Method for producing deuterated anthracene compounds, reaction compositions, deuterated anthracene compounds, and compositions

Abstract

The present disclosure relates to a method for preparing a deuterated anthracene compound, which comprises reacting a halogenated benzene having at least one deuterium with an enolate to synthesize the deuterated anthracene compound, a reaction composition, a deuterated anthracene compound, and a composition.

Description

[Technical field]

[0001] This specification claims the benefit of the filing date of Korean Patent Application No. 10-2021-0016149, filed with the Korean Intellectual Property Office on February 4, 2021, the entire contents of which are incorporated herein by reference.

[0002] SUMMARY OF THE DISCLOSURE This disclosure relates to methods for making deuterated anthracene compounds, reaction compositions, deuterated anthracene compounds, and compositions. [Background technology]

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

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

[0005] In the case of anthracene derivatives used as materials for organic light-emitting devices, HOMO and LUMO are distributed in anthracene. When hydrogen in anthracene is deuterized, the vibrational energy in the molecule of CD bond is reduced compared to CH bond, which reduces the interaction between molecules and improves the life span of organic light-emitting devices.

[0006] Hydrogen-deuterium exchange is the most widely used technique for deuteration of aromatic compounds. Hydrogen-deuterium exchange uses organic solvents such as Aceton-d6, DMSO-d6, DMF-d7, MeOH-d4, Toluene-d5, Benzene-d6, or deuterium oxide (D2O) as a deuterium source, and is carried out using acid / base catalysts, supercritical heating, transition metal catalysts, etc. This hydrogen-deuterium exchange method requires that the material to be deuterized must withstand reaction conditions such as high temperature and high pressure, requires multiple treatments to achieve a high level of deuteration, and uses a large amount of relatively expensive deuteration reagents, making it inefficient in terms of cost and time.

[0007] In order to generalize deuterated aromatic compounds as materials for organic light-emitting devices, a production method that can reduce costs by using less deuterium source is required. Summary of the Invention [Problem to be solved by the invention]

[0008] The present disclosure is directed to methods for making deuterated anthracene compounds, reaction compositions, deuterated anthracene compounds, and compositions. [Means for solving the problem]

[0009] One embodiment of the present specification provides a method for producing a deuterated anthracene compound, comprising the step of reacting a halogenated benzene having at least one deuterium with an enolate represented by the following Chemical Formula 1 to synthesize a deuterated anthracene compound: [Chemical formula 1] [ka]

[0010] Another embodiment of the present specification provides a method for producing a deuterated anthracene compound, comprising reacting a halogenated benzene-d5 with an enolate of the following formula 1 to synthesize a compound of the following formula 2: [Chemical formula 1] [ka] [Chemical formula 2] [ka] In the above Chemical Formula 2, b is an integer of 1-8.

[0011] Another embodiment of the present disclosure provides a reaction composition comprising a halogenated benzene having at least one deuterium and an enolate of the following formula 1: [Chemical formula 1] [ka]

[0012] Another embodiment of the present disclosure provides a reaction composition that includes a halogenated benzene-d5, trimethyl(vinyloxy)silane, 2,2,6,6-tetramethylpiperidine, an alkyl lithium, and a solvent.

[0013] Another embodiment of the present specification provides a reaction composition including a halogenated benzene having at least one deuterium; a compound represented by the following formula 7 or 8; a base; an alkyl lithium; and a solvent. [Chemical formula 7] [ka] [Chemical formula 8] [ka] In the above Chemical Formulae 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

[0014] Another embodiment of the present specification provides a deuterated anthracene compound produced by the above-mentioned production method.

[0015] Another embodiment of the present disclosure provides a composition comprising an intermediate of formula 9: [Chemical formula 9] [ka] In the above Chemical Formula 9, a is an integer of 1 to 4. Effect of the Invention

[0016] The manufacturing method of one embodiment herein has the advantage of using less deuterium source, reducing costs.

[0017] The manufacturing methods of other embodiments herein have the advantage of reducing the overall process time for producing deuterated anthracene compounds. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] This specification will be explained in detail below.

[0019] The hydrogen-deuterium exchange method is mainly used as a technique for deuterizing aromatic compounds. This hydrogen-deuterium exchange method requires that the material to be deuterized must withstand reaction conditions such as high temperature and high pressure, and may require multiple treatments to achieve a high level of deuterium exchange rate, and requires a large amount of a relatively expensive deuterium source, making it inefficient in terms of cost and time.

[0020] This invention relates to a method for synthesizing deuterated anthracene directly from benzene-d6 or halogenated benzene-d5, rather than using a hydrogen-deuterium exchange method, and using the deuterated anthracene as an intermediate for an organic light-emitting material, thereby dramatically reducing the amount of benzene-d6 or halogenated benzene-d5 used.

[0021] In addition, in the case of anthracene derivatives used as materials for organic light-emitting devices, the HOMO and LUMO are distributed in anthracene, so the conversion rate of replacing hydrogen in anthracene with deuterium is important. However, when deuterizing an anthracene derivative in the final state in which a substituent is applied to the 9th, 10th, etc. position of anthracene, it is easy to deuterate the substituent substituted on the anthracene located relatively outside, but it is difficult to replace hydrogen in anthracene that is not substituted with a substituent with deuterium. Therefore, it is no exaggeration to say that the deuterium replacement rate of anthracene derivatives depends on how much hydrogen in anthracene located inside is replaced with deuterium.

[0022] However, since the method for producing a deuterated anthracene compound of the present invention is a bottom-up method in which deuterated anthracene is directly synthesized from benzene-d6 or halogenated benzene-d5, hydrogen atoms at the remaining positions of anthracene except for the 9th and 10th positions are substituted with deuterium atoms before a substituent is substituted at the 9th or 10th position.

[0023] Therefore, in the deuterated anthracene compound produced by the method for producing a deuterated anthracene compound of the present invention, most of the hydrogen atoms of anthracene that are not substituted with a substituent are substituted with deuterium, and an anthracene compound with a high deuterium substitution rate can be more easily produced.

[0024] The present specification provides a method for producing a deuterated anthracene compound, comprising synthesizing the deuterated anthracene compound from benzene-d6 or a halogenated benzene having at least one deuterium.

[0025] The present disclosure provides a method for preparing a deuterated anthracene compound, comprising the steps of: reacting a halogenated benzene having at least one deuterium with an enolate of the following Chemical Formula 1 to synthesize a deuterated anthracene compound:

[0026] In one embodiment of the present specification, the halogenated benzene having at least one deuterium may be halogenated benzene-d5.

[0027] In one embodiment of the present specification, the deuterated anthracene compound may be a compound represented by the following formula 2:

[0028] The present disclosure provides a method for preparing a deuterated anthracene compound, comprising reacting a halogenated benzene-d5 with an enolate of the following formula 1 to synthesize a compound of the following formula 2: [Chemical formula 1] [ka] [Chemical formula 2] [ka] In the above Chemical Formula 2, b is an integer of 1-8.

[0029] In Chemical Formula 2 of one embodiment of the present specification, b is the number of deuterium atoms, which may be 1 to 8 depending on the number of deuterium atoms substituted.

