Process for preparation of deuterated aromatic compounds

Abstract

The present invention relates to a process for preparing a deuterated compound and to a deuterated compound prepared by said process.

Description

[0001] The present invention relates to a method for preparing a deuterated compound and to a deuterated compound prepared by said method.

[0002] Deuterium is one of two stable isotopes of hydrogen and its natural abundance is about 0.0156% (0.312 mass %) of all naturally occurring hydrogen in the oceans.

[0003] Deuterated compounds are known in which the deuterium level is deliberately enriched and deuterated aromatic compounds are often used in the study of chemical reactions or metabolic transformation processes. Deuterated aromatic compounds are also used as starting materials for pharmaceutical compounds or markers.

[0004] The use of deuterated organic or organometallic compounds in electronic devices is also well known. More particularly, as disclosed, for example, in WO 2010 / 099534, WO 2011 / 050888 or J. Phys. Chem. C 2007, 111, 3490 - 3494, the use of deuterated organic or organometallic compounds in organic light emitting diodes (OLEDs) can significantly improve the performance of OLEDs in terms of efficiency and lifetime. The synthesis of deuterated compounds can be quite challenging and also expensive. Deuterated compounds can be obtained by reacting structural units together, where at least one structural unit is partially or fully deuterated (as in WO 2011 / 050888) or by deuterating a synthesized compound (as in WO 2010 / 099534).

[0005] For example, an undeuterated compound can be treated with a deuterated acid such as D2SO4 or D3PO4 for several hours to obtain a deuterated compound.

[0006] An undeuterated compound can also be reacted in a deuterated solvent in the presence of a Lewis acid such as aluminum trichloride to obtain a deuterated compound.

[0007] There are also some deuteration methods using high temperature and voltage or radiation.

[0008] There are other deuteration methods using D2 gas, D2O or a deuterated solvent such as C6D6 as a deuterium source for H - D exchange by metal catalysis, as in WO 2016 / 073425 or KR101978651.

[0009] A method for deuterating aromatic compounds using an acid catalyst and a deuterated aromatic solvent as a deuterium source is also disclosed in the prior art, for example in WO 2011 / 053334.

[0010] Generally, deuteration methods are expensive and time-consuming. Therefore, there is always a need for deuteration methods for forming various deuterated compounds that can be used in OLEDs and for forming deuterated structural units that can be used in synthesizing deuterated compounds.

[0011] In addition, known chemical H-D exchange methods generally need to be carried out under harsh conditions in order to obtain a high degree of deuteration, and the disadvantage is that impurities may be formed simultaneously. On the other hand, when carried out under mild conditions, only a low degree of deuteration can be achieved. Therefore, there is also a need for a deuteration method that can be carried out under mild conditions and still produce a high degree of deuteration.

[0012] The term "deuterated compound" herein refers to a compound in which deuterium is present at least 100 times the natural abundance level. A higher degree of deuteration than in nature can be achieved by using structural units that have been pre-enriched with deuterium by a deuteration method or by subjecting a compound to a deuteration method.

[0013] Hereinafter, the term H-D exchange method and the term deuteration method are methods aimed at replacing one or more hydrogens in a compound with deuterium atoms.

[0014] According to the present invention, the degree of deuteration corresponds to the percentage (in %) of the number of deuterium atoms in a compound to the total number of deuterium atoms and protium atoms in the compound, as follows:

[0015] Degree of deuteration (%) = (N D * 100) / (N P + N D )

[0016] Where:

[0017] N D is the number of deuterium atoms in the compound

[0018] N P is the number of deuterium and protium atoms in the compound

[0019] Unless otherwise stated, the term hydrogen in the present invention refers to the protium isotope of hydrogen, which accounts for more than 99.98% of the hydrogen naturally present in the ocean.

[0020] The term "deuterated compound" corresponds to a compound in which at least one hydrogen atom is replaced by a deuterium atom and in which the deuterium abundance at each deuterated position in the compound is higher than the natural abundance of deuterium, which is about 0.015%. In order to be a "deuterated compound", the compound / precursor must undergo a deuterium enrichment or deuteration process.

