KR20230127935A - Method for preparing deuterated aromatic compounds and reactant composition of deuteration - Google Patents

Abstract

The present specification relates to a method for preparing a deuterated aromatic compound and a deuterated reaction composition.

Description

Method for producing deuterated aromatic compounds and deuterated reaction composition

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2022-0025256 filed with the Korean Intellectual Property Office on February 25, 2022, all of which are incorporated herein.

The present specification relates to a method for preparing a deuterated aromatic compound and a deuterated reaction composition.

Compounds containing deuterium are used for various purposes. For example, compounds containing deuterium are widely used not only as labeling compounds for identification of chemical reaction mechanisms or identification of metabolism, but also for drugs, pesticides, organic EL materials, and other purposes.

A method of substituting an aromatic compound with deuterium is known to improve the lifespan of an organic light emitting diode (OLED) material. The principle of this effect is that the LUMO energy of the C-D bond is lowered than that of the C-H bond when deuterium is substituted, thereby improving the lifetime characteristics of the OLED material.

When the deuteration reaction is performed on one or more aromatic compounds using the existing non-homogeneous catalytic reaction, there is a problem in that by-products due to side reactions are continuously generated. This is due to the hydrogenation reaction generated by hydrogen gas, and an attempt was made to increase the purity through a purification process after the reaction to remove it, but it was difficult to have high purity because there was no difference in terms of melting point or solubility from existing materials. In order to improve this, the reaction must be performed at a very high temperature (about 220 ° C. or more) to react without hydrogen gas, which may cause stability problems in the process.

The present specification is intended to provide a method for preparing a deuterated aromatic compound and a deuterated reaction composition.

An exemplary embodiment of the present specification proceeds with a deuteration reaction of the aromatic compound using a solution containing an aromatic compound containing one or more aromatic rings, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent. It includes the step of doing, wherein the organic solvent is a substituted or unsubstituted hydrocarbon chain; A substituted or unsubstituted aliphatic hydrocarbon ring; Or it provides a method for producing a deuterated aromatic compound selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon rings.

In addition, another exemplary embodiment of the present specification includes an aromatic compound including one or more aromatic rings, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent, wherein the organic solvent is a substituted or unsubstituted hydrocarbon. chain; A substituted or unsubstituted aliphatic hydrocarbon ring; Or it provides a deuteration reaction composition selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon rings.

In addition, the present specification provides a deuterated aromatic compound prepared by the above method.

In addition, the present specification provides an electric device including the deuterated aromatic compound.

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

The manufacturing method of the second embodiment according to the present specification has a high deuterium substitution rate.

The manufacturing method of the third embodiment according to the present specification has the advantage of high purity of the obtained compound.

In the manufacturing method of the fourth embodiment according to the present specification, a deuteration reaction is possible at a lower pressure.

In the manufacturing method of the fifth embodiment according to the present specification, a deuteration reaction is possible at a lower temperature.

Hereinafter, this specification will be described in detail.

An exemplary embodiment of the present specification proceeds with a deuteration reaction of the aromatic compound using a solution containing an aromatic compound containing one or more aromatic rings, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent. It includes the step of doing, wherein the organic solvent is a substituted or unsubstituted hydrocarbon chain; A substituted or unsubstituted aliphatic hydrocarbon ring; Or it provides a method for producing a deuterated aromatic compound selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon rings.

The method for producing a deuterated aromatic compound of the present specification is characterized in that there is no hydrogen supply step.

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

In order to remove the generated by-products, a process of increasing purity through a purification process after the reaction is required, and even if such a purification process is performed, it is difficult to manufacture with high purity because the by-products do not differ from the target material in terms of melting point or solubility.

The method for producing a deuterated aromatic compound of the present specification uses an organic compound that can be hydrolyzed by heavy water instead of a metal catalyst, which is a heterogeneous catalyst, and does not require a metal catalyst and a supply of hydrogen gas to activate it. It has the advantage of not generating impurities.

Meanwhile, when a metal catalyst is used during the deuteration reaction, the compound to be deuterated reacts with a reactive group, that is, a halogen group, a hydroxyl group, etc., so that the compound to be deuterated may react with the metal catalyst in the deuteration reaction using a metal catalyst There was no choice but to be limited to compounds having a reactive group with low reactivity or no reactive group.

Since the method for producing a deuterated aromatic compound of the present specification uses an organic compound capable of hydrolysis by heavy water instead of a metal catalyst, which is a heterogeneous catalyst, a compound having a reactive group such as a halogen group or a hydroxyl group can also be selected as a target compound for deuteration. can Specifically, after deuteration of an intermediate compound having a reactive group such as a halogen group or a hydroxyl group, a reaction of substituting an additional aromatic substituent into the reactive group may be performed.

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

The manufacturing method according to the present specification has the advantage of high purity of the obtained compound.

The manufacturing method according to the present specification is capable of deuteration reaction at a lower pressure.

The production method according to the present specification is capable of deuteration reaction at a lower temperature.

The method for preparing a deuterated aromatic compound of the present specification includes preparing a solution containing an aromatic compound containing at least one aromatic ring, heavy water (D ₂ O), an organic compound hydrolyzable by the heavy water, and an organic solvent. includes

Preparing a solution containing an aromatic compound containing one or more aromatic rings, heavy water (D ₂ O), an organic compound hydrolyzable by the heavy water, and an organic solvent includes one or more aromatic rings in a reactor. A solution containing an aromatic compound, heavy water (D ₂ O), an organic compound hydrolyzable by the heavy water, and an organic solvent is introduced, or an aromatic compound containing one or more aromatic rings, heavy water (D ₂ O), A solution may be prepared by individually introducing an organic compound and an organic solvent that can be hydrolyzed by heavy water into a reactor.

The organic compound capable of being hydrolyzed by heavy water is not particularly limited as long as it has a reactive group capable of being decomposed by heavy water, and may include, for example, at least one compound of Chemical Formulas 1 to 4 below.

[Formula 1]

R1-C(O)OC(O)-R2

[Formula 2]

R3-S(O ₂ )OS(O ₂ )-R4

[Formula 3]

R5-C(O)O-R6

[Formula 4]

R7-CONH-R8

In Chemical Formulas 1 to 4, R1 to R8 are the same as or different from each other, and each independently represents a monovalent organic group.

In an exemplary embodiment of the present specification, R1 and R2 may be the same substituent.

In an exemplary embodiment of the present specification, R3 and R4 may be the same substituent.

In an exemplary embodiment of the present specification, R5 and R6 may be the same substituent.

In one embodiment of the present specification, R7 and R8 may be the same substituent.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently an alkyl group unsubstituted or substituted with a halogen group; Or it may be an aryl group unsubstituted or substituted with a halogen group.

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

In an exemplary embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group; Alternatively, it may be an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a halogen group.

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

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

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently may be a substituent represented by Formula 5 or Formula 6 below.

[Formula 5]

-(CH ₂ ) _l (CF ₂ ) _m (CF ₃ ) _n (CH ₃ ) _1-n

[Formula 6]

-C(H) _a ((CH ₂ ) _l (CF ₂ ) _m CF ₃ ) _3-a

In Chemical Formulas 5 and 6, l and m are each an integer from 0 to 10, and n and a are each 0 or 1.

In an exemplary embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently may be a substituent represented by Formula 5.

In an exemplary embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently -CF ₃ , -CH ₂ CH ₃ or -CH ₃ may be.

In one embodiment of the present specification, the organic compound capable of hydrolysis by heavy water is trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, or acetic anhydride. And it may include at least one of methanesulfonic anhydride.

In one embodiment of the present specification, the organic compound hydrolyzable by heavy water may include trifluoromethanesulfonic anhydride.

In one embodiment of the present specification, the organic compound hydrolyzable by heavy water may include trifluoroacetic anhydride.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include acetic anhydride.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include methanesulfonic anhydride.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include trifluoromethanesulfonic anhydride and trifluoroacetic anhydride.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include trifluoromethanesulfonic anhydride and acetic anhydride.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include methanesulfonic anhydride and trifluoroacetic anhydride.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include trifluoromethanesulfonic anhydride and acetic anhydride.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include at least one of the compounds represented by Chemical Formulas 1 and 2. When at least one of the compounds of Chemical Formulas 1 and 2 is added to heavy water, hydrolysis with heavy water easily occurs even at room temperature.