[0030] In one embodiment of the present invention, b is 1 in formula 2.

[0031] In one embodiment of the present invention, b is 2 in formula 2.

[0032] In one embodiment of the present invention, b is 3 in formula 2.

[0033] In one embodiment of the present specification, in formula 2, b is 4.

[0034] In one embodiment of the present invention, b is 5 in formula 2.

[0035] In one embodiment of the present specification, in formula 2, b is 6.

[0036] In one embodiment of the present invention, b is 7 in formula 2.

[0037] In one embodiment of the present specification, in Chemical Formula 2, b is 8. When b is 8, Chemical Formula 2 may be the following Chemical Formula 2-1. [Chemical formula 2-1] [ka] In one embodiment of the present specification, the enolate of Formula 1 may be formed from trimethyl(vinyloxy)silane.

[0038] In one embodiment of the present specification, the step of synthesizing the compound of Chemical Formula 2 may be performed by using a solution containing halogenated benzene-d5; a compound of Chemical Formula 7 or 8 described below; a base; an alkyl lithium; and a solvent.

[0039] In one embodiment of the present specification, the base serves to adjust the pH of the reaction solution, and for example, tetramethylpiperidine may be used.

[0040] In one embodiment of the present specification, the alkyl lithium serves to form LiTMP (Lithium 2,2,6,6-tetramethylpiperidine) with the enolate of Formula 1, and the formed enolate serves as a starting material for forming an anthracene skeleton, and LiTMP serves to convert a halogenated benzene into benzyne.

[0041] In one embodiment of the present specification, the alkyl lithium may be butyl lithium.

[0042] In one embodiment of the present specification, the solvent is not particularly limited as long as it dissolves or does not dissolve the reaction starting material, intermediate, and product, and provides an environment in which the product can maintain its shape. The solvent may be selected from ether solvents or hydrocarbon solvents, for example, from the group consisting of tetrahydropyran and cyclohexane.

[0043] The method for producing a deuterated anthracene compound of the present specification may include a step of synthesizing a compound of the following Formula 3 using a solution containing the compound of Formula 2 and a first halogen donor.

[0044] The method for producing a deuterated anthracene compound of the present specification may include a step of synthesizing a compound of the following Chemical Formula 3 using a solution containing the compound of Chemical Formula 2 and a first halogen donor; and a step of reacting the above-mentioned Chemical Formula 3 with L1-Ar1 to synthesize a compound of the following Chemical Formula 4. [Chemical formula 3] [ka] [Chemical formula 4] [ka] In the above chemical formulas 3 and 4, X1 is a halogen group, L1 is a leaving group, Ar1 is deuterium; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group, and b is an integer of 1 to 8.

[0045] In Chemical Formula 3 of one embodiment of the present specification, b is the number of deuterium atoms, which may be 1 to 8 depending on the number of deuterium atoms substituted.

[0046] In one embodiment of the present invention, b is 1 in formula 3.

[0047] In one embodiment of the present invention, b is 2 in formula 3.

[0048] In one embodiment of the present invention, b is 3 in formula 3.

[0049] In one embodiment of the present invention, b is 4 in formula 3.

[0050] In one embodiment of the present invention, b is 5 in formula 3.

[0051] In one embodiment of the present invention, b is 6 in formula 3.

[0052] In one embodiment of the present specification, in formula 3, b is 7.

[0053] In one embodiment of the present specification, in Chemical Formula 3, b is 8. When b is 8, Chemical Formula 3 may be the following Chemical Formula 3-1. [Chemical formula 3-1] [ka] In the above Chemical Formula 3-1, X1 is defined as in the above Chemical Formula 3.

[0054] In Chemical Formula 4 of one embodiment of the present specification, b is the number of deuterium atoms, which may be 1 to 8 depending on the number of deuterium atoms substituted.

[0055] In one embodiment of the present specification, in formula 4, b is 1.

[0056] In one embodiment of the present invention, b is 2 in formula 4.

[0057] In one embodiment of the present invention, b is 3 in formula 4.

[0058] In one embodiment of the present specification, in formula 4, b is 4.

[0059] In one embodiment of the present invention, b is 5 in formula 4.

[0060] In one embodiment of the present invention, b is 6 in formula 4.

[0061] In one embodiment of the present invention, b is 7 in formula 4.

[0062] In one embodiment of the present specification, in Chemical Formula 4, b is 8. When b is 8, the Chemical Formula 4 may be the following Chemical Formula 4-1. [Chemical formula 4-1] [ka] In the above Chemical Formula 4-1, Ar1 is defined as in the above Chemical Formula 4.

[0063] In one embodiment of the present specification, X1 is fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0064] In one embodiment of the present specification, X1 is chlorine (-Cl), bromine (-Br), or iodine (-I).

[0065] In one embodiment of the present specification, X1 is bromine (-Br).

[0066] In one embodiment of the present specification, Ar1 is deuterium; a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

[0067] In one embodiment of the present specification, Ar1 is deuterium; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

[0068] In one embodiment of the present specification, Ar1 is deuterium; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms.

[0069] In one embodiment of the present specification, Ar1 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted xanthenyl group, a substituted or unsubstituted thioxanthenyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzocarbazolyl group, or a substituted or unsubstituted dibenzocarbazolyl group.

[0070] In one embodiment of the present specification, Ar1 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group.

[0071] In one embodiment of the present specification, Ar1 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group.

[0072] In one embodiment of the present specification, Ar1 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolyl group.

[0073] In one embodiment of the present specification, Ar1 is a substituted or unsubstituted naphthyl group.

[0074] In one embodiment of the present specification, Ar1 is a naphthyl group.

[0075] In one embodiment of the present specification, the formula 4 has any one of the following structures: [ka] [ka] [ka] [ka] [ka] Here, b is an integer from 1 to 8.

[0076] In one embodiment of the present specification, the first halogen donor for synthesizing the compound of Chemical Formula 3 is not particularly limited as long as it can provide a halogen to the 9-position of the compound of Chemical Formula 2. For example, it may be selected from the group consisting of CuBr2, N-bromosuccinimide (NBS), and Br2.

[0077] The method for producing a deuterated anthracene compound of the present specification may include a step of synthesizing a compound of the following Chemical Formula 5 using a solution containing the compound of Chemical Formula 4 and a second halogen donor; and a step of reacting the compound of Chemical Formula 5 with L2-Ar2 to synthesize a compound of the following Chemical Formula 6. [Chemical formula 5] [ka] [Chemical formula 6] [ka] In the above chemical formulas 5 and 6, X2 is a halogen group, L2 is a leaving group, Ar1 and Ar2 are the same or different and each independently represents deuterium; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group, and b is an integer of 1 to 8.

[0078] In one embodiment of the present specification, in formula 5, b is 1.

[0079] In one embodiment of the present invention, b is 2 in formula 5.

[0080] In one embodiment of the present invention, b is 3 in formula 5.

[0081] In one embodiment of the present invention, b is 4 in formula 5.

[0082] In one embodiment of the present invention, b is 5 in formula 5.

[0083] In one embodiment of the present invention, b is 6 in formula 5.