[0021] The problem solved by the present invention is to provide a deuteration method that is particularly suitable as a method for forming deuterated organic materials and that can be carried out under mild conditions and still produce a high degree of deuteration.

[0022] Surprisingly, it has been found that the method described in more detail below solves this problem. In particular, the deuteration method of the present invention produces deuterated materials with a high degree of deuteration while the synthesis conditions are mild. The deuterated compounds obtained by the method of the present invention enable OLEDs to have very good performance in terms of lifetime and efficiency. Therefore, the method described below and the compounds obtained by said method are the objects of the present invention.

[0023] Therefore, the present invention provides a method for preparing a deuterated compound, the method comprising, in the following order:

[0024] (a) performing a first deuteration reaction of a compound by the H-D exchange method to form a first deuterated compound with a degree of deuteration x;

[0025] (b) performing a second deuteration reaction of the first deuterated compound by the H-D exchange method to form a second deuterated compound with a degree of deuteration y;

[0026] wherein the H-D exchange method in steps (a) and (b) is selected from H-D exchange catalyzed by an acid and H-D exchange catalyzed by a metal;

[0027] wherein

[0028] if the H-D exchange method in step (a) is H-D exchange catalyzed by a metal, then the H-D exchange method in step (b) is H-D exchange catalyzed by an acid, or

[0029] if the H-D exchange method in step (a) is H-D exchange catalyzed by an acid, then the H-D exchange method in step (b) is H-D exchange catalyzed by a metal, and

[0030] wherein after step (b), the degrees of deuteration x and y satisfy the following condition (Equation 1):

[0031] y≥1.3x (Equation 1).

[0032] Preferably, after step (b), y≥1.5x. More preferably, after step (b), y≥2x.

[0033] Preferably, after step (a), x≥30%, and after step (b), y≥50%.

[0034] More preferably, after step (a), x≥40%, and after step (b), y≥80%, very preferably ≥90%.

[0035] The degree of deuteration is experimentally determined by quantitatively 1 measuring the degree of deuteration of the compound by 1H-NMR.

[0036] H-D exchange carried out by metal catalysis is herein considered to refer to a method of exchanging hydrogen for deuterium in a compound by homogeneous metal catalysis or heterogeneous metal catalysis in combination with a deuteration source. H-D exchange carried out by acid catalysis is considered to refer to a method of exchanging hydrogen for deuterium in a compound by using a deuterated Brønsted acid or Lewis acid in combination with a deuterium source. Such methods are described in more detail in Angew. Chem. Int Ed. (Angewandte Chemie International Edition) 2007, 46, 7744 - 7765.

[0037] Preferably, the method includes a step of separating the product after step (a) and before step (b), such that the method includes the following steps in the following order:

[0038] (a) Performing a first deuteration reaction of a compound by an H-D exchange method to form a first deuterated compound having a degree of deuteration x;

[0039] (a-1) Separating the first deuterated compound;

[0040] (b) Performing a second deuteration reaction of the first deuterated compound by an H-D exchange method to form a second deuterated compound having a degree of deuteration y;

[0041] wherein the symbols x and y have the same meanings as described above.

[0042] It is also preferred to separate the deuterated compound after step (b). The separation of the compound in step (a-1) or after step (b) is carried out by known techniques. This can include extraction, precipitation, filtration, distillation, chromatography or similar techniques.

[0043] According to a preferred embodiment, the H-D exchange method in step (a) is H-D exchange carried out by metal catalysis, and the H-D exchange method in step (b) is H-D exchange carried out by acid catalysis.

[0044] According to another preferred embodiment, the H-D exchange method in step (a) is H-D exchange carried out by acid catalysis, and the H-D exchange method in step (b) is H-D exchange carried out by metal catalysis.

[0045] Preferably, the H-D exchange carried out by metal catalysis is selected from H-D exchange carried out by heterogeneous metal catalysis.