In one embodiment of the present specification, the organic compound capable of hydrolysis by heavy water includes at least one of the compounds of Formulas 1 and 2, and further includes at least one of the compounds of Formulas 3 and 4. can When the organic compound capable of hydrolysis by heavy water includes at least one of the compounds of Formulas 1 and 2, at least one of the compounds of Formulas 3 and 4 having a relatively slow hydrolysis reaction is added to cause an exothermic reaction. The temperature generated by the phosphorus hydrolysis reaction can be controlled.

In one embodiment of the present specification, when the organic compound capable of hydrolysis by heavy water includes at least one of the compounds of Formulas 3 and 4, at least one of the compounds of Formulas 1 and 2 is further included. can do. The hydrolysis reaction can be accelerated by adding the compounds represented by Chemical Formulas 1 and 2, in which the hydrolysis reaction occurs relatively easily.

In the organic compound capable of being hydrolyzed by heavy water, the weight ratio of at least one of the compounds of Formulas 3 and 4 to at least one of the compounds of Formulas 1 and 2 is 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.

According to an exemplary embodiment according to the present specification, the content of the organic compound hydrolyzable by the heavy water may be 1 wt% or more and 70 wt% or less based on the total mass of the remaining components except for the aromatic compound in the composition. In this case, it is possible to increase the affinity between the aromatic compound and heavy water, which do not mix with each other, and has the advantage of increasing the deuterium substitution reactivity.

According to an exemplary embodiment according to the present specification, the solution includes an organic solvent.

When an organic solvent is not used, when the concentration of a hydrolyzed organic compound having deuterium is generated over a certain level by a hydrolysis reaction of an organic compound capable of hydrolysis, the deuterium-containing hydrolyzed organic compound generates small and medium and target substances. Phosphorus aromatic compounds are mixed with each other so that the deuterium substitution reaction occurs well.

However, since the organic compound hydrolyzed by heavy water itself is a super acid, the increase in the concentration of the hydrolyzed organic compound causes side reactions to occur easily, which can lower the purity. In addition, handling a solution containing a large amount of hydrolyzed organic compounds in a work-up process after the reaction may be dangerous in terms of stability.

On the other hand, compared to the deuteration reaction without an organic solvent, when an organic solvent is used together, the amount of organic compounds that can be hydrolyzed by heavy water can be reduced by 30 to 90%, resulting in increased purity and improved stability. can

At this time, the organic solvent that can be used for the reaction must be able to dissolve both the reactants and the reaction products under the reaction conditions.

When an organic solvent is not used, the concentration of deuterium-substituted trifluoromethanesulfonic acid formed by the hydrolysis reaction of added trifluoromethanesulfonic anhydride as an organic compound capable of hydrolysis by heavy water is As a result, the deuterium substitution reaction occurs well.

However, since trifluoromethanesulfonic acid itself is a super acid, an increase in the concentration of trifluoromethanesulfonic acid can also cause side reactions to occur, reducing purity. In addition, handling a solution containing a large amount of trifluoromethanesulfonic acid in a work-up process after the reaction may be dangerous in terms of stability.

On the other hand, when an organic solvent is used together, the amount of trifluoromethnae sulfonic anhydride used can be reduced by 30 to 90% compared to the conventional method, thereby increasing purity and improving stability.

The organic solvent may be a substituted or unsubstituted aliphatic hydrocarbon compound; And it may be selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon compounds. At this time, 'aromatic' refers to a compound in which pi electrons are delocalized by forming a ring by alternately connecting single bonds and double bonds. 'Aliphatic' refers to linear or cyclic and saturated and unsaturated hydrocarbon compounds other than aromatic hydrocarbon compounds. Specifically, the aliphatic hydrocarbon compound may have both a chain structure and a ring structure, and is a saturated aliphatic hydrocarbon when it consists of only a single bond, such as methane. It is an unsaturated aliphatic hydrocarbon if it contains a double or triple bond like ethylene. The main chain of the aliphatic hydrocarbon chain is a straight or branched hydrocarbon chain, and may be substituted with additional substituents.

The organic solvent may include a substituted or unsubstituted hydrocarbon chain; A substituted or unsubstituted aliphatic hydrocarbon ring; And it may be selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon ring. The organic solvent may include a hydrocarbon chain unsubstituted or substituted with an alkyl group or a halogen group; An aliphatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group; and an aromatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group.

In the present specification, the hydrocarbon chain 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 carbon number of the hydrocarbon chain is 1 to 30. According to another embodiment, the hydrocarbon chain has 1 to 20 carbon atoms. According to another embodiment, the hydrocarbon chain has 1 to 10 carbon atoms. Specific examples of the hydrocarbon chain include methane, ethane, propane, n-propane, isopropane, butane, n-butane, isobutane, tert-butane, pentane, n-pentane, hexane, n-hexane, heptane, n-heptane, octane, n-octane, etc. and may be further substituted.

In the present specification, the organic solvent is a substituted or unsubstituted hydrocarbon chain, and is a hydrocarbon chain substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted hydrocarbon chain having 1 to 60 carbon atoms, and a hydrocarbon chain having 1 to 60 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted hydrocarbon chain having 1 to 50 carbon atoms, and a hydrocarbon chain having 1 to 50 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted hydrocarbon chain having 1 to 40 carbon atoms, and a hydrocarbon chain having 1 to 40 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted hydrocarbon chain having 1 to 30 carbon atoms, and a hydrocarbon chain having 1 to 30 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted hydrocarbon chain having 1 to 20 carbon atoms, and a hydrocarbon chain having 1 to 20 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted hydrocarbon chain having 1 to 10 carbon atoms, and a hydrocarbon chain having 1 to 10 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the aliphatic hydrocarbon ring is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the aliphatic hydrocarbon ring has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the aliphatic hydrocarbon ring is 3 to 20. According to another embodiment, the carbon number of the aliphatic hydrocarbon ring is 3 to 6. Specifically, it may be cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, decalin, etc., and may be further substituted.

In the present specification, the organic solvent is a substituted or unsubstituted aliphatic hydrocarbon ring, and is a substituted or unsubstituted aliphatic hydrocarbon ring with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 60 carbon atoms, and an aliphatic hydrocarbon ring having 3 to 60 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 50 carbon atoms, and an aliphatic hydrocarbon ring having 3 to 50 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 40 carbon atoms, and an aliphatic hydrocarbon ring having 3 to 40 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 30 carbon atoms, and an aliphatic hydrocarbon ring having 3 to 30 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 20 carbon atoms, and an aliphatic hydrocarbon ring having 3 to 20 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 10 carbon atoms, and an aliphatic hydrocarbon ring having 3 to 10 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the aromatic hydrocarbon ring is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be monocyclic or polycyclic. According to one embodiment, the aromatic hydrocarbon ring has 6 to 39 carbon atoms. According to one embodiment, the aromatic hydrocarbon ring has 6 to 30 carbon atoms. Specific examples include benzene, naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, fluorene, and the like, and may be further substituted.

In the present specification, the organic solvent is a substituted or unsubstituted aromatic hydrocarbon ring, and is a substituted or unsubstituted aromatic hydrocarbon ring with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 60 carbon atoms, and an aromatic hydrocarbon ring having 6 to 60 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, and an aromatic hydrocarbon ring having 6 to 50 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 40 carbon atoms, and an aromatic hydrocarbon ring having 6 to 40 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, and an aromatic hydrocarbon ring having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 20 carbon atoms, and an aromatic hydrocarbon ring having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In the present specification, the organic solvent is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 10 carbon atoms, and an aromatic hydrocarbon ring having 6 to 10 carbon atoms substituted or unsubstituted with an alkyl group or a halogen group.

In order for the deuterium substitution reaction to occur well, heavy water, which is a source of heavy hydrogen, and an aromatic compound to be replaced with heavy hydrogen must be in one phase. However, heavy water and an aromatic compound, which is a target material, basically do not mix well.