[0084] In one embodiment of the present invention, b is 7 in formula 5.

[0085] In one embodiment of the present specification, in Chemical Formula 5, b is 8. When b is 8, Chemical Formula 5 may be the following Chemical Formula 5-1. [Chemical formula 5-1] [ka] In the above Chemical Formula 5-1, Ar1 and X2 are defined as in Chemical Formula 5.

[0086] In one embodiment of the present invention, b is 1 in formula 6.

[0087] In one embodiment of the present invention, b is 2 in formula 6.

[0088] In one embodiment of the present invention, b is 3 in formula 6.

[0089] In one embodiment of the present invention, b is 4 in formula 6.

[0090] In one embodiment of the present invention, b is 5 in formula 6.

[0091] In one embodiment of the present invention, b is 6 in formula 6.

[0092] In one embodiment of the present invention, b is 7 in formula 6.

[0093] In one embodiment of the present specification, in Chemical Formula 6, b is 8. When b is 8, the Chemical Formula 6 may be the following Chemical Formula 6-1. [Chemical formula 6-1] [ka] In the above Chemical Formula 6-1, Ar1 and Ar2 are defined as in Chemical Formula 6.

[0094] In one embodiment of the present specification, X2 is fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0095] In one embodiment of the present specification, X2 is chlorine (-Cl), bromine (-Br), or iodine (-I).

[0096] In one embodiment of the present specification, X2 is bromine (-Br).

[0097] In one embodiment of the present specification, Ar2 is deuterium; a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

[0098] In one embodiment of the present specification, Ar2 is deuterium; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

[0099] In one embodiment of the present specification, Ar2 is deuterium; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms.

[0100] In one embodiment of the present specification, Ar2 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted xanthenyl group, a substituted or unsubstituted thioxanthenyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzocarbazolyl group, or a substituted or unsubstituted dibenzocarbazolyl group.

[0101] In one embodiment of the present specification, Ar2 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group.

[0102] In one embodiment of the present specification, Ar2 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group.

[0103] In one embodiment of the present specification, Ar2 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolyl group.

[0104] In one embodiment of the present specification, Ar2 is deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted dibenzofuranyl group.

[0105] In one embodiment of the present specification, Ar2 is deuterium, a phenyl group, a naphthyl group, or a dibenzofuranyl group.

[0106] In one embodiment of the present specification, L1 and L2 are -B(OH)2.

[0107] In one embodiment of the present specification, L1-Ar1 and L2-Ar2 each have one of the following structures: [ka] [ka] [ka] .

[0108] In one embodiment of the present specification, the formula 5 has any one of the following structures: [ka] [ka] [ka] [ka] [ka] Here, b is an integer from 1 to 8.

[0109] In one embodiment of the present specification, the formula 6 is any one of the following structures: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] Here, b is an integer from 1 to 8.

[0110] In one embodiment of the present specification, the second halogen donor for synthesizing the compound of Chemical Formula 5 is not particularly limited as long as it can provide a halogen to the 10-position of the compound of Chemical Formula 4. For example, it may be selected from the group consisting of CuBr2, N-bromosuccinimide (NBS), and Br2.

[0111] The method for preparing a deuterated anthracene compound of the present invention may further include a step of synthesizing benzene-d6 into a halogenated benzene having at least one deuterium using a third halogen donor before the step of synthesizing the compound of Chemical Formula 2. Specifically, this may be a step of synthesizing benzene-d6 into a halogenated benzene-d5 using a third halogen donor.

[0112] In one embodiment of the present specification, the third halogen donor is not particularly limited as long as it can replace at least one deuterium in benzene-d6 with a halogen. For example, it may be selected from the group consisting of KBrO3, bromine, and hydrogen bromide.

[0113] The present specification provides a reaction composition comprising a halogenated benzene having at least one deuterium and an enolate of the following formula 1: [Chemical formula 1] [ka]

[0114] In one embodiment of the present specification, the enolate of Chemical Formula 1 may be formed from Chemical Formula 7 or Chemical Formula 8 below. [Chemical formula 7] [ka] [Chemical formula 8] [ka] In the above Chemical Formulae 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

[0115] Another embodiment of the present disclosure provides a reaction composition comprising a halogenated benzene having at least one deuterium; a compound represented by the following formula 7 or 8; a base; an alkyl lithium; and a solvent. [Chemical formula 7] [ka] [Chemical formula 8] [ka] In the above Chemical Formulas 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

[0116] In one embodiment of the present specification, the enolate of Chemical Formula 1 is dissociated from Chemical Formula 7 or Chemical Formula 8.

[0117] In one embodiment of the present specification, L3 and L4 are not particularly limited as long as they can be eliminated to form the enolate of Chemical Formula 1, and specifically, they may be a leaving group that can be eliminated by an alkyl lithium, i.e., butyl lithium (BuLi).

[0118] In one embodiment of the present specification, L3 may be a silyl group unsubstituted or substituted with an alkyl group.

[0119] In one embodiment of the present specification, L3 may be a silyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.

[0120] In one embodiment of the present specification, L3 may be a silyl group unsubstituted or substituted with an alkyl group having 1 to 5 carbon atoms.

[0121] In one embodiment of the present specification, L3 may be a trialkylsilyl group.

[0122] In one embodiment of the present specification, L3 may be a trimethylsilyl group.

[0123] In one embodiment of the present specification, said L4 is hydrogen.

[0124] In one embodiment of the present specification, said L3 is a trialkylsilyl group and said L4 is hydrogen.

[0125] In one embodiment of the present specification, the enolate of Formula 1 may be formed from trimethyl(vinyloxy)silane or acetaldehyde.

[0126] In one embodiment of the present specification, a trimethylsilyl group is eliminated from the trimethyl(vinyloxy)silane, and the enolate of the formula 1 is dissociated. The dissociated enolate of the formula 1 is reacted with halogenated benzene-d5 to synthesize the compound of the formula 2.

[0127] In one embodiment of the present specification, hydrogen is eliminated from acetaldehyde by alkyl lithium, i.e., butyl lithium (BuLi), as shown in the following reaction formula, and the enolate of Chemical Formula 1, which has a more stable structure, is obtained. In this case, the lithium cation, which is a monovalent cation, stabilizes the enolate of Chemical Formula 1 as a counterion. [ka]

[0128] The reaction composition can be described in the above-mentioned method for producing a deuterated anthracene compound.

[0129] The present specification provides a deuterated anthracene compound produced by the above-mentioned production method.

[0130] Another embodiment of the present disclosure provides a deuterated anthracene compound of formula 10: [Chemical formula 10] [ka] In the above Chemical Formula 10, Ar1 and Ar2 are the same or different and each independently represents hydrogen; deuterium; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group; and b is an integer of 1 to 8.

[0131] In one embodiment of the present invention, b is 1 in formula 10.

[0132] In one embodiment of the present invention, b is 2 in formula 10.

[0133] In one embodiment of the present invention, b is 3 in formula 10.

[0134] In one embodiment of the present invention, b is 4 in formula 10.

[0135] In one embodiment of the present invention, b is 5 in formula 10.

[0136] In one embodiment of the present invention, b is 6 in formula 10.