[0046] More preferably, the H-D exchange carried out by metal catalysis includes the following steps in the following order:

[0047] MC-1) Mixing a compound or a first deuterated compound, a solvent, a metal catalyst and a deuterium source;

[0048] MC-2) Heat to cause a reaction.

[0049] Preferably, step MC-2) is carried out at a temperature of 40°C to 250°C, more preferably 80°C to 200°C, even more preferably 100°C to 140°C.

[0050] In addition, step MC-2) is preferably carried out at a pressure of 1 atm to 20 atm, preferably 1 to 10 atm, more preferably 1 to 5 atm.

[0051] It is also preferred that step MC-2) is carried out under an inert gas, which is preferably selected from N2, He, and argon.

[0052] The reaction can also be carried out under reflux. Then, the solvent can be selected accordingly so as to reach the desired reaction temperature.

[0053] Preferably, step MC-2) is carried out for a period of 1 to 200 hours, preferably 1 to 100 hours, more preferably 1 to 50 hours, depending on the reaction time. Typically, step MC-2) is carried out for a period of 10 to 30 hours.

[0054] It is also preferred that step MC-2) is carried out in a closed vessel reactor.

[0055] The deuterium source in the H-D exchange carried out by metal catalysis preferably includes one of the following deuterium sources: deuterium oxide (D2O), deuterated benzene, more particularly benzene-D6, deuterated toluene, more particularly toluene-D5 and toluene-D8, deuterated xylene, more particularly xylene-D 10 , CDCl3, CD3OD, and mixtures thereof. More preferably, the deuterium source in the H-D exchange carried out by metal catalysis is D2O. In the context of the present invention, deuterium oxide also refers to heavy water.

[0056] The metal catalyst in the H-D exchange carried out by metal catalysis is preferably selected from metal catalysts comprising platinum, palladium, rhodium, ruthenium, nickel, cobalt, their oxides, their complexes, or combinations thereof. The H-D exchange carried out by metal catalysis can be carried out by homogeneous metal catalysis or heterogeneous metal catalysis. Soluble metal catalyst complexes are used for the homogeneous metal catalysis, while the metal catalyst is insoluble in the heterogeneous metal catalysis. In the case of the heterogeneous metal catalysis, the metal of the metal catalyst is preferably deposited on a solid phase that is insoluble in the composition. The solid phase can be a suitable material, such as carbon, such as activated carbon or carbon black, silicate, molecular sieve, or polymer. The solid phase is stable under the reaction conditions.

[0057] More preferably, the metal catalyst comprises or is a heterogeneous transition metal catalyst selected from platinum, palladium, their oxides or combinations thereof. Particularly preferably, the metal catalyst is a heterogeneous transition metal catalyst selected from platinum on carbon (Pt / C), palladium on carbon (Pd / C), platinum(IV) oxide on carbon (PtO2 / C), palladium(II) hydroxide on carbon (Pd(OH)2 / C), palladium(II) chloride on carbon (PdCl2 / C) or combinations thereof. Most preferably, the metal catalyst is a combination of platinum on carbon (Pt / C) and palladium on carbon (Pd / C). In the case of a combination of Pt / C and Pd / C, the ratio by weight of Pt / C to Pd / C is preferably a mixture of 10:1 to 1:2, preferably 7:1 to 1:1, especially 5:1 to 1:1.

[0058] The molar ratio of the metal catalyst to the compound to be deuterated is preferably 2:1 to 100:1, especially 2:1 to 70:1, preferably 2:1 to 30:1. At higher amounts of catalyst, generally fewer by-products are formed.

[0059] The metal catalyst is usually stored in a water-wetted state. Preferably, the metal catalyst is dried before use in H-D exchange by metal catalysis to improve the activity of the catalyst.

[0060] When drying the heterogeneous metal catalyst, the drying step is preferably carried out at a temperature of 20 °C to 200 °C, preferably 20 °C to 100 °C, particularly preferably under reduced pressure, especially below 100 mbar. The drying step is preferably carried out until the water content, as measured by the Karl-Fischer method, is below 5 wt%, preferably below 2 wt%, preferably below 1 wt%. Most preferably, the drying step is carried out at a temperature of 50 °C to 70 °C and under a reduced pressure of below 50 mbar, particularly preferably at a temperature of 50 °C to 70 °C and a reduced pressure of 30 mbar, most preferably at a temperature of 55 °C to 75 °C and a reduced pressure of 1 to 30 mbar. The drying step is preferably carried out for a period of at least 24 hours, especially at least 48 hours. Preferably, the drying step is carried out between 24 hours and 96 hours, especially between 48 hours and 96 hours.

[0061] The drying step of the metal catalyst is preferably carried out in air or an inert gas such as nitrogen or argon. No activation with hydrogen or deuterium occurs.

[0062] Preferably, the solvent in the H-D exchange carried out by metal catalysis includes solvents selected from aromatic solvents, ethers, alcohols, alkanes, cycloalkanes, acids, amides, esters, and mixtures thereof. A suitable solvent is a solvent in which the compound to be deuterated is at least partially soluble. If a deuterated aromatic solvent (e.g., benzene-d6) is used, the solvent can also serve as a deuterium source. In this case, an additional deuterium source (e.g., deuterium oxide) can be present, or the deuterated aromatic compound is the sole deuterium source.

[0063] According to a preferred embodiment, the solvent includes alkanes, preferably cycloalkanes, and very preferably cycloalkanes containing at least one ring with 6 or more aliphatic carbon atoms. Examples of suitable cycloalkanes are cyclohexane, methylcyclohexane, and also fused cycloalkanes such as decalin (cis- or trans-decalin and mixtures thereof).

[0064] According to another preferred embodiment, the solvent includes ethers, preferably aliphatic ethers, which can be cyclic or straight-chain, and which preferably contain 4 to 18 carbon atoms and 1 to 4 oxygen atoms, more preferably 4 to 12 carbon atoms and 1 to 3 oxygen atoms, and even more preferably 4 to 8 carbon atoms and 1 to 2 oxygen atoms. Preferably, the ether as the solvent is a cyclic aliphatic ether. Examples of suitable ethers are cyclic ethers such as 1,4-dioxane, tetrahydropyran (THP), tetrahydrofuran (THF), aliphatic monoethers such as tert-butyl methyl ether, tert-butyl ethyl ether, dibutyl ether; aliphatic diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Particularly preferred are cyclic ethers such as 1,4-dioxane, tetrahydropyran, tetrahydrofuran, especially 1,4-dioxane or tetrahydropyran. Alkane, tetrahydropyran (THP), tetrahydrofuran (THF), aliphatic monoethers such as tert-butyl methyl ether, tert-butyl ethyl ether, dibutyl ether; aliphatic diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Particularly preferred are cyclic ethers such as 1,4-dioxane, tetrahydropyran, tetrahydrofuran, especially 1,4-dioxane or tetrahydropyran. Preferably, in the H-D exchange carried out by metal catalysis, the amount of the solvent used is such that the organic compound is at least partially dissolved, and the deuterium source: solvent ratio measured by volume is preferably 2:1 to 1:50, preferably 1:1 to 1:30, especially 1:1.5 to 1:30, and most especially 1:1.5 to 1:10. Here, the ideal amount depends on the solubility of the compound. Alkane or tetrahydropyran.

[0065] Preferably, in the H-D exchange carried out by metal catalysis, the amount of the solvent used is such that the organic compound is at least partially dissolved, and the deuterium source: solvent ratio measured by volume is preferably 2:1 to 1:50, preferably 1:1 to 1:30, especially 1:1.5 to 1:30, and most especially 1:1.5 to 1:10. Here, the ideal amount depends on the solubility of the compound.

[0066] Additional examples of suitable solvents for the H-D exchange carried out by metal catalysis include, but are not limited to, methanol, ethanol, isopropanol, acetic acid, N,N-dimethylformamide, benzene, toluene, xylene, mesitylene, and mixtures thereof.

[0067] According to a preferred embodiment of the present invention, the solvent in the H-D exchange carried out by metal catalysis consists of at least two solvents selected identically or differently from alkanes, ethers, and alcohols.

[0068] It can be advantageous to use at least one aliphatic ether as a solvent for organic compounds containing at least one NH functional group, especially aromatic or heteroaromatic compounds. Thus, the process according to the invention is particularly suitable for intermediate stages having such free NH functional groups in OLED production. The NH functional group means an NH group as well as an NH2 group. They can be, for example, primary or secondary amines and carbazole compounds or carbazole derivatives.

[0069] In one embodiment of the invention, the mixture in step MC-1) further comprises at least one additive to improve deuteration and / or reduce by-products. Preferably, the at least one additive is selected from alkylamines, preferably alkylamines having an alkyl group with 1 to 40 carbon atoms, where non-adjacent CH2 groups can be replaced by O and at least two alkyl groups can form a ring with each other, metal salts and / or metal oxides selected from salts or oxides of palladium, platinum, rhodium, ruthenium, silver, gold, copper, nickel or cobalt, where preferably salts or oxides of silver or palladium, especially Pd(II), are preferred. In the case of the salts, they can be, for example, chlorides, bromides, iodides, nitrates, sulfates, carboxylates such as acetates, propionates, pivalates, for example Pd(OAc)2, Ag(OAc) or Pd(OPiv)2. Particularly preferred are carboxylates such as Pd(OAc)2, Ag(OAc) or Pd(OPiv)2.

[0070] Preferred alkylamines are alkylamines having at least two, preferably three, especially alkyl groups with 1 to 40 carbon atoms, where non-adjacent CH2 groups can be replaced by O and at least two alkyl groups can form a ring. Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl. Preferred are alkylamines (tertiary amines) having three alkyl groups with 1 to 5 carbon atoms, and alkylamines having three alkyl groups, two of which form a ring, where the ring can contain an O atom.

[0071] Examples of such amines are triethylamine, dimethylethylamine, diethylmethylamine, diisopropylethylamine, preferably triethylamine. Examples of cyclic amines are morpholine derivatives, especially N-alkylmorpholines such as N-methylmorpholine, N-ethylmorpholine, N-propylmorpholine.

[0072] Preferably, the amine used is soluble in the composition.

[0073] More particularly, alkylamines, silver salts and / or palladium salts promote deuteration and reduce the formation of by-products. This may allow the reaction to proceed for a longer time or at a higher temperature. The use of the additive may depend on the compound to be deuterated.

[0074] Depending on the reaction procedure and the organic compound, different amounts of the additive may be used. Preferably, the at least one additive is used in a molar ratio of additive to organic compound of 1:2 to 1:100, preferably 1:2 to 1:50, particularly 1:2 to 1:30.

[0075] Preferably, the H-D exchange carried out by acid catalysis is selected from the H-D exchange carried out by homogeneous acid catalysis.

[0076] More preferably, the H-D exchange carried out by acid catalysis comprises the following steps:

[0077] AC-1) Mixing the compound or the first deuterated compound with a deuterated solvent;

[0078] AC-2) Treating the reaction mixture of step AC-1) with an acid catalyst having a pKa of 0 or lower in water.

[0079] Preferably, step AC-2) is carried out under an inert gas, which is preferably selected from N2, He, and argon.

[0080] It is also preferred that step AC-2) is carried out at a controlled temperature of -90°C to 120°C, preferably -50°C to 100°C, more preferably 10°C to 40°C.

[0081] Step AC-2) is generally carried out for a period of 0.5 to 200 hours, preferably 1 to 100 hours, more preferably 1 to 50 hours.

[0082] Preferably, the acid catalyst has a pKa of -5 or lower in water at 20°C.

[0083] More preferably, the acid catalyst is selected from Bronsted acids, and even more preferably from strong or super strong Bronsted acids. The acid catalyst preferably has a pKa of -10 or lower in water at 20°C.

[0084] According to a preferred embodiment, the acid catalyst is a deuterated acid catalyst.

[0085] According to another preferred embodiment, the acid catalyst is not deuterated.

[0086] Examples of acid catalysts are H2SO4, D2SO4, CF3CO2H, CF3CO2D, CH3SO3H, CH3SO3D, C6H6SO3H, C6H6SO3D, CF3SO3H, CF3SO3D, FSO3H, FSO3D, and mixtures thereof, with more preferred acid catalysts being super Bronsted acids such as CF3SO3H and CF3SO3D.

[0087] According to a preferred embodiment, the deuterated solvent in the H-D exchange by acid catalysis is a deuterated organic solvent. More preferably, the deuterated solvent in the H-D exchange by acid catalysis is a deuterated aromatic solvent.

[0088] Examples of suitable deuterated solvents for H-D exchange by acid catalysis are deuterated benzene, more particularly benzene-D6, deuterated toluene, more particularly toluene-D5, toluene-D8, deuterated xylene, more particularly xylene-D 10 , CDCl3, CD3OD, and mixtures thereof.

[0089] Preferably, in the H-D exchange by acid catalysis, the deuterated solvent serves as a deuterium source. Thus, after the H-D exchange by acid catalysis, the degree of deuteration in the deuterated solvent decreases.

[0090] According to a preferred embodiment of the present invention, the deuterated solvent used in the H-D exchange by acid catalysis is re-enriched with deuterium by introducing the deuterated solvent into the reaction mixture of the H-D exchange by metal catalysis after the H-D exchange by acid catalysis. In this way, the degree of deuteration of the deuterated solvent increases and it can be reused in the H-D exchange by acid catalysis.

[0091] Preferably, the compound to be deuterated is an organic compound.

[0092] More preferably, the compound to be deuterated includes an aromatic ring system, a heteroaromatic ring system, an aromatic amine, or an organometallic compound. It should be understood that the aromatic ring system, heteroaromatic ring system, aromatic amine, and organometallic compound may be substituted by one or more substituents such as halogen, alkyl groups, aromatic or heteroaromatic ring systems.

[0093] The following definitions of chemical groups apply for the purposes of this application:

[0094] An aryl group in the sense of the present invention contains 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms; a heteroaryl group in the sense of the present invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O, and S. This represents the basic definition. If in the description of the present invention, other preferred embodiments are indicated, for example, regarding the number of aromatic ring atoms or the heteroatoms present, these preferred embodiments apply.

[0095] An aryl group or a heteroaryl group is herein considered to refer to a simple aromatic ring, i.e., benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, or thiophene, or a fused (condensed) aromatic or heteroaromatic polycycle, such as naphthalene, phenanthrene, quinoline, or carbazole. A fused (condensed) aromatic or heteroaromatic polycycle in the sense of the present application consists of two or more simple aromatic or heteroaromatic rings fused to each other.

[0096] An aryl or heteroaryl group that can be substituted by the above groups in each case and can be linked to an aromatic or heteroaromatic ring system via any desired position is particularly considered to refer to a group derived from the following substances: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo - 5,6 - quinoline, benzo - 6,7 - quinoline, benzo - 7,8 - quinoline, phenothiazine, phen azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinimidazole, azole, benzo azole, naphtho azole, anthra azole, phenanthro azole, iso azole, 1,2 - thiazole, 1,3 - thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, aza - carbazole, benzocarboline, phenanthroline, 1,2,3 - triazole, 1,2,4 - triazole, benzotriazole, 1,2,3 - diazole, 1,2,4 - diazole, 1,2,5 - diazole, 1,3,4 - Diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0097] The aryloxy group as defined according to the present invention is considered to mean an aryl group as defined above bonded via an oxygen atom. A similar definition applies to the heteroaryloxy group.

[0098] The aromatic ring system in the sense of the present invention contains 6 to 60 carbon atoms in the ring system, preferably 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms. The heteroaromatic ring system in the sense of the present invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and / or S. The aromatic or heteroaromatic ring system in the sense of the present invention is intended to be considered to mean the following system, which does not have to contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups can additionally be connected via non-aromatic units (preferably less than 10% of the non-H atoms), such non-aromatic units being, for example, sp 3 hybridized C, Si, N or O atoms, sp 2 hybridized C or N atoms, or sp hybridized C atoms. Thus, for example, systems in which two or more aryl groups are connected, for example, via a straight-chain or cyclic alkyl, alkenyl or alkynyl group or via a silyl group, such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also intended to be considered aromatic ring systems in the sense of the present invention. In addition, systems in which two or more aryl or heteroaryl groups are connected to each other via a single bond, for example, such as biphenyl, terphenyl or diphenyltriazine, are also considered aromatic or heteroaromatic ring systems in the sense of the present invention.

[0099] An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may also be substituted by groups in each case and may be linked to the aromatic or heteroaromatic group via any desired position, is particularly considered to refer to a group derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, bibenzylidene, terphenyl, terbenzylidene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indeno[1,2-b]fluorene, trindene, isotrindene, spirotrindene, spiroisotrindene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indeno[1,2-b]carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phen azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinimidazole, azole, benzo azole, naphtho azole, anthra azole, phenanthro azole, iso azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaphenanthrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phen oxazine, phenothiazine, fluoranthene ring, naphthyridine, azacarbazole, benzocarbazole, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, or a combination of these groups.

[0100] For the purposes of the present invention, a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, in which individual H atoms or CH2 groups may additionally be substituted by the groups mentioned above under the definition of the said groups, is preferably considered to mean the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl group having 1 to 40 carbon atoms is preferably considered to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0101] For the purposes of the present application, the term that two groups may form a ring with each other is intended to be considered in particular to mean that the two groups are connected to each other by a chemical bond. This is illustrated by the following scheme:

[0102]

[0103] However, in addition, the above term is also intended to be considered to mean that in the case where one of the two groups represents hydrogen, the second group is bonded at the bonding position of the hydrogen atom, thereby forming a ring. This is illustrated by the following scheme:

[0104]

[0105] When two groups form a ring with each other, it is preferred that the two groups are adjacent groups. Adjacent groups in the sense of the present invention are groups bonded to atoms directly connected to each other or groups bonded to the same atom.

[0106] According to a preferred embodiment, the compound to be deuterated comprises an aromatic ring system. More preferably, the compound to be deuterated is an aromatic ring system selected from aromatic ring systems having 6 to 60 aromatic ring atoms, which may be substituted by one or more groups R R Substituted. Preferred aromatic ring systems are selected from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, bibenzylidene, terphenyl, terbenzylidene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indeno[1,2-b]fluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, and combinations of these groups, which may be substituted by one or more groups R R Substituted, wherein

[0107] R R Each occurrence, independently of one another, represents H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar)2, S(═O)Ar, S(═O)2Ar, N(R’)2, N(Ar)2, NO2, Si(R’)3, B(OR’)2, OSO2R’, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more groups R’, wherein in each case one or more non-adjacent CH2 groups may be replaced by R’C═CR’, C≡C, Si(R’)2, Ge(R’)2, Sn(R’)2, C═O, C═S, C═Se, P(═O)(R’), SO, SO2, O, S or CONR’, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may be substituted by one or more groups R’, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R’; wherein two groups R R May together form an aliphatic or aromatic ring system which may be substituted by one or more groups R’;

[0108] Ar, each occurrence, independently of one another, is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may also be substituted by one or more groups R’;

[0109] R’ is the same or different at each occurrence and represents H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S, and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.

[0110] According to another preferred embodiment, the compound to be deuterated comprises a heteroaromatic ring system. More preferably, the compound to be deuterated comprises a heteroaromatic ring system selected from substituted or unsubstituted heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which heteroaromatic ring system may be substituted by one or more groups R R substituted. Preferred heteroaromatic ring systems are selected from furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indeno[1,2-c]carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phen azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzo oxazole, naphtho oxazole, anthra oxazole, phenanthro oxazole, iso oxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaphenanthrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperopyrene, pyrazine, phenazine, phen oxazine, phenothiazine, fluorene ring, naphthyridine, azacarbazole, benzocarbazole, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indazole and benzothiadiazole, or combinations of these groups, which may be substituted by one or more groups R R where R R is as defined above.

[0111] According to a preferred embodiment, the compound to be deuterated is a heteroaromatic compound selected from compounds of formula (h-1) or (h-2):

[0112]

[0113] wherein:

[0114] K is Ar 10 or -L 1 -N(Ar)2;

[0115] Z is C-R Z ; or two adjacent groups Z together form a fused ring;

[0116] R Z is in each case the same or different and is selected from H, D, F, Cl, Br, I, N(Ar)2, N(R)2, OAr, SAr, CN, NO2, OR, SR, COOR, C(=O)N(R)2, Si(R)3, B(OR)2, C(=O)R, P(=O)(R)2, S(=O)R, S(=O)2R, OSO2R, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group in each case may be substituted by one or more R groups, where one or more non-adjacent CH2 groups may be replaced by Si(R)2, C=O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system, the aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R groups;

[0117] L 1 is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and may be substituted by one or more R groups;

[0118] Ar 10is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R groups;

[0119] R Z is in each case the same or different and is H, D, F, Cl, Br, I, N(Ar)2, N(R)2, OAr, SAr, CN, NO2, OR, SR, COOR, C(=O)N(R)2, Si(R)3, B(OR)2, C(=O)R, P(=O)(R)2, S(=O)R, S(=O)2R, OSO2R, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R groups, where one or more non-adjacent CH2 groups may be replaced by Si(R)2, C=O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system, the aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may in each case be substituted by one or more R groups; simultaneously, two R Z groups may also together form a ring system;

[0120] E is independently in each occurrence a single bond or the group C(R 0 )2;

[0121] R 0 is independently in each occurrence selected from a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, which may in each case be substituted by one or more R' groups;

[0122] x, y are independently selected from 0 or 1, where when x or y is 0, then the corresponding group E is absent; and x + y = 1 or 2; and

[0123] R, each occurrence being the same or different, represents H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, N(R')₂, N(Ar)₂, NO₂, Si(R')₃, B(OR')₂, OSO₂R', a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more groups R', wherein in each case one or more non-adjacent CH₂ groups may be replaced by R'C═CR', C≡C, Si(R')₂, Ge(R')₂, Sn(R')₂, C═O, C═S, C═Se, P(═O)(R'), SO, SO₂, O, S or CONR', and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may be substituted by one or more groups R', or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R'; wherein two groups R may together form an aliphatic or aromatic ring system which may be substituted by one or more groups R';

[0124] Ar, each occurrence being the same or different, is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may also be substituted by one or more groups R';

[0125] R', each occurrence being the same or different, represents H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, wherein in each case one or more non-adjacent CH₂ groups may be replaced by SO, SO₂, O, S, and wherein one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.

[0126] More preferably, the compound to be deuterated is a heteroaromatic compound selected from the compounds of formulas (h-1-1) to (h-1-3), (h-2-1) to (h-2-2) and (h-3-1):

[0127]

[0128]

[0129] wherein the symbols and notations have the following meanings:

[0130] M is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R groups;

[0131] E 1 is independently, each time it appears, a single bond or the group C(R 0 )2; where R 0 has the same meaning as in claim 28;

[0132] Ar 5 is the same or different, each time it appears, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R groups;

[0133] R T 、R V 、R 6 are the same or different in each case and are selected from H, D, F, Cl, Br, I, N(Ar)2, N(R)2, OAr, SAr, CN, NO2, OR, SR, COOR, C(=O)N(R)2, Si(R)3, B(OR)2, C(=O)R, P(=O)(R)2, S(=O)R, S(=O)2R, OSO2R, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may be substituted by one or more R groups in each case, where one or more non-adjacent CH2 groups may be replaced by Si(R)2, C=O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system, the aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may be substituted by one or more R groups in each case; simultaneously, two R T groups may together form a ring system, