naphthalene-1-yl)anthracene to obtain deuterium-substituted 9-bromoanthracene.

[0176] [Comparative Example 2] 1g of 9-(naphthalene-1-yl)anthracene, heavy water (D 2 15 ml of toluene, 0.5 g of 10% Pt / C, and 10 ml of toluene solvent were placed in a high-pressure reactor, and the head of the reactor was covered to seal the inside. A gas containing hydrogen was blown into the reactants for 3 to 5 minutes per minute while stirring. The atmosphere in the reactor was then maintained as a gas atmosphere and the reaction was carried out at a temperature of 130°C for 24 hours. After completion, the temperature was lowered and the catalyst was removed by passing through a filter, followed by MgSO 4The deuterium oxide was removed using a rotary evaporator, and the mixture was filtered. The solvent was then removed using a rotary evaporator to obtain deuterium-substituted 9-(naphthalene-1-yl)anthracene.

[0177] [Comparative Example 3] A deuterium substitution reaction was carried out by adding 9-bromoanthracene instead of 9-(naphthalene-1-yl)anthracene in the same manner as in Comparative Example 2. As a result, 9-bromoanthracene substituted with deuterium was obtained, but it was confirmed that most of the anthracene was substituted with deuterium and had lost a bromine group.

[0178] [Experimental Example 1] The purity, deuterium substitution rate, and hydrogenated compound ratio were measured for Examples 1 to 18 and Comparative Examples 2 and 3, and the results are shown in Table 1 below.

[0179] The purity and the ratio of hydrogenated compounds were determined by dissolving the reacted sample in tetrahydrofuran solvent for HPLC and integrating the spectrum at a wavelength of 254 nm via HPLC. The mobile phase solvent used was a 5:5 mixture of acetonitrile and tetrahydrofuran, mixed with 1% formic acid, and water.

[0180] The sample after the deuteration reaction was quantified and dissolved in a solvent for NMR measurement to produce a sample sample, and an arbitrary compound whose peak does not overlap with the compound before the deuteration reaction was quantified in the same amount as the sample and dissolved in the same solvent for NMR measurement to produce an internal standard sample. 1 NMR measurement graphs were obtained using H-NMR.

[0181] 1When assigning H-NMR peaks, the internal standard peak was set to 1, and the relative integration value for each position of the sample after the deuteration reaction was calculated.

[0182] If all positions in the sample are replaced with deuterium after the deuteration reaction, no peaks related to hydrogen will appear, and the deuterium replacement rate will be determined to be 100%. On the other hand, if hydrogen at all positions is not replaced with deuterium, a peak for hydrogen that is not replaced with deuterium will appear.

[0183] Based on this, in this experiment, the deuterium substitution rate is calculated by subtracting the integral value of the peak due to unsubstituted hydrogen in the NMR measurement graph of the sample sample from the integral value of the peak related to hydrogen in the NMR measurement graph of the internal standard sample where deuterium is not substituted. This value is a relative integral value for each position, and represents the ratio of the peak that is substituted with deuterium and does not appear in the corresponding peak.

[0184] after that, 1 The substitution rate at each position of the sample was calculated using the weight of the sample and the weight of the internal standard used in preparing the H-NMR measurement sample, and the relative integral value.

[0185] [Table 1] [Table 1]

[0186] [Table 2]

[0187] In Examples 1 to 18, the reaction is carried out under acid conditions, so that the reaction can proceed at normal pressure without increasing the pressure. On the other hand, in Comparative Examples 2 and 3, the deuterium substitution reaction was carried out in a high-pressure reactor using a catalyst, and the deuterium substitution reaction only occurred at a pressure higher than normal pressure, at least 5 bar. Furthermore, when the reaction is carried out using 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, the side reaction products formed in this way are difficult to separate, and the yield is greatly reduced even during separation.

[0188] Example 18 and Comparative Example 3 are experiments in which the target compound had a leaving group. Although the starting materials were different, all of them contained a leaving group (-Br). Comparative Example 3 was an experiment in which deuterium was replaced at high pressure using a catalyst. These experiments were conducted to confirm whether the leaving group remained attached properly after the deuterium replacement reaction without falling off. In Example 18, the leaving group remained attached properly even after the deuterium replacement reaction, but in Comparative Example 3, a peak due to anthracene from which the bromine group, the leaving group, had fallen off was confirmed through HPLC-Mass analysis.

[0189] [Experimental Example 2] Comparison element example 1 A glass substrate coated with a 1,400 Å thick thin film of ITO (Indium Tin Oxide) was placed in distilled water containing detergent and ultrasonically cleaned. The detergent used was Decon (Fischer Co.). TM The CON705 product was used, and the distilled water used was distilled water that had been secondarily filtered through a 0.22μm sterilizing filter manufactured by Millipore Co. The ITO was washed for 30 minutes, then washed twice with distilled water, and ultrasonically cleaned for 10 minutes. After the distilled water washing was completed, the substrate was ultrasonically cleaned for 10 minutes each with isopropyl alcohol, acetone, and methanol solvents, dried, and then transferred to a plasma cleaner. The substrate was also cleaned for 5 minutes using oxygen plasma, and then transferred to a vacuum deposition machine.

[0190] On the ITO transparent electrode thus prepared, HT and PD were thermally vacuum deposited in a thickness of 100 Å in a weight ratio of 95:5 to form a hole injection layer, and then only the HT material was deposited in a thickness of 1100 Å to form a hole transport layer. On top of that, a compound represented by EB was thermally vacuum deposited in a thickness of 50 Å as an electron blocking layer. Then, BH-A and a compound represented by BD were vacuum deposited in a weight ratio of 96:4 to form a light emitting layer in a thickness of 200 Å. Then, ET and a compound represented by Liq were thermally vacuum deposited in a weight ratio of 1:1 to form a 360 Å as an electron transport layer, and then a compound represented by Liq was vacuum deposited in a thickness of 5 Å to form an electron injection layer. Magnesium and silver were sequentially deposited in a weight ratio of 10:1 to form a 220 Å thickness and aluminum was deposited in a thickness of 1000 Å on the electron injection layer to form a cathode, and an organic light emitting device was manufactured. [ka]

[0191] Element example 1 An organic light-emitting device was prepared in the same manner as in Comparative Device Example 1, except that the compound prepared in Example 17 (BH-A substituted with deuterium) was used instead of BH-A as the host compound of the light-emitting layer in Comparative Device Example 1.

[0192] Comparative element example 2 to comparative element example 3 An organic light-emitting device was produced in the same manner as in Comparative Experimental Example 1, except that the compounds shown in Table 2 were used instead of BH-A as the host compound in the light-emitting layer in Comparative Experimental Example 1. In Table 2 below, the compounds BH-B and BH-C are as follows. [ka]

[0193] A current was applied to the organic light-emitting devices manufactured in the previous Experimental Example and Comparative Experimental Example, and the voltage, efficiency, and lifespan (T95) were measured. The results are shown in Table 2 below. At this time, the voltage and efficiency were 10 mA / cm 2 The T95 value was measured at a current density of 20 mA / cm.2 This refers to the time it takes for the brightness to decrease to 95% of the initial brightness.

[0194] [Table 2] [Table 3]

Claims

1. The method includes a step of carrying out a deuteration reaction of the aromatic compound using a solution containing heavy water, an organic compound that can be hydrolyzed by the heavy water, an aromatic compound containing 1 to 30 hydrocarbon aromatic rings, and an organic solvent, The organic solvent is selected from the group consisting of a hydrocarbon chain substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an aliphatic hydrocarbon ring substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an aromatic hydrocarbon ring substituted or unsubstituted with a group selected from an alkyl group and a halogen group; an alkene compound substituted or unsubstituted with a group selected from an alkyl group and a halogen group; a straight or branched hetero chain; dioxane; and a substituted or unsubstituted aromatic hetero ring. The organic compound that can be hydrolyzed by heavy water includes at least one compound represented by the following chemical formulas 1 and 2: [Chemical formula 1] R1-C(O)OC(O)-R2 [Chemical formula 2] 2019-02-20 ２ )OS(O ２ )-R4 In the above Chemical Formulas 1 and 2, R1 is a substituent of the following chemical formula 5 or 6: R2 to R4 are the same or different and each independently represents a monovalent organic group that is unsubstituted or substituted with a halogen group; [Chemical formula 5] -(CH ２ ) ｌ (CF ２ ) ｍ (CF ３ ) ｎ (CH ３ ) １－ｎ [Chemical formula 6] -C(H) ａ ((CH ２ ) ｌ (CF ２ ) ｍ CF ３ ) ３－ａ In the above Chemical Formulas 5 and 6, l and m are each an integer from 0 to 10; n is 0, a is 0 or 1.

2. The method for producing a deuterated aromatic compound according to claim 1, wherein the organic solvent is selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, dioxane, diethyl ether, 1,2-dimethoxyethane, decalin, 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.

3. 3. The method for producing a deuterated aromatic compound according to claim 1, wherein the organic compound that can be hydrolyzed by heavy water includes at least one of trifluoromethanesulfonic anhydride, acetic anhydride, methanesulfonic anhydride, methyl acetate, ethyl acetate, and dimethylacetamide.

4. The step of carrying out a deuteration reaction of the aromatic compound includes: providing a solution containing an aromatic compound having 1 to 30 hydrocarbon aromatic rings, heavy water, an organic compound that can be hydrolyzed by the heavy water, and an organic solvent; and The method for producing a deuterated aromatic compound according to any one of claims 1 to 3, comprising a step of heating the solution to cause a deuteration reaction of the aromatic compound to proceed.

5. The method for producing a deuterated aromatic compound according to claim 4, wherein the temperature at which the solution is heated to cause the deuteration reaction of the aromatic compound to proceed is 80°C or higher and 140°C or lower.

Images