[0137] In one embodiment of the present invention, b is 7 in formula 10.

[0138] In one embodiment of the present specification, in Chemical Formula 10, b is 8. When b is 8, Chemical Formula 10 may be the following Chemical Formula 10-1. [Chemical formula 10-1] [ka] In the above Chemical Formula 10-1, Ar1 and Ar2 are defined as in Chemical Formula 10.

[0139] In one embodiment of the present specification, the deuterated anthracene compound may include a compound represented by the following chemical formula A: [Chemical formula A] [ka] In the above chemical formula A, L21 to L23 are the same or different and each independently represents a direct bond; a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; R21 to R27 are the same or different and each independently represent a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; Ar21 to Ar23 are the same or different and each independently represents a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; a is 0 or 1.

[0140] Yet another embodiment of the present disclosure provides a compound of formula 9: [Chemical formula 9] [ka] In the above Chemical Formula 9, a is an integer of 1 to 4.

[0141] In one embodiment of the present specification, the compound of Chemical Formula 9 is an intermediate obtained by reacting the dissociated enolate of Chemical Formula 1 with a benzyne intermediate formed from halogenated benzene-d5 in a 1:1 ratio, and when the compound of Chemical Formula 9 reacts with the benzyne intermediate formed from halogenated benzene-d5, the compound of Chemical Formula 2 is formed.

[0142] In one embodiment of the present specification, in formula 9, a is 1.

[0143] In one embodiment of the present specification, in formula 9, a is 2.

[0144] In one embodiment of the present specification, in formula 9, a is 3.

[0145] In one embodiment of the present specification, in Chemical Formula 9, a is 4. When a is 4, the Chemical Formula 9 may be the following Chemical Formula 9-1. [Chemical formula 9-1] [ka]

[0146] In one embodiment of the present specification, the compound of formula 9-1 is an intermediate obtained by reacting the dissociated enolate of formula 1 with a benzyne intermediate formed from halogenated benzene-d5 in a 1:1 ratio, and when the compound of formula 9-1 reacts with the benzyne intermediate formed from halogenated benzene-d5, the compound of formula 2-1 is formed. [ka]

[0147] Yet another embodiment of the present specification provides a composition comprising an intermediate of formula 9: [Chemical formula 9] [ka] In the above Chemical Formula 9, a is an integer of 1 to 4.

[0148] In one embodiment of the present specification, the composition may further include a compound of formula 4 or 6 below. [Chemical formula 4] [ka] [Chemical formula 6] [ka] In the above Chemical Formulas 4 and 6, Ar1 and Ar2 are the same or different and each independently represents deuterium; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group; and b is an integer of 1 to 8.

[0149] In one embodiment of the present specification, the composition containing the intermediate of Chemical Formula 9 may be a solution in a step of synthesizing a deuterated anthracene compound by reacting a halogenated benzene having at least one deuterium with the enolate of Chemical Formula 1.

[0150] In one embodiment of the present specification, the compound of Chemical Formula 9 is an intermediate before being synthesized into the product deuterated anthracene compound, and during the process of synthesis of the deuterated anthracene compound, the compound of Chemical Formula 9 is produced several times and then disappears while forming the deuterated anthracene compound. In addition, even after the synthesis of the deuterated anthracene compound is completed, an intermediate that has not yet become the deuterated anthracene compound may remain.

[0151] In one embodiment of the present specification, even after the deuterated anthracene compound is obtained by purification, the compound of Chemical Formula 9 may remain as an impurity.

[0152] Therefore, the composition containing the intermediate of Chemical Formula 9 may mean a solution during which a synthesis reaction according to the production method of the present specification is in progress, a solution after the synthesis reaction according to the production method of the present specification has been completed, or a deuterated anthracene compound obtained after the synthesis reaction according to the production method of the present specification has been completed.

[0153] In this case, the deuterated anthracene compound obtained after the synthesis reaction can contain two or more isotopes with different molecular weights depending on the number of substituted deuterium, and therefore can be expressed as a composition containing two or more compounds with different deuterium substitution numbers.

[0154] In one embodiment of the present specification, even if hydrogen atoms of the substituents of Ar1 and Ar2 are not replaced with deuterium, the deuterated anthracene compound obtained after completion of the synthesis reaction exhibits a life-improving effect similar to that of an anthracene compound having a deuterium substitution rate of a certain level or higher (80% or higher) without performing an additional deuterium substitution reaction, since the HOMO and LUMO of the anthracene derivative are distributed in anthracene.

[0155] Since an additional deuteration substitution reaction is not required, an excess deuterium source for the deuteration substitution reaction is not required, which is advantageous in terms of cost and allows the production of a deuterated anthracene compound at low cost.

[0156] In one embodiment of the present specification, in the deuterated anthracene compound of the present specification, most of the 1- to 10-positions of anthracene that are not "substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocycles" are substituted with deuterium.

[0157] In one embodiment of the present specification, the deuterated anthracene compound of the present specification may have a deuterium substitution rate at positions 1 to 10 of anthracene that are not "substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocycles" of 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.

[0158] In one embodiment of the present specification, in the case of a deuterated anthracene compound having a "substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocycle" substituted only at the 9- and 10-positions, the number of deuterium substitutions of the deuterated anthracene compound may be 5 or more, 6 or more, 7 or more, or 8.

[0159] In one embodiment of the present specification, in the case of a deuterated anthracene compound having a "substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocycle" substituted only at the 9-position, the number of deuterium substitutions of the deuterated anthracene compound may be 5 or more, 6 or more, 7 or more, 8 or more, or 9.

[0160] In one embodiment of the present specification, in the case of a deuterated anthracene compound having "substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocycles" substituted only at the 2-, 9-, and 10-positions, the number of deuterium substitutions of the deuterated anthracene compound may be 5 or more, 6 or more, or 7.

[0161] In one embodiment of the present specification, in the case of a deuterated anthracene compound having no positions substituted with a “substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocycle” at positions 1 to 10, the number of deuterium substitutions of the deuterated anthracene compound may be 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10.

[0162] In this specification, examples of the substituents are described below, but are not limited to these.

[0163] The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of the substitution is not limited as long as it is a position at which a hydrogen atom is substituted, i.e., a position at which a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different.

[0164] In this specification, the term "substituted or unsubstituted" means that the group is substituted with one or more substituents selected from the group consisting of halogen group, nitrile group, nitro group, hydroxy group, amine group, silyl group, boron group, alkoxy group, alkyl group, cycloalkyl group, aryl group, and heterocyclic group, or that the group is substituted with a substituent in which two or more of the above-mentioned substituents are linked, or that the group does not have any substituent. For example, the "substituent in which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and can be interpreted as a substituent in which two phenyl groups are linked.

[0165] As used herein, examples of halogen groups include fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0166] As used herein, a silyl group has the formula -SiY a Y b Y c and Y a , Y b , and Y c may be hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

[0167] As used herein, a boron group is represented by the formula -BY d Y e and Y d and Y e may be hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Specific examples of the boron group include, but are not limited to, a dimethyl boron group, a diethyl boron group, a tert-butyl methyl boron group, a diphenyl boron group, and a phenyl boron group.

[0168] In this specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the alkyl group has 1 to 30 carbon atoms. According to another embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an n-pentyl group, a hexyl group, an n-hexyl group, a heptyl group, an n-heptyl group, an octyl group, and an n-octyl group.

[0169] In this specification, the alkoxy group may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferable that the number of carbon atoms is 1 to 20. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, and n-decyloxy.

[0170] The alkyl groups, alkoxy groups, and other substituents containing alkyl moieties described herein include either straight or branched chain groups.

[0171] In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0172] In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 39 carbon atoms. According to one embodiment, the aryl group has 6 to 30 carbon atoms. As the monocyclic aryl group, there are exemplified, but not limited to, a phenyl group, a biphenyl group, a terphenyl group, and a quaterphenyl group. As the polycyclic aryl group, there are exemplified, but not limited to, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and a triphenylenyl group.

[0173] As used herein, the fluorene group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

[0174] When the fluorene group is substituted, [ka] However, the present invention is not limited to these.

[0175] In the present specification, the heterocyclic group is a cyclic group containing one or more heteroatoms selected from N, O, P, S, Si, and Se, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to one embodiment, the number of carbon atoms of the heterocyclic group is 2 to 36. Examples of the heterocyclic group include, but are not limited to, a pyridine group, a pyrrole group, a pyrimidine group, a quinoline group, a pyridazine group, a furan group, a thiophene group, an imidazole group, a pyrazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a benzocarbazole group, a benzonaphthofuran group, a benzonaphthothiophene group, an indenocarbazole group, and an indolocarbazole group.

[0176] In this specification, the heteroaryl group may be the same as the heterocyclic group described above, except that the heteroaryl group is aromatic.

[0177] In this specification, the amine group may be selected from the group consisting of -NH2; an alkylamine group; an N-alkylarylamine group; an arylamine group; an N-arylheteroarylamine group; 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, but are not limited to, a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, an N-phenylnaphthylamine group, a ditolylamine group, an N-phenyltolylamine group, a triphenylamine group, an N-phenylbiphenylamine group, an N-phenylnaphthylamine group, an N-biphenylnaphthylamine group, an N-naphthylfluorenylamine group, an N-phenylphenanthrenylamine group, an N-biphenylphenanthrenylamine group, an N-phenylfluorenylamine group, an N-phenylterphenylamine group, an N-phenanthrenylfluorenylamine group, and an N-biphenylfluorenylamine group.

[0178] As used herein, an N-alkylarylamine group refers to an amine group in which the N of the amine group is substituted with an alkyl group and an aryl group.

[0179] As used herein, an N-arylheteroarylamine group refers to an amine group in which the N of the amine group is substituted with an aryl group and a heteroaryl group.

[0180] As used herein, an N-alkylheteroarylamine group refers to an amine group in which the N of the amine group is substituted with an alkyl group and a heteroaryl group.

[0181] In this specification, the alkyl group, aryl group, and heteroaryl group in the alkylamine group, N-alkylarylamine group, arylamine group, N-arylheteroarylamine group, N-alkylheteroarylamine group, and heteroarylamine group are the same as the above-mentioned exemplary alkyl group, aryl group, and heteroaryl group, respectively.

[0182] In one embodiment of the present specification, the deuterated anthracene compound may have any one of the following structures: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

[0183] Theoretically, if all hydrogen in a deuterated compound is replaced with deuterium, that is, if the deuterium replacement rate is 100%, the life characteristics will be most ideally improved. However, there are problems such as the need for extreme conditions due to steric hindrance and the compound being destroyed by side reactions before being deuterized, so in reality it is difficult to achieve a deuteration rate of 100% for all hydrogen in a compound, and even if a deuteration rate of nearly 100% is achieved, the return on investment is not good when the process time and cost are taken into consideration.

[0184] In this specification, a deuterated compound having one or more deuterium atoms produced by a deuteration reaction is produced as a composition having two or more isotopes whose molecular weights differ depending on the number of substituted deuterium atoms, and therefore the position where the deuterium is substituted in the structure is omitted.

[0185] In the compound of the above structure, at least one of the positions where hydrogen is omitted and which is represented or substituted by hydrogen may be substituted by deuterium.

[0186] The present specification provides an electronic device including a deuterated anthracene compound produced by the above-mentioned production method.

[0187] The present specification provides an electronic device including the deuterated anthracene compound described above.

[0188] The present specification provides a method for producing an electronic device, comprising the step of producing an electronic device using the deuterated anthracene compound described above.

[0189] The electronic device and the method for manufacturing the electronic device may refer to the applicable descriptions among those described above, and redundant descriptions will be omitted.

[0190] The electronic device is not particularly limited as long as it is an element in which the above-mentioned deuterated anthracene compound can be used, and may be, for example, an organic light-emitting device, an organic phosphorescent device, an organic solar cell, an organic photoreceptor, an organic transistor, or the like.

[0191] The electronic device includes a first electrode; a second electrode; and one or more organic layers provided between the first electrode and the second electrode, and one or more of the organic layers may include the deuterated anthracene compound described above.

[0192] The present specification provides an organic light-emitting device including the deuterated anthracene compound described above.

[0193] The present specification provides an organic light-emitting device including a deuterated anthracene compound produced by the above-mentioned production method.

[0194] In one embodiment of the present specification, the organic light-emitting element includes a first electrode; a second electrode; and an organic layer provided between the first electrode and the second electrode, and the organic layer includes the deuterated anthracene compound.

[0195] In one embodiment of the present specification, the organic layer includes a light-emitting layer containing the deuterated anthracene compound.

[0196] The organic layer of the organic light-emitting device of the present specification may have a single-layer structure, or may have a multi-layer structure in which two or more organic layers are laminated. For example, the organic layer of the present specification may have one to three layers. The organic light-emitting device of the present specification may have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. as the organic layer. However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number of organic layers.

[0197] When the organic light emitting device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

[0198] For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic layer, and a cathode on a substrate. In this case, a metal or a conductive metal oxide or an alloy thereof may be deposited on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form an anode, and an organic layer including a hole injection layer, a hole transport layer, an emitting layer, and an electron transport layer may be formed thereon, and a material usable as a cathode may be deposited thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.

[0199] In addition, the material of each layer may be formed as an organic layer by a solution coating method as well as a vacuum deposition method during the manufacture of the organic light-emitting device, where the solution coating method refers to, but is not limited to, spin coating, dip coating, doctor blade, inkjet printing, screen printing, spraying, roll coating, etc.

[0200] In one embodiment herein, the first electrode is an anode and the second electrode is a cathode.

[0201] According to another embodiment, the first electrode is a cathode and the second electrode is an anode.

[0202] In another embodiment, the organic light-emitting device may be a normal type organic light-emitting device having a structure in which an anode, one or more organic layers, and a cathode are sequentially laminated on a substrate.

[0203] In one embodiment, the organic light-emitting device may be an inverted-type organic light-emitting device in which a cathode, one or more organic layers, and an anode are sequentially laminated on a substrate.

[0204] In this specification, the materials of the cathode, the organic layer, and the anode are not particularly limited, except that at least one of the organic layers contains a deuterated anthracene compound, and any material known in the art may be used.

[0205] In this specification, the above-mentioned deuterated anthracene compound can be used in electronic devices such as organic phosphorescent devices, organic solar cells, organic photoconductors, organic transistors, etc., based on the same principles as those applied to organic light-emitting devices. For example, the organic solar cell may have a structure including a cathode, an anode, and a photoactive layer provided between the cathode and the anode, and the photoactive layer may include the deuterated anthracene compound selected above. EXAMPLES

[0206] The present invention will be described in more detail below with reference to examples. However, the following examples are merely for the purpose of illustrating the present invention and are not intended to limit the present invention. Throughout the examples, (D) b , (D) c , (D) d , (D) e , (D) f and (D) g Each of the numbers b to g indicates the number of deuterium substitutions, and since the number and position of deuterium substitutions of individual compounds among the obtained compounds and the obtained compounds may vary depending on the deuterium conversion rate of each reaction, the numbers of deuterium substitutions b to g and the substitution positions are not specified. In this case, b is an integer of 1 to 8, c is an integer of 1 to 6, d is an integer of 1 to 5, e is an integer of 1 to 4, f is an integer of 1 to 7, and g is an integer of 1 to 7.

[0207] [Measurement of deuterium conversion rate and deuterium conversion rate of anthracene] In this specification, the deuterium conversion rate and the deuterium conversion rate of anthracene were measured by nuclear magnetic resonance (NMR) analysis. The detailed NMR analysis method is as follows.

[0208] After N-NMR analysis of a compound not substituted with deuterium, a material with the same structure as the compound analyzed by N-NMR but with hydrogen substituted with deuterium and an internal standard were mixed and analyzed by H-NMR. If hydrogen is 100% substituted with deuterium, hydrogen peaks at the positions substituted with deuterium cannot be observed in H-NMR, so the deuterium substitution rate for each position can be measured from the H-NMR analysis results of the product not substituted with deuterium and the H-NMR analysis results of the deuterium-substituted material.

[0209] However, in Production Examples 1 to 14 described later, depending on the substituent, the hydrogen position of anthracene may overlap with the hydrogen position of the substituent in H-NMR. In this specification, when a substituent is introduced into 9-bromo-10-(1-naphthyl)anthracene-d8, the deuterium substitution rate of anthracene is replaced with the deuterium substitution rate of 9-bromo-10-(1-naphthyl)anthracene-d8.

[0210] [Example]

[0211] [Production Example 1] Synthesis of bromobenzene-d5 [ka] Benzene-d6 [Benzene-d6, deuterium conversion rate 99%] (100g, 1.18mol) was added to 30wt% H2SO4 (240ml, 7.34mol) and stirred at 40℃. KBrO3 was added in five portions and the reaction was monitored using high performance liquid chromatography (HPLC). After the reaction was completed, the layers were separated to obtain 1-bromobenzene-2,3,4,5,6-d5 (140g, 73%, deuterium conversion rate 99%).

[0212] [Production Example 2] Synthesis of anthracene-d8 [ka] Under nitrogen, lithium 2,2,6,6-tetramethylpiperidine (LiTMP) (26.2 g, 0.185 mol) was added to anhydrous tetrahydropyran (THP) (100 mL) and stirred at 0°C. While maintaining the temperature, trimethyl(vinyloxy)silane (7.2 g, 0.062 mol), 2.5 M n-BuLi (98.7 mL, 0.247 mol), and bromobenzene-d5 (20 g, 0.123 mol) were added in that order, and the temperature was raised to reflux. After 30 minutes, the mixture was cooled, quenched by adding 100 mL of water, and the aqueous layer was removed using a separatory funnel. The organic layer was removed with MgSO4 and filtered through a silica pad. The filtrate was purified by column chromatography to obtain anthracene-d8 (5 g, 0.025 mol, yield 40%, deuterium conversion rate of anthracene at positions 1 to 8 99%). MS(GC)m / z:186

[0213] [Production Example 3] 9-Bromoanthracene-d8 [ka] Anthracene-d8 (10.0 g, 0.054 mol), copper(II) bromide (24.0 g, 0.107 mol), and CHCl3 (200 mL) were added to a round-bottom flask and stirred under reflux. After 24 hours, the reaction solution was cooled to room temperature and filtered to remove insoluble matter. The filtrate was distilled under reduced pressure using a rotary evaporator and then purified by column chromatography to obtain 9-bromoanthracene-d8 (12.8 g, 0.048 mol, yield 90%, deuterium conversion rate of anthracene at positions 1 to 8 99%).

[0214] [Production Example 4] 9-(1-naphthyl)anthracene-d8 [ka] 9-Bromoanthracene-d8 (10 g, 0.038 mol), 1-naphthaleneboronic acid (7.8 g, 0.045 mol), 1,4-dioxane (100 mL), potassium phosphate (24.0 g, 0.113 mol), H2O (30 mL), and tetrakis(triphenylphosphine)palladium(0) (TTP) (0.44 g, 1 mol%) were added to a round-bottom flask and then heated to reflux. After 5 hours, the reaction solution was cooled and the aqueous layer was removed using a separatory funnel. The organic layer was dried over MgSO4 and then filtered through a silica pad. The filtrate was distilled under reduced pressure and purified by column chromatography to obtain 9-(1-naphthyl)anthracene-d8 (8.84 g, 75% yield, 99% deuterium conversion rate of anthracene at positions 1 to 8). MS(LC / MS)m / z:312

[0215] [Production Example 5] 9-Bromo-10-(1-naphthyl)anthracene-d8 [ka] 9-(1-naphthyl)anthracene (5 g, 0.016 mol) and N,N-dimethylformamide (DMF) (30 mL) were placed in a round-bottom flask, and N-bromosuccinimide (NBS) (2.8 g, 0.016 mol) was added while stirring. After 5 hours, water (100 mL) was added and the resulting crystals were filtered. The filtered solid was dissolved in chloroform (50 mL), washed with water (15 mL), dried over MgSO4, and then filtered. The filtrate was distilled under reduced pressure and purified by column chromatography to obtain 9-bromo-10-(1-naphthyl)anthracene (5.64 g, 90% yield, 99% deuterium conversion rate of anthracene at positions 1 to 8). MS(LC / MS)m / z:390

[0216] [Production Example 6] Synthesis of BH1 [ka] A round-bottom flask was charged with 9-bromo-10-(1-naphthyl)anthracene-d8 (10 g, 0.026 mol), (4-(naphthalen-2-yl)phenyl)boronic acid (7.6 g, 0.031 mol), 1,4-dioxane (200 mL), potassium phosphate (10.8 g, 0.052 mol), H2O (32.4 mL), and bis(tri-tert-butylphosphine)palladium(0) (BTP) (0.13 g, 0.0026 mol) and heated to reflux. After 5 h, the reaction was cooled and the aqueous layer was removed in a separatory funnel. The organic layer was dried over MgSO4 and filtered through a silica pad. The filtrate was distilled under reduced pressure and then purified by column chromatography to obtain BH1 (8.5 g, yield 65%, deuterium conversion rate of anthracene 99%, m / s(M+H) 515).

[0217] [Production Example 7] Synthesis of BH2 [ka] BH2 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 7 (yield 8.1 g, yield 73%, deuterium conversion rate of anthracene 99%, m / s(M+H) 439).

[0218] [Production Example 8] Synthesis of BH3 [ka] BH3 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 8 (yield 9.3 g, yield 70%, deuterium conversion rate of anthracene 99%, m / s(M+H) 479).

[0219] [Production Example 9] Synthesis of BH4 [ka] BH4 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 9 (yield 9.1 g, yield 75%, deuterium conversion rate of anthracene 99%, m / s(M+H) 479).

[0220] [Production Example 10] Synthesis of BH5 [ka] BH5 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 10 (yield 8.7 g, yield 65%, deuterium conversion rate of anthracene 99%, m / s(M+H) 529).

[0221] [Production Example 11] Synthesis of BH6 [ka] BH6 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 11 (yield 9.4 g, yield 70%, deuterium conversion rate of anthracene 99%, m / s(M+H) 529).

[0222] [Production Example 12] Synthesis of BH7 [ka] BH7 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 12 (yield 11.5 g, yield 80%, deuterium conversion rate of anthracene 99%, m / s(M+H) 569).

[0223] [Production Example 13] Synthesis of BH8 [ka] BH8 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 13 (yield 10.1 g, yield 70%, deuterium conversion rate of anthracene 99%, m / s(M+H) 569).

[0224] [Production Example 14] Synthesis of BH9 [ka] BH9 was synthesized in the same manner as in Preparation Example 6, except that a reactant having a different structure was used in Preparation Example 14 (yield 8.9 g, yield 65%, deuterium conversion rate of anthracene 99%, m / s(M+H) 534).

[0225] [Comparative Synthesis Example 1] Synthesis of BH10 [ka] 9-Bromo-10-(1-naphthyl)anthracene (10 g, 0.026 mol), (4-(naphthalen-2-yl)phenyl)boronic acid (7.6 g, 0.031 mol), 1,4-dioxane (200 mL), potassium phosphate (10.8 g, 0.052 mol), H2O (32.4 mL), and bis(tri-tert-butylphosphine)palladium(0) (0.13 g, 0.0026 mol) were added to a round-bottom flask and then heated to reflux. After 5 hours, the reaction solution was cooled and the aqueous layer was removed using a separatory funnel. The organic layer was dried over MgSO4 and then filtered through a silica pad. The filtrate was distilled under reduced pressure and purified by column chromatography to obtain BH10 (10.2 g, yield 65%, m / s (M+H) 506).

[0226] [Comparative Synthesis Example 2] Synthesis of BH11 [ka] BH11 was synthesized in the same manner as in Comparative Synthesis Example 1, except that a reactant having a different structure was used in Comparative Synthesis Example 2 (yield: 8.4 g, yield: 75%, m / s (M+H) 430).

[0227] [Comparative Synthesis Example 3] Synthesis of BH12 [ka] BH10 (10g, 0.020mol), benzene-d6 (475g, 5.65mol), and trifluoromethanesulfonic acid (TfOH) (13.5g, 0.09mol) were added to a round-bottom flask and then heated to 70°C. After 2 hours, the reaction solution was cooled, neutralized by adding 150ml of 2M K3PO4 (aq), and the aqueous layer was removed using a separatory funnel. The organic layer was dried with MgSO4 and then filtered through a silica pad. The filtrate was distilled under reduced pressure and purified by column chromatography to obtain BH12 (9.4g, yield 90%, deuterium conversion rate 87%, deuterium conversion rate of anthracene 91%). Here, the molecular weight distribution of BH12 was confirmed [cal.m / s: 532, exp.m / s (M+H) 524~533].

[0228] [Comparative Synthesis Example 4] Synthesis of BH13 [ka] BH13 was synthesized in the same manner as in Comparative Synthesis Example 3, except that BH11 was used instead of BH10 (yield 8.1 g, yield 78%, deuterium conversion rate 85%, deuterium conversion rate of anthracene 87.5%). Here, the molecular weight distribution of BH13 was confirmed [cal.m / s: 452, exp.m / s (M+H) 443-452].

[0229] [Evaluation example] Fabrication of OLED elements A glass substrate coated with a 150 nm-thick thin film of ITO (indium tin oxide) was placed in distilled water containing detergent and ultrasonically washed. The detergent used was a product of Fischer Co., and the distilled water used was distilled water that had been filtered a second time with a Millipore Co. filter. The ITO was washed for 30 minutes, and then ultrasonically washed twice with distilled water for 10 minutes. After the distilled water washing was completed, the substrate was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transferred to a plasma cleaner. The substrate was also washed for 5 minutes using nitrogen plasma, and then transferred to a vacuum evaporator. The following HAT-CN compound was thermally vacuum deposited on the ITO transparent electrode thus prepared to form a hole injection layer to a thickness of 5 nm. Next, HT1 was thermally vacuum deposited to a thickness of 100 nm, and then HT2 was thermally vacuum deposited to a thickness of 10 nm to form a hole transport layer. Next, BH1 to BH11 as hosts and BD as a dopant (weight ratio of 97:3) were simultaneously vacuum-deposited to form a 20 nm-thick light-emitting layer. Next, ET was vacuum-deposited to a thickness of 20 nm to form an electron transport layer. Next, LiF was vacuum-deposited to a thickness of 0.5 nm to form an electron injection layer. Next, aluminum was vacuum-deposited to a thickness of 100 nm to form a cathode, thereby manufacturing an organic light-emitting device.

[0230] The structures of the compounds used in the examples are as follows: [ka] [ka] [ka]

[0231] In the organic light-emitting devices manufactured in Examples 1 to 9 and Comparative Examples 1 to 4, 2 The driving voltage and luminous efficiency were measured at a current density of 20 mA / cm 2The time (LT) required for the luminance to reach 95% of the initial luminance was measured at the current density of 1000 mA. The results are shown in Table 1 below.

[0232] [Table 1]

[0233] According to Table 1, it can be seen that Examples 1 to 9 using compounds substituted with deuterium have lower driving voltages, higher luminous efficiencies, or longer lifetimes than Comparative Examples 1 and 2 using compounds not substituted with deuterium.

[0234] In particular, when Example 1, which uses BH1 having the same backbone structure, and Comparative Example 1, which uses BH10, it can be seen that the lifetime of Example 1, in which deuterium is substituted, is significantly longer than that of Comparative Example 1. In addition, when Example 2, which uses BH2 having the same backbone structure, and Comparative Example 2, which uses BH11, it can be seen that the lifetime of Example 2, in which deuterium is substituted, is significantly longer than that of Comparative Example 2.

[0235] BH1 used in Example 1 and BH12 used in Comparative Example 3 also have the same backbone structure. In this case, BH1 was introduced after deuterium had already been substituted during the synthesis of anthracene using benzene-d6 that had been deuterized by the bottom-up method. Deuterium was substituted at 99% of the 8 substitution positions based on anthracene, and deuterium was substituted at 30.7% of the 26 substitution positions based on the entire BH10 compound. In contrast, BH12 was prepared by synthesizing BH10 according to Comparative Synthesis Example 1, and then substituting deuterium into BH10 through a deuteration process according to Comparative Synthesis Example 3. As a result, deuterium was substituted at 91% of the 8 substitution positions based on anthracene, and deuterium was substituted at 87% of the 26 substitution positions based on the entire BH10 compound. As a result, the lifetime of Comparative Example 3 using BH12 with a high deuterium conversion rate based on all compounds is longer than that of Example 1, but it can be confirmed that Example 1 shows a life effect of 95% ((175 / 185) x 100) of the life of Comparative Example 3 with a deuterium conversion rate of 87% based on all compounds, despite the deuterium conversion rate of 30.7% based on all compounds. In addition, BH1 in Example 1 directly synthesizes anthracene using benzene-d6 that has already been deuterated, so that a separate deuteration process is not performed, and while the process is simplified, the efficiency of improving the lifetime by deuterated anthracene is high.

[0236] This effect can also be confirmed by comparing BH2 used in Example 2 with BH13 used in Comparative Example 4. Specifically, it can be confirmed that Example 2, although the deuterium conversion rate based on all compounds is 36%, exhibits a life effect of 96% ((186 / 194) x 100) of the life of Comparative Example 3, in which the deuterium conversion rate based on all compounds is 85%.

Claims

1. The method includes the step of synthesizing a deuterated anthracene compound by reacting a halogenated benzene having at least one deuterium with an enolate represented by the following Formula 1: The enolate of Formula 1 is formed from the following Formula 7 or Formula 8, or from trimethyl(vinyloxy)silan or acetaldehyde. [Chemical formula 1] 【Chemistry 1】 。 [Chemical formula 7] 【Chemistry 9】 [Chemical formula 8] 【Chemistry 10】 In the above Chemical Formulas 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

2. The method includes reacting halogenated benzene-d5 with an enolate represented by the following formula 1 to synthesize a compound represented by the following formula 2: The enolate of Formula 1 is formed from the following Formula 7 or Formula 8, or from trimethyl(vinyloxy)silan or acetaldehyde. [Chemical formula 1] 【Chemistry 2】 [Chemical formula 2] 【Chemistry 3】 [Chemical formula 7] 【Chemistry 9】 [Chemical formula 8] 【Chemistry 10】 In the above formula 2, b is an integer of 1 to 8; In the above Chemical Formulas 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

3. 2. The method for producing a deuterated anthracene compound according to claim 1, wherein the halogenated benzene having at least one deuterium is halogenated benzene-d5.

4. The method for producing the deuterated anthracene compound according to any one of claims 1 to 3, wherein the deuterated anthracene compound is a compound represented by the following formula 2: [Chemical formula 2] 【Chemistry 4】 In the above formula 2, b is an integer of 1 to 8.

5. synthesizing a compound represented by the following formula 3 using a solution containing the compound represented by the formula 2 and a first halogen donor; and The method for preparing the deuterated anthracene compound according to claim 2 or 4, comprising reacting the compound represented by formula 3 with L1-Ar1 to synthesize a compound represented by formula 4: [Chemical formula 3] 【Chemistry 5】 [Chemical formula 4] 【Chemistry 6】 In the above Chemical Formulas 3 and 4, X1 is a halogen group and L1 is a leaving group; Ar1 is deuterium; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group; b is an integer from 1 to 8.

6. synthesizing a compound of the following formula 5 using a solution containing the compound of the formula 4 and a second halogen donor; and The method for preparing the deuterated anthracene compound according to claim 5, comprising reacting the compound represented by Formula 5 with L2-Ar2 to synthesize a compound represented by Formula 6: [Chemical formula 5] 【Chemistry 7】 [Chemical formula 6] 【Chemistry 8】 In the above Chemical Formulas 5 and 6, X2 is a halogen group and L2 is a leaving group; Ar1 and Ar2 are the same or different and each independently represents deuterium; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group; b is an integer from 1 to 8.

7. The method for producing a deuterated anthracene compound according to claim 1, further comprising the step of synthesizing a halogenated benzene-d5 from benzene-d6 using a third halogen donor before the step of synthesizing the deuterated anthracene compound.

8. The method for producing a deuterated anthracene compound according to claim 1 , wherein the enolate of Chemical Formula 1 is formed according to the following Chemical Formula 7 or Chemical Formula 8: [Chemical formula 7] 【Chemistry 9】 [Chemical formula 8] 【Chemistry 10】 In the above Chemical Formulas 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

9. The method for producing a deuterated anthracene compound according to claim 1 , wherein the enolate of Chemical Formula 1 is formed from trimethyl(vinyloxy)silan or acetaldehyde.

10. The step of synthesizing the compound of Formula 2 includes: The method for producing the hydrogenated anthracene compound according to claim 2 or 4, wherein the compound of the formula 2 is synthesized using a solution containing halogenated benzene-d5; a compound of the following formula 7 or 8; a base; an alkyl lithium; and a solvent: [Chemical formula 7] 【Chemistry 11】 [Chemical formula 8] 【Chemistry 12】 In the above Chemical Formulas 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

11. The method for producing a deuterated anthracene compound according to claim 5, wherein the formula 4 is any one of the following structures: 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 Here, b is an integer from 1 to 8.

12. The method for producing a deuterated anthracene compound according to claim 6, wherein the formula 5 is any one of the following structures: 【Chemistry 18】 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemical 22】 Here, b is an integer from 1 to 8.

13. The method for producing a deuterated anthracene compound according to claim 6, wherein the formula 6 is any one of the following structures: 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemical 29】 【Chemistry 30】 【Chemistry 31】 【Chemistry 32】 【Chemical 33】 【Chemical 34】 【Chemistry 35】 【Chemical 36】 【Chemical 37】 【Chemical Formula 38】 【Chemical 39】 【Chemistry 40】 【Chemistry 41】 【Chemistry 42】 【Chemistry 43】 【Chemistry 44】 【Chemistry 45】 【Chemistry 46】 【Chemistry 47】 【Chemistry 48】 【Chemistry 49】 【Chemistry 50】 【Chemistry 51】 【Chemistry 52】 Here, b is an integer from 1 to 8.

14. A reaction composition for a reaction for synthesizing a deuterated anthracene compound, comprising: a halogenated benzene having at least one deuterium; a compound represented by the following formula 7 or 8; a base; an alkyl lithium; and a solvent: [Chemical formula 7] 【Chemistry 56】 [Chemical formula 8] 【Chemistry 57】 In the above Chemical Formulas 7 and 8, L3 and L4 are the same or different and each independently represents a leaving group.

15. A reaction composition for a reaction for synthesizing a deuterated anthracene compound according to claim 14, in which an enolate of the following formula 1 is dissociated from the formula 7 or the formula 8: [Chemical formula 1] 【Chemistry 58】 。

16. 16. A reaction composition for a reaction to synthesize a deuterated anthracene compound according to claim 14 or 15, wherein L3 is a trialkylsilyl group and L4 is hydrogen.

Images