When a certain amount of hydrolyzed organic compounds are generated, both heavy water and aromatic compounds are dissolved by the hydrolyzed organic compounds, and a deuterium substitution reaction occurs. For example, when a certain amount of trifluoromethanesulfonic acid, a super acid, is generated by hydrolysis, both heavy water and aromatic compounds are dissolved by trifluoromethanesulfonic acid, and deuterium substitution is performed. A reaction takes place.

In order to dissolve all substances added and produced in the deuterium substitution reaction, the organic solvent must be well mixed with heavy water and must be able to dissolve aromatic compounds to some extent.

As the organic solvent, an aliphatic hydrocarbon ring substituted with a halogen group rather than a hydrocarbon chain substituted with a halogen group; Or it is selected from the group consisting of an aromatic hydrocarbon ring substituted with a halogen group. Specifically, there is a risk of explosion when a hydrocarbon chain substituted with a strong base and a halogen group meet during a process using a strong base after the deuterium substitution process. In order to eliminate this risk of explosion, when a halogen-substituted organic solvent is selected as an organic solvent, an aliphatic hydrocarbon ring substituted with a halogen group; Alternatively, it is preferable to select an aromatic hydrocarbon ring substituted with a halogen group.

The organic solvent is decalin, cyclohexane, methylcyclohexane, ethylcyclohexane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene , 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene and 1,2,3,4-tetrachlorobenzene.

In one embodiment of the present specification, the organic solvent may be a single solvent or a mixed solvent in which two or more solvents are mixed. When the solvent of 2 is mixed as the organic solvent, the mixing ratio of the first solvent and the second solvent is 1:10 to 10:1, 1:9 to 9:1, 1:8 to 8:1, 1:7 to 7 :1, 1:6 to 6:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1 or 2:3 to 3:1. Specifically, when the solvent of 2 is mixed as the organic solvent, the mixing ratio of the first solvent and the second solvent may be 2 to 3:1 to 2.

If the content of the organic solvent is too large, the deuterium substitution rate is reduced, and conversely, if the content of the organic solvent is too small, the reactants are not well dissolved and the deuterium substitution rate is reduced. Preferably, the mass ratio of the organic solvent to the mass of the aromatic compound may be 4 to 40 times, specifically 4 to 16 times.

According to one embodiment according to the present specification, the solution is characterized in that it does not contain a metal catalyst, and an organic compound capable of hydrolysis by heavy water performs its role instead. Through this, problems caused by adding a metal catalyst, for example, the need to supply hydrogen gas, the need to remove impurities by hydrogen gas, and process equipment that can maintain and withstand high reaction temperature and high pressure What needs to be done is addressed.

According to one embodiment according to the present specification, the solution includes heavy water.

According to one embodiment according to the present specification, the content of the heavy water may be 0.1 times or more and 30 times or less of the weight of the aromatic compound. In this case, there is an advantage in that deuterium can be efficiently replaced from heavy water.

According to one embodiment according to the present specification, the solution may include an additional deuterium source together with deuterated water. The deuterium source may be a deuterated aromatic solvent, for example, benzene-d6 or toluene-d8.

According to one embodiment according to the present specification, the content of the additional deuterium source may be 0.1 times or more and 30 times or less of the weight of the aromatic compound. In this case, there is an advantage in that reactivity can be increased and exotherm can be reduced during the reaction.

In one embodiment of the present specification, the aromatic compound is an aromatic compound containing one or more aromatic rings, and specifically, an aromatic compound containing 1 or more and 30 or less aromatic rings. At this time, the meaning of one or more aromatic rings may include one or more monocyclic, polycyclic, or a combination of aromatic rings, or one or more basic aromatic rings (eg, benzene rings). For example, a carbazole ring means one aromatic ring, or means that two benzene rings are connected or three rings containing a benzene ring are condensed based on a benzene ring as a basic unit and a ring condensed therewith. can do.

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

In one embodiment of the present specification, the aromatic ring may be a substituted or unsubstituted monocyclic or polycyclic hydrocarbon aromatic ring, or a substituted or unsubstituted monocyclic or polycyclic heteroaromatic ring. For example, the 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 dibenzofuran, or a substituted or unsubstituted dibenzothiophene. , substituted or unsubstituted carbazole, and the like.

In one embodiment of the present specification, the aromatic compound may be a heteroaromatic compound, and the heteroaromatic compound may be a carbazole-based compound, a dibenzofuran-based compound, a dibenzothiophene-based compound, a pyridine-based compound, or a pyrimidine-based compound. , or may be a triazine-based compound. The heteroaromatic compound refers to a compound containing heterogeneous elements such as O, S, N, Si, P, Se, etc. in addition to carbon constituting the backbone, and hydrogen substituted on the backbone may be substituted with another substituent. The kind of substituent is not specifically limited.

In one embodiment of the present specification, the heteroaromatic compound is a compound containing at least one of O, S and N, and a substituted or unsubstituted heteroaromatic ring.

In one embodiment of the present specification, the heteroaromatic compound is a compound containing a heteroaromatic ring containing a substituted or unsubstituted oxygen atom.

In one embodiment of the present specification, the heteroaromatic compound is a compound containing a heteroaromatic ring containing a substituted or unsubstituted nitrogen atom.

In one embodiment of the present specification, the heteroaromatic compound is a compound containing a heteroaromatic ring containing a substituted or unsubstituted sulfur element.

In one embodiment of the present specification, the heteroaromatic compound may be a carbazole-based compound, specifically substituted or unsubstituted carbazole; or a substituted or unsubstituted carbazole having an additional ring to which an adjacent group is bonded.

Carbazole having an additional ring to which the adjacent group is bonded may be substituted or unsubstituted benzocarbazole; Substituted or unsubstituted dibenzocarbazole; Substituted or unsubstituted furocarbazole; Or it may be a substituted or unsubstituted indolocarbazole.

In one embodiment of the present specification, the heteroaromatic compound may be a dibenzofuran-based compound, specifically substituted or unsubstituted dibenzofuran; Or it may be a substituted or unsubstituted dibenzofuran having an additional ring to which adjacent groups are bonded.

In one embodiment of the present specification, the heteroaromatic compound may be a dibenzothiophene-based compound, specifically substituted or unsubstituted dibenzothiophene; or a substituted or unsubstituted dibenzothiophene having an additional ring to which an adjacent group is bonded.

In one embodiment of the present specification, the heteroaromatic compound is a substituted or unsubstituted indole; A substituted or unsubstituted benzofuran; A substituted or unsubstituted benzothiophene; Substituted or unsubstituted benzoxazole; Substituted or unsubstituted benzothiazole; substituted or unsubstituted benzoimidazole; A substituted or unsubstituted anthraquinone; substituted or unsubstituted xanthen; Substituted or unsubstituted thioxanthen; substituted or unsubstituted pyridine; A substituted or unsubstituted pyrimidine; A substituted or unsubstituted triazine; or dihydroindolocarbazole.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and in the case of two or more substitutions , Two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" refers to a halogen group; nitrile group; nitro group; hydroxy group; amine group; silyl group; boron group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, or is substituted with a substituent in which two or more substituents from among the above exemplified substituents are connected, or does not have any substituents. For example, “a substituent in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

In the present specification, the silyl group may be represented by a chemical formula of -SiY _a Y _b Y _c , wherein Y _a , Y _b and Y _c are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like, but is not limited thereto. don't

In the present specification, the boron group may be represented by the chemical formula -BY _d Y _e , wherein Y _d and Y _e are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The boron group specifically includes, but is not limited to, a dimethyl boron group, a diethyl boron group, a tert-butylmethyl boron group, a diphenyl boron group, a phenyl boron group, and the like.

In the present specification, the alkyl group may be straight or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 30. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -Hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, etc., but is not limited thereto.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, 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., but is not limited thereto. .

Alkyl groups, alkoxy groups, and substituents containing other alkyl moieties described herein include both straight-chain and branched forms.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, there are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but are not limited thereto.

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 number of carbon atoms of the aryl group is 6 to 39. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto no.

In the present specification, the fluorene group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

When the fluorene group is substituted, , spirofluorene groups such as; (9,9-dimethylfluorene group), and It may be a substituted fluorene group such as (9,9-diphenylfluorene group). However, it is not limited thereto.

In the present specification, the heterocyclic group is a ring group containing one or more of N, O, P, S, Si and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. According to one embodiment, the carbon number of the heterocyclic group is 2 to 36. Examples of the heterocyclic group include 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, but are not limited thereto.

In the present specification, the heterocyclic group described above may be applied except that the heteroaryl group is aromatic.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-biphenylnaphthylamine group , N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenane A trenyl fluorenyl amine group, an N-biphenyl fluorenyl amine group, and the like, but are not limited thereto.

In the present specification, the N-alkylarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and an aryl group.

In the present specification, the N-arylheteroarylamine group refers to an amine group in which N of the amine group is substituted with an aryl group and a heteroaryl group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and a heteroaryl group.

In the present specification, an alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine group; The alkyl, aryl and heteroaryl groups in the N-alkylheteroarylamine group and the heteroarylamine group are the same as the above-mentioned alkyl groups, aryl groups and heteroaryl groups, respectively.

In one embodiment of the present specification, the aromatic compound to participate in the deuteration reaction may be any one of Formulas 7 to 10 below. Through the deuteration reaction, at least one hydrogen in the selected compound is replaced with deuterium.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 7 to 10,

X, X1 and X2 are each independently O, S or NR;

R is hydrogen; heavy hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

A1 to A8 are each independently hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

B1 to B5 are each independently hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

E1 to E3 are each independently hydrogen; degassing; 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,

Y1 to Y6 are each independently hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

At least one of Z1 to Z3 is N, and the others are each independently CH or N,

b5 is an integer from 1 to 6, and when b5 is 2 or more, B5 is the same as or different from each other;

y5 is 1 or 2, and when y5 is 2, Y5 are the same as or different from each other,

y6 is an integer of 1 to 4, and when y6 is 2 or more, Y6 are the same as or different from each other.

In one embodiment of the present specification, X is O.

In one embodiment of the present specification, X is S.

In one embodiment of the present specification, X is NR, R is hydrogen; heavy hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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.

In one embodiment of the present specification, X is NR, R is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, at least one of A1 to A8 is a leaving group; hydroxyl group; A substituted or unsubstituted amine group; or a cyano group, and the others are each 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 heterocyclic group.

In one embodiment of the present specification, at least one of B1 to B5 is a leaving group; hydroxyl group; A substituted or unsubstituted amine group; or a cyano group, and the others are each 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 heterocyclic group.

In one embodiment of the present specification, at least one of Y1 to Y6 is a leaving group; hydroxyl group; A substituted or unsubstituted amine group; or a cyano group, and the others are each 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 heterocyclic group.

In one embodiment of the present specification, any one of Z1 to Z3 is N, and the others are CH.

In one embodiment of the present specification, two of Z1 to Z3 are N and the others are CH.

In one embodiment of the present specification, all of Z1 to Z3 are N.

In one embodiment of the present specification, at least one of E1 to E3 is a leaving group, and the others are each independently hydrogen; degassing; 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.

In one embodiment of the present specification, the aromatic compound may have any one of the following structures.

Here, L 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.

The method for producing a deuterated aromatic compound of the present specification may further include replacing the internal air of the reactor with nitrogen or an inert gas.

In the step of deuterating the aromatic compound, deuteration may be performed at room temperature without applying heat or by heating the solution. At this time, the room temperature may be a natural temperature without heating or cooling, specifically in the range of 20 ± 5 ° C.

In the method for producing a deuterated aromatic compound of the present specification, the step of proceeding the deuteration reaction of the aromatic compound,

Preparing a solution containing an aromatic compound containing at least one aromatic ring, heavy water (D ₂ O), an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent; and

The step of heating the solution to proceed with the deuteration reaction of the aromatic compound may be included.

In the step of heating the reactor to deuterate the aromatic compound, the solution is heated to 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, Alternatively, it may be a step of heating to a temperature of 80 ° C or higher, and specifically a step of heating to a temperature of 80 ° C or higher and 140 ° C or lower.

At this time, the deuterium reaction time is reacted for 3 hours or more after completing the temperature increase. Specifically, the deuterium reaction may be reacted for 3 hours or more and 24 hours or less after completing the temperature increase, and preferably for 6 hours or more and 18 hours or less.

The method for preparing a deuterated aromatic compound of the present specification further includes obtaining the deuterated aromatic compound after the deuteration step. The method for obtaining may be performed by a method known in the art, and is not particularly limited.

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 is 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%.

The higher the purity of the obtained deuterated aromatic compound, the better. Specifically, the purity of the obtained deuterated aromatic compound is 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%.

The present specification provides a deuterated aromatic compound prepared by the above-described production method.

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

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 of organic synthesis, and the leaving group refers to a reactive group that is chemically changed by being eliminated from the final compound or combined with other reactants. Accordingly, the type of the leaving group and the position at which the leaving group is bound are determined according to the method of organic synthesis and the position of the substituent in the final compound.

In one embodiment of the present specification, the leaving group may be selected from the group consisting of a halogen group and a boronic acid group.

In one embodiment of the present specification, the deuterated aromatic compound including a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group may be any one of Formulas 7 to 10 below. .

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 7 to 10,

X, X1 and X2 are each independently O, S or NR;

R is hydrogen; heavy hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

At least one of A1 to A8 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 others are each independently hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; cyano group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

At least one of B1 to B5 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 others are each independently hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

At least one of E1 to E3 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 others are each independently hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

At least one of Y1 to Y6 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 others are each independently hydrogen; degassing; hydroxyl group; A substituted or unsubstituted amine group; 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,

At least one of Z1 to Z3 is N, and the others are each independently CH or N,

b5 is an integer from 1 to 6, and when b5 is 2 or more, B5 is the same as or different from each other;

y5 is 1 or 2, and when y5 is 2, Y5 are the same as or different from each other,

y6 is an integer of 1 to 4, and when y6 is 2 or more, Y6 are the same as or different from each other.

In one embodiment of the present specification, the compounds of Chemical 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.

In one embodiment of the present specification, the deuterated aromatic compound including a substituent selected from the group consisting of a leaving group, a hydroxyl group, a substituted or unsubstituted amine group, and a cyano group has any one of the following structures, each of which structure is substituted with one or more deuterium.

Here, L 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.

Theoretically, when all hydrogens of the deuterated compound are replaced with deuterium, that is, when the deuterium substitution rate is 100%, the lifespan characteristic is improved most ideally. However, there are problems such as extreme conditions required due to steric hindrance or the compound being destroyed before deuteration due to side reactions. Even if it is obtained closely, the investment efficiency is not good considering the time and cost of the process.

In the present specification, since a deuterated compound having one or more deuterium atoms produced through a deuteration reaction is prepared as a composition having two or more isotopes having different molecular weights depending on the number of deuterium atoms substituted, the positions where deuterium atoms are substituted in the above structure are omitted. do.

In the compound of the above structure, at least one of the positions where the hydrogen indicated or substituted by hydrogen is omitted may be substituted with deuterium.

The present specification provides a deuteration reaction composition including an aromatic compound including at least one aromatic ring, heavy water (D ₂ O), an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent.

The deuterated reaction composition may refer to the description of the solution in the above-described preparation method.

In one embodiment of the present specification, the organic compound capable of being hydrolyzed by heavy water may include at least one compound of Chemical Formulas 1 to 4 below.

[Formula 1]

R1-C(O)OC(O)-R2

[Formula 2]

R3-S(O ₂ )OS(O ₂ )-R4

[Formula 3]

R5-C(O)O-R6

[Formula 4]

R7-CONH-R8

In Formulas 1 to 4,

R1 to R8 are the same as or different from each other, and are each independently a monovalent organic group.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently an alkyl group unsubstituted or substituted with a halogen group; Or it may be an aryl group unsubstituted or substituted with a halogen group.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently may be a substituent represented by Formula 5 or Formula 6 below.

[Formula 5]

-(CH ₂ ) _l (CF ₂ ) _m (CF ₃ ) _n (CH ₃ ) _1-n

[Formula 6]

-C(H) _a ((CH ₂ ) _l (CF ₂ ) _m CF ₃ ) _3-a

In Formulas 5 and 6,

l and m are each an integer from 0 to 10;

n and a are each 0 or 1.

In one embodiment of the present specification, the organic compound capable of hydrolysis by heavy water is trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, or acetic anhydride. And it may include at least one of methanesulfonic anhydride.

The organic solvent may be a substituted or unsubstituted aliphatic hydrocarbon compound; And it may be selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon compounds.

The organic solvent may include a substituted or unsubstituted hydrocarbon chain; A substituted or unsubstituted aliphatic hydrocarbon ring; And it may be selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon ring. The organic solvent may include a hydrocarbon chain unsubstituted or substituted with an alkyl group or a halogen group; An aliphatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group; and an aromatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group.

As the organic solvent, an aliphatic hydrocarbon ring substituted with a halogen group rather than a hydrocarbon chain substituted with a halogen group; Or it is selected from the group consisting of an aromatic hydrocarbon ring substituted with a halogen group. Specifically, there is a risk of explosion when a hydrocarbon chain substituted with a strong base and a halogen group meet during a process using a strong base after the deuterium substitution process. In order to eliminate this risk of explosion, when a halogen-substituted organic solvent is selected as an organic solvent, an aliphatic hydrocarbon ring substituted with a halogen group; Alternatively, it is preferable to select an aromatic hydrocarbon ring substituted with a halogen group.

The organic solvent is chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-trichlorobenzene, It may be selected from the group consisting of 3,5-trichlorobenzene and 1,2,3,4-tetrachlorobenzene.

The present specification provides an electronic device including the deuterated aromatic compound described above.

The present specification provides a method for manufacturing an electronic device including the step of manufacturing an electronic device using the above-described deuterated aromatic compound.

The electronic device and the manufacturing method of the electronic device may refer to the description of the composition, and duplicate descriptions will be omitted.

The electronic device is not particularly limited as long as it can use the above-described deuterated aromatic compound, and may be, for example, an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor, or an organic transistor.

The electronic device may include a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, and one or more layers of the organic material layers may include the above-described deuterated aromatic compound.

The present specification provides an organic light emitting device including the deuterated aromatic compound described above.

In one embodiment of the present specification, the organic light emitting device includes a first electrode; a second electrode provided to face the first electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes the deuterated aromatic compound.

In one embodiment of the present specification, the organic material layer includes a light emitting layer including the deuterated aromatic compound.

The organic material 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 material layers are stacked. For example, the organic material layer of the present specification may be composed of 1 to 3 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, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

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

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or conductive metal oxide or alloy thereof on the substrate to form an anode And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound of Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method during the manufacture of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

In one embodiment of the present specification, the first electrode is an anode and the second electrode is a cathode.

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

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

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

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

In this specification, the above-described deuterated aromatic compound may be used in electronic devices including organic phosphorescent devices, organic solar cells, organic photoreceptors, organic transistors, and the like, in a similar principle to that applied to organic light emitting devices. For example, the organic solar cell may have a structure including a cathode, an anode, and a photoactive layer provided between the cathode and anode, and the photoactive layer may include the selected deuterated compound.

Hereinafter, the present specification will be described in more detail through examples. However, the following examples are only for exemplifying the present specification, and are not intended to limit the present specification.

[Example]

[Example 1]

In the flask, 5 g of 11,12-dihydroindolo [2,3-a] carbazole, 30 ml of heavy water (D ₂ O), methanesulfonic anhydride 10 g of anhydride and 40 ml of chlorobenzene were added, stirred at room temperature for 1 hour, and then reacted at 120° C. for 18 hours. After completion of the reaction, the temperature was lowered to 5° C. or less, and potassium carbonate was added to neutralize the pH to 7-8. After washing with water, residual moisture is removed with magnesium sulfate (MgSO ₄ ), and then filtered and the solvent is removed using a vacuum rotary evaporator to obtain deuterium-substituted 11,12-dihydroindolo [2, 3-a]carbazole (11,12-dihydroindolo[2,3-a]carbazole) was obtained.

[Example 2]

Using the same method as in Example 1, but changing the organic solvent to 1,2-dichlorobenzene instead of chlorobenzene, 11, 12-dihydroindolo [2] substituted with deuterium ,3-a] carbazole (11,12-dihydroindolo [2,3-a] carbazole) was obtained.

[Example 3]

Using the same method as in Example 1, but changing the organic solvent to 1,2,4-trichlorobenzene instead of chlorobenzene, 11, 12-dihydroindole substituted with deuterium Rho[2,3-a]carbazole (11,12-dihydroindolo [2,3-a]carbazole) was obtained.

[Example 4]

The same method as in Example 1 was used, but the hydrolysis compound was changed to trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride to produce 11,12-dihydroindole substituted with deuterium. [2,3-a] carbazole (11,12-dihydroindolo [2,3-a] carbazole) was obtained.

[Example 5]

The same method as in Example 1 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2-dichloro instead of chlorobenzene It was changed to benzene (1,2-dichlorobenzene) to obtain deuterium-substituted 11,12-dihydroindolo [2,3-a] carbazole (11,12-dihydroindolo [2,3-a] carbazole) .

[Example 6]

The same method as in Example 1 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2,4 instead of chlorobenzene - 11, 12-dihydroindolo [2,3-a] carbazole (11,12-dihydroindolo [2,3-a ]carbazole) was obtained.

[Example 7]

5 g of 3-bromocarbazole, 24 ml of heavy water (D ₂ O), 7.1 g of methanesulfonic anhydride and 30 ml of chlorobenzene were added to the flask, stirred at room temperature for 1 hour, and then heated to 110 ° C. was reacted for 18 hours. After completion of the reaction, the temperature was lowered to 5° C. or less, and potassium carbonate was added to neutralize the pH to 7-8. After washing with water, residual moisture is removed with magnesium sulfate (MgSO ₄ ), and then filtered and the solvent is removed using a vacuum rotary evaporator to obtain deuterium-substituted 3-bromocarbazole. got it

[Example 8]

Using the same method as in Example 7, but changing the organic solvent to 1,2-dichlorobenzene instead of chlorobenzene, 3-bromocarbazole substituted with deuterium got

[Example 9]

Using the same method as in Example 7, but changing the organic solvent to 1,2,4-trichlorobenzene instead of chlorobenzene, 3-bromocarbazole substituted with deuterium (3-bromocarbazole) was obtained.

[Example 10]

The same method as in Example 7 was used, but the hydrolysis compound was changed to trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride to obtain deuterium-substituted 3-bromocarbazole (3- bromocarbazole) was obtained.

[Example 11]

The same method as in Example 7 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2-dichloro instead of chlorobenzene By changing to benzene (1,2-dichlorobenzene), deuterium-substituted 3-bromocarbazole was obtained.

[Example 12]

The same method as in Example 7 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2,4 instead of chlorobenzene - It was changed to trichlorobenzene (1,2,4-trichlorobenzene) to obtain 3-bromocarbazole substituted with deuterium.

[Example 13]

The same method as in Example 7 was used, but the organic solvent was changed to use 30 ml of chlorobenzene and 10 ml of decalin (3: 1) instead of chlorobenzene, so that deuterium-substituted 3-broth Mocarbazole (3-bromocarbazole) was obtained.

[Example 14]

The same method as in Example 7 was used, but the organic solvent was changed to using 30 ml of chlorobenzene and 10 ml of methylcyclohexane (3: 1) instead of chlorobenzene, thereby deuterium-substituted 3 -Bromocarbazole (3-bromocarbazole) was obtained.

[Example 15]

The same method as in Example 7 was used, but the organic solvent was 1,2,4-trichlorobenzene (1,2,4-trichlorobenzene) 30ml and methylcyclohexane (methylcyclohexnae) 20ml (3: 2 ) was changed to use together to obtain deuterium-substituted 3-bromocarbazole.

[Example 16]

The same method as in Example 7 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was chlorobenzene instead of chlorobenzene. 30 ml and 10 ml (3: 1) of decalin were used together to obtain deuterium-substituted 3-bromocarbazole.

[Example 17]

The same method as in Example 7 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was chlorobenzene instead of chlorobenzene. 30ml and 10ml (3:1) of methylcyclohexane were used together to obtain deuterium-substituted 3-bromocarbazole.

[Example 18]

The same method as in Example 7 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2,4 instead of chlorobenzene - Trichlorobenzene (1,2-dichlorobenzene) 30ml and methylcyclohexane (methylcyclohexane) 20ml (3: 2) was changed to use together to obtain 3-bromocarbazole substituted with deuterium.

[Example 19]

5 g of 2-bromodibenzofuran, 18 ml of heavy water (D ₂ O), 7.1 g of methanesulfonic anhydride and 30 ml of chlorobenzene were added to the flask, and after stirring at room temperature for 1 hour, the temperature was 130 The reaction was carried out for 18 hours at ° C. After completion of the reaction, the temperature was lowered to 5° C. or less, and potassium carbonate was added to neutralize the pH to 7-8. After washing with water, removing residual moisture with magnesium sulfate (MgSO ₄ ), filtering and removing the solvent using a vacuum rotary evaporator to obtain deuterium-substituted 2-bromodibenzofuran got

[Example 20]

Using the same method as in Example 19, but changing the organic solvent to 1,2-dichlorobenzene instead of chlorobenzene, deuterium-substituted 2-bromodibenzofuran ) was obtained.

[Example 21]

Using the same method as in Example 19, but changing the organic solvent to 1,2,4-trichlorobenzene instead of chlorobenzene, 2-bromodibenzo substituted with deuterium Furan (2-bromodibenzofuran) was obtained.

[Example 22]

Using the same method as in Example 19, but changing the hydrolysis compound to trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, deuterium-substituted 2-bromodibenzofuran (2 -bromodibenzofuran) was obtained.

[Example 23]

The same method as in Example 19 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2-dichloro instead of chlorobenzene It was changed to benzene (1,2-dichlorobenzene) to obtain 2-bromodibenzofuran substituted with deuterium.

[Example 24]

The same method as in Example 19 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2,4 instead of chlorobenzene - It was changed to trichlorobenzene (1,2,4-trichlorobenzene) to obtain 2-bromodibenzofuran substituted with deuterium.

[Example 25]

In the flask, 2-chloro-4,6-diphenyl-1,3,5-triazine 5g, heavy water (D ₂ O) 22.4ml , 6.5 g of methanesulfonic anhydride and 30 ml of chlorobenzene were added, stirred at room temperature for 1 hour, and then reacted at 120° C. for 10 hours. After completion of the reaction, the temperature was lowered to 5° C. or less, and potassium carbonate was added to neutralize the pH to 7-8. After washing with water, residual water was removed with magnesium sulfate (MgSO ₄ ), and then filtered and the solvent was removed using a vacuum rotary evaporator to obtain deuterium-substituted 2-chloro-4,6-diphenyl- 1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) was obtained.

[Example 26]

Using the same method as in Example 25, but changing the organic solvent to 1,2-dichlorobenzene instead of chlorobenzene, 2-chloro-4,6-diphenyl substituted with deuterium -1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) was obtained.

[Example 27]

Using the same method as in Example 25, but changing the organic solvent to 1,2,4-trichlorobenzene instead of chlorobenzene, 2-chloro-4 substituted with deuterium ,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) was obtained.

[Example 28]

The same method as in Example 25 was used, but the hydrolysis compound was changed to trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride to obtain 2-chloro-4,6- substituted with deuterium. Diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) was obtained.

[Example 29]

The same method as in Example 25 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2-dichloro instead of chlorobenzene 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3, 5-triazine) was obtained.

[Example 30]

The same method as in Example 25 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2,4 instead of chlorobenzene - 2-chloro-4,6-diphenyl-1,3,5-triazine substituted with deuterium by changing to trichlorobenzene (1,2,4-trichlorobenzene) -1,3,5-triazine) was obtained.

[Example 31]

5 g of 2-bromodibenzothiophene, 22.8 ml of heavy water (D ₂ O), 6.6 g of methanesulfonic anhydride and 30 ml of chlorobenzene were added to the flask, and the mixture was stirred at room temperature for 1 hour. After that, the reaction was performed at 120° C. for 18 hours. After completion of the reaction, the temperature was lowered to 5° C. or less, and potassium carbonate was added to neutralize the pH to 7-8. After washing with water, residual moisture is removed with magnesium sulfate (MgSO ₄ ), and then filtered and the solvent is removed using a vacuum rotary evaporator to obtain deuterium-substituted 2-bromodibenzothiophene ) was obtained.

[Example 32]

Using the same method as in Example 31, but changing the organic solvent to 1,2-dichlorobenzene instead of chlorobenzene, deuterium substituted 2-bromodibenzofuran (2-bromodibenzothiophene ) was obtained.

[Example 33]

Using the same method as in Example 31, but changing the organic solvent to 1,2,4-trichlorobenzene instead of chlorobenzene, 2-bromodibenzo substituted with deuterium Thiophene (2-bromodibenzothiophene) was obtained.

[Example 34]

The same method as in Example 31 was used, but the hydrolysis compound was changed to trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride to obtain deuterium-substituted 2-bromodibenzothiophene ( 2-bromodibenzothiophene) was obtained.

[Example 35]

The same method as in Example 31 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2-dichloro instead of chlorobenzene. It was changed to benzene (1,2-dichlorobenzene) to obtain 2-bromodibenzothiophene substituted with deuterium.

[Example 36]

The same method as in Example 31 was used, but the hydrolysis compound was trifluoromethanesulfonic anhydride instead of methanesulfonic anhydride, and the organic solvent was 1,2,4 instead of chlorobenzene - It was changed to trichlorobenzene (1,2,4-trichlorobenzene) to obtain 2-bromodibenzothiophene substituted with deuterium.

[Comparative Example 1]

11, 12-dihydroindolo [2,3-a] carbazole (11,12-dihydroindolo [2,3-a] carbazole) 1g, heavy water (D ₂ O) 26ml, 10wt% Pd / C 0.2g, 10 ml of xylene was put into the high-pressure reactor and the head of the reactor was covered to seal the inside. While stirring, a gas containing 4% hydrogen was blown into the reaction mixture for 3 to 5 minutes per minute. Then, the atmosphere in the reactor maintained a gaseous atmosphere containing 4% hydrogen, and the reaction was performed at an oil bath temperature of 170° C. for 24 hours. After completion of the deuterium substitution reaction, the temperature is lowered, the inside of the reactor is substituted with outside air, and then the temperature of the oil bath is raised to 170° C., and the dehydrogenation reaction is performed for 17 hours. After completion of the dehydrogenation reaction, lower the temperature and filter to remove the catalyst, remove heavy water using MgSO ₄ , filter, remove the solvent using a vacuum rotary evaporator, and replace it with deuterium. 11,12-dihydroindolo [2,3-a] carbazole was obtained.

[Comparative Example 2]

The same method as in Comparative Example 1 was used, but the organic solvent was changed to ethylcyclohexane instead of xylene to obtain deuterium-substituted 11,12-dihydroindolo[2,3-a]carbazole ( 11,12-dihydroindolo [2,3-a] carbazole) was obtained.

[Comparative Example 3]

Using the same method as in Comparative Example 1, instead of 11,12-dihydroindolo [2,3-a] carbazole, 2-bromodibenzofuran ( 2-bromodibenzofuran) was subjected to deuterium substitution. As a result, 9-bromodibenzofuran substituted with deuterium was obtained, but dibenzofurane substituted with deuterium, which lost most of the bromine group, was confirmed.

[Experimental Example 1]

Purity, deuterium substitution rate, and hydrogenated compound ratio for Examples 1 to 36 and Comparative Examples 1 to 3 were measured, and the results are shown in Tables 1 and 2 below.

Purity and ratio of hydrogenated compounds were obtained by dissolving the reacted sample in tetrahydrofuran solvent for HPLC and integrating the spectrum at a wavelength of 254 nm through HPLC. At this time, as a mobile phase solvent, a mixture of acetonitrile and tetrahydrofuran in a ratio of 5:5 and 1% formic acid and water were used.

A sample sample obtained by quantifying a sample after the deuteration reaction and dissolving it in a solvent for NMR measurement, and an internal standard in which an arbitrary compound whose peak does not overlap with the compound before the deuteration reaction is quantified in the same amount as the sample and dissolved in the same solvent for NMR measurement. sample was made. NMR measurement graphs were obtained using ¹ H-NMR for each of the prepared sample and internal standard samples.

When assigning the ¹ H-NMR peak, the internal standard peak was set to 1 to obtain a relative integration value for each position of the deuterated sample.

If deuterium is substituted at all positions in the sample after the deuteration reaction, no peak related to hydrogen appears at all, and in this case, the deuterium substitution rate is determined to be 100%. On the other hand, if hydrogen at all positions is not substituted with deuterium, peaks of hydrogen that are not substituted with deuterium appear.

Based on this, in this experiment, the deuterium substitution rate is the integral value of the peak related to hydrogen in the NMR measurement graph of the internal standard sample in which deuterium is not substituted, and the integral value of the peak by unsubstituted hydrogen in the NMR measurement graph of the sample sample. find the value minus This value is a relative integration value for each position, and indicates the ratio of substitution with deuterium, which does not appear as a corresponding peak due to substitution with deuterium.

Then, the substitution rate for each position of the sample was calculated using the weight of the sample used to make the ¹ H-NMR measurement sample, the weight of the internal standard, and the relative integral value.

reactant organic solvent hydrolysis compound water
(%) Deuterium substitution rate (%) Hydrogenated Compound Ratio (%) reaction
temperature
(℃) reaction pressure
(bar) Example 1 11,12-dihydroindolo[2,3-a]carbazole chlorobenzene methanesulfonic
anhydride 98.1 86.9 0 120 normal pressure Example 2 11,12-dihydroindolo[2,3-a]carbazole 1,2-dichlorobenzene methanesulfonic
anhydride 97.5 82.4 0 120 normal pressure Example 3 11,12-dihydroindolo[2,3-a]carbazole 1,2,4-trichlorobenzene methanesulfonic
anhydride 98.7 82.1 0 120 normal pressure Example 4 11,12-dihydroindolo[2,3-a]carbazole chlorobenzene Trifluoromethanesulfonic Anhydride 94.7 83.5 0 120 normal pressure Example 5 11,12-dihydroindolo[2,3-a]carbazole 1,2-dichlorobenzene Trifluoromethanesulfonic Anhydride 95.1 84.9 0 120 normal pressure Example 6 11,12-dihydroindolo[2,3-a]carbazole 1,2,4-Trichlorobenzene Trifluoromethanesulfonic Anhydride 95.4 84.3 0 120 normal pressure Example 7 3-bromocarbazole chlorobenzene methanesulfonic
anhydride 92.3 69.8 0 110 normal pressure Example 8 3-bromocarbazole 1,2-dichlorobenzene methanesulfonic
anhydride 91.9 70.5 0 110 normal pressure Example 9 3-bromocarbazole 1,2,4-trichlorobenzene methanesulfonic
anhydride 92.7 71.7 0 110 normal pressure Example 10 3-bromocarbazole chlorobenzene Trifluoromethanesulfonic Anhydride 89.9 70.6 0 110 normal pressure Example 11 3-bromocarbazole 1,2-dichlorobenzene Trifluoromethanesulfonic Anhydride 90.6 71.2 0 110 normal pressure Example 12 3-bromocarbazole 1,2,4-trichlorobenzene Trifluoromethanesulfonic Anhydride 90.1 72.5 0 110 normal pressure Example 13 3-bromocarbazole chlorobenzene,
decalin methanesulfonic
anhydride 95.8 65.4 0 110 normal pressure Example 14 3-bromocarbazole chlorobenzene,
methylcyclohexane methanesulfonic
anhydride 94.4 67.2 0 110 normal pressure Example 15 3-bromocarbazole 1,2,4-trichlorobenzene;
methylcyclohexane methanesulfonic
anhydride 93.8 66.8 0 110 normal pressure Example 16 3-bromocarbazole chlorobenzene,
decalin Trifluoromethanesulfonic Anhydride 93.7 68.7 0 110 normal pressure Example 17 3-bromocarbazole chlorobenzene,
methylcyclohexane Trifluoromethanesulfonic Anhydride 93.2 69.1 0 110 normal pressure Example 18 3-bromocarbazole 1,2,4-trichlorobenzene;
methylcyclohexane Trifluoromethanesulfonic Anhydride 94.6 67.6 0 110 normal pressure Example 19 2-Bromodibenzofuran chlorobenzene methanesulfonic
anhydride 97.5 76.5 0 130 normal pressure Example 20 2-Bromodibenzofuran 1,2-dichlorobenzene methanesulfonic
anhydride 96.9 76.9 0 130 normal pressure Example 21 2-Bromodibenzofuran 1,2,4-trichlorobenzene methanesulfonic
anhydride 97.2 77.7 0 130 normal pressure Example 22 2-Bromodibenzofuran chlorobenzene Trifluoromethanesulfonic Anhydride 98.9 81.4 0 130 normal pressure Example 23 2-Bromodibenzofuran 1,2-dichlorobenzene Trifluoromethanesulfonic Anhydride 98.4 81.6 0 130 normal pressure Example 24 2-Bromodibenzofuran 1,2,4-trichlorobenzene Trifluoromethanesulfonic Anhydride 98.6 83.2 0 130 normal pressure Example 25 2-chloro-4,6-diphenyl-1,3,5-triazine chlorobenzene methanesulfonic
anhydride 96.8 73.4 0 120 normal pressure Example 26 2-chloro-4,6-diphenyl-1,3,5-triazine 1,2-dichlorobenzene methanesulfonic
anhydride 96.4 72.9 0 120 normal pressure Example 27 2-chloro-4,6-diphenyl-1,3,5-triazine 1,2,4-trichlorobenzene methanesulfonic
anhydride 96.2 73.2 0 120 normal pressure Example 28 2-chloro-4,6-diphenyl-1,3,5-triazine chlorobenzene Trifluoromethanesulfonic Anhydride 95.3 75.2 0 120 normal pressure Example 29 2-chloro-4,6-diphenyl-1,3,5-triazine 1,2-dichlorobenzene Trifluoromethanesulfonic Anhydride 94.7 76.5 0 120 normal pressure Example 30 2-chloro-4,6-diphenyl-1,3,5-triazine 1,2,4-trichlorobenzene Trifluoromethanesulfonic Anhydride 95.1 74.8 0 120 normal pressure Example 31 2-Bromodibenzothiophene chlorobenzene methanesulfonic
anhydride 98.8 71.2 0 120 normal pressure Example 32 2-Bromodibenzothiophene 1,2-dichlorobenzene methanesulfonic
anhydride 98.3 72.6 0 120 normal pressure Example 33 2-Bromodibenzothiophene 1,2,4-trichlorobenzene methanesulfonic
anhydride 97.7 71.8 0 120 normal pressure Example 34 2-Bromodibenzothiophene chlorobenzene Trifluoromethanesulfonic Anhydride 97.6 69.5 0 120 normal pressure Example 35 2-Bromodibenzothiophene 1,2-dichlorobenzene Trifluoromethanesulfonic Anhydride 97.5 70.9 0 120 normal pressure Example 36 2-Bromodibenzothiophene 1,2,4-trichlorobenzene Trifluoromethanesulfonic Anhydride 96.2 68.2 0 120 normal pressure

reactant organic solvent catalyst water
(%) Deuterium substitution rate (%) Hydrogenated Compound Ratio (%) reaction
temperature
(℃) reaction pressure
(bar) Comparative Example 1 11,12-dihydroindolo[2,3-a]carbazole xylene 10wt% Pd/C 98.1 83.7 4 170 6.4 Comparative Example 2 11,12-dihydroindolo[2,3-a]carbazole ethylcyclohexane 10wt% Pd/C 99.3 80.4 4 170 7.3 Comparative Example 3 2-Bromodibenzofuran xylene 10wt% Pd/C 98.9 88.2 4 170 6.8

Examples 1 to 6 use chlorobenzene, 1,2-dichlorobenzene or 1,2,4-trichlorobenzene as an organic solvent for 11,12-dihydroindolo[2,3-a]carbazole, respectively Then, a deuterium substitution reaction was performed using methanesulfonic anhydride or trifluoromethanesulfonic anhydride as a hydrolysis compound. Examples 7 to 12 use chlorobenzene, 1,2-dichlorobenzene or 1,2,4-trichlorobenzene as the organic solvent for 3-bromocarbazole, respectively, and methanesulfonic anhydride or triple as the hydrolysis compound. A deuterium substitution reaction was performed using loromethanesulfonic anhydride. Examples 13 to 18 use a solvent obtained by mixing chlorobenzene or 1,2,4-trichlorobenzene with decalin or methylcyclohexane as an organic solvent for 3-bromocarbazole, and the hydrolysis compound is methanesulfonic anhydride Alternatively, a deuterium substitution reaction was performed using trifluoromethanesulfonic anhydride. Examples 19 to 24 use chlorobenzene, 1,2-dichlorobenzene or 1,2,4-trichlorobenzene as an organic solvent for 2-bromodibenzofuran, and methanesulfonic anhydride or triple as a hydrolysis compound. A deuterium substitution reaction was performed using loromethanesulfonic anhydride. Examples 25 to 30 use chlorobenzene, 1,2-dichlorobenzene or 1,2,4-trichlorobenzene as an organic solvent for 2-chloro-4,6-diphenyl-1,3,5-triazine. and a deuterium substitution reaction was performed using methanesulfonic anhydride or trifluoromethanesulfonic anhydride as a hydrolysis compound. Examples 31 to 36 use chlorobenzene, 1,2-dichlorobenzene or 1,2,4-trichlorobenzene as organic solvents for 2-bromodibenzothiophene, and methanesulfonic anhydride or A deuterium substitution reaction was performed using trifluoromethanesulfonic anhydride.

Purity and deuterium substitution rate vary depending on the solubility of the reactant in an organic solvent and the solubility in deuterium that provides deuterium. A substituted or unsubstituted aliphatic hydrocarbon ring; And when a substituted or unsubstituted aromatic hydrocarbon ring is used as an organic solvent, the organic solvent and heavy water do not mix well. increases to dissolve the reactant.

In Examples 1 to 36, compounds having good solubility in organic solvents and affinity for deuterium tend to have higher substitution rates with deuterium. However, the purity tends to be slightly opposite to the deuterium substitution rate. The higher the solubility in organic solvents and heavy water, the better the reactivity, resulting in an increase in impurities due to side reactions. For this reason, it is necessary to optimize the reaction conditions for each material in order to increase both the deuterium substitution rate and purity. In Examples 13 to 18, a deuterium substitution reaction was performed using a halogen-substituted aromatic hydrocarbon ring compound and an aliphatic hydrocarbon ring compound together as an organic solvent. This is because when the experiment was conducted in the meantime, when using an aliphatic hydrocarbon ring compound, the deuterium substitution rate was slightly low, but the purity was high.

Since Examples 1 to 36 also reacted under acid conditions, the reaction proceeded at normal pressure without increasing the pressure. In Comparative Examples 1 to 3, deuterium substitution was performed in a high-pressure reactor using a catalyst, but the desired result could be obtained only when the deuterium substitution was performed at a pressure of at least 5 bar or higher than atmospheric pressure. In addition, when proceeding using a high-pressure reactor, a side reaction in which the double bond of the aromatic ring is partially reduced occurs, and the side reaction material formed in this way is difficult to separate, and even if it is separated, the yield is greatly reduced. In addition, the ratio of the hydrogenation compound used when substituting heavy hydrogen at high pressure was fixed at 4%. This is because more side reactions occur when the hydrogenation compound is 100%.

Examples 19 to 24 and Comparative Example 3 were tested on the same 2-bromodibenzofuran. This is the condition of substituting deuterium using a compound capable of hydrolysis by deuterium even when there is a leaving group such as bromine (Examples 19 to 24) and the condition of substituting deuterium at high pressure using a catalyst (Comparative Example 3). to compare the differences. In Examples 19 to 24, the leaving group was well attached even after the deuterium substitution reaction, but in Comparative Example 3, a peak due to naphthalene with some leaving bromine groups was confirmed through HPLC.

Claims (12)

Using a solution containing an aromatic compound containing at least one aromatic ring, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent, proceeding with a deuteration reaction of the aromatic compound,
The organic solvent may include a substituted or unsubstituted hydrocarbon chain; A substituted or unsubstituted aliphatic hydrocarbon ring; And a method for producing a deuterated aromatic compound selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon ring. The method according to claim 1, wherein the organic solvent is a hydrocarbon chain unsubstituted or substituted with an alkyl group or a halogen group; An aliphatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group; And a method for producing a deuterated aromatic compound selected from the group consisting of an aromatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group. The method according to claim 1, wherein the organic solvent is decalin, cyclohexane, methylcyclohexane, ethylcyclohexane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2, of a deuterated aromatic compound selected from the group consisting of 3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene and 1,2,3,4-tetrachlorobenzene manufacturing method. The method for preparing a deuterated aromatic compound according to claim 1, wherein the organic compound capable of being hydrolyzed by deuterated water includes at least one compound of Formulas 1 to 4 below:
[Formula 1]
R1-C(O)OC(O)-R2
[Formula 2]
R3-S(O ₂ )OS(O ₂ )-R4
[Formula 3]
R5-C(O)O-R6
[Formula 4]
R7-CONH-R8
In Formulas 1 to 4,
R1 to R8 are the same as or different from each other, and are each independently a monovalent organic group. The method according to claim 1, wherein the deuterated aromatic organic compound capable of hydrolysis by deuterated water includes at least one of trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride and methanesulfonic anhydride. A method for preparing the compound. The method according to claim 1, wherein the step of proceeding the deuteration reaction of the aromatic compound,
preparing a solution containing an aromatic compound containing at least one aromatic ring, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent; and
Method for producing a deuterated aromatic compound comprising the step of heating the solution to proceed with the deuteration reaction of the aromatic compound. An aromatic compound containing at least one aromatic ring, heavy water, an organic compound capable of being hydrolyzed by the heavy water, and an organic solvent,
The organic solvent may include a substituted or unsubstituted hydrocarbon chain; A substituted or unsubstituted aliphatic hydrocarbon ring; And a deuteration reaction composition selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon ring. The method according to claim 7, wherein the organic solvent is a hydrocarbon chain unsubstituted or substituted with an alkyl group or a halogen group; An aliphatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group; And a deuteration reaction composition selected from the group consisting of an aromatic hydrocarbon ring unsubstituted or substituted with an alkyl group or a halogen group. The method according to claim 8, wherein the organic solvent is decalin, cyclohexane, methylcyclohexane, ethylcyclohexane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2, A deuteration reaction composition selected from the group consisting of 3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene and 1,2,3,4-tetrachlorobenzene. The deuterated reaction composition according to claim 7, wherein the organic compound capable of being hydrolyzed by deuterated water includes at least one compound of Formulas 1 to 4 below:
[Formula 1]
R1-C(O)OC(O)-R2
[Formula 2]
R3-S(O ₂ )OS(O ₂ )-R4
[Formula 3]
R5-C(O)O-R6
[Formula 4]
R7-CONH-R8
In Formulas 1 to 4,
R1 to R8 are the same as or different from each other, and are each independently a monovalent organic group. The deuteration reaction of claim 7, wherein the organic compound capable of being hydrolyzed by deuterated water includes at least one of trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, acetic anhydride, and methanesulfonic anhydride. composition. A deuterated aromatic compound prepared by the method of any one of claims 1 to 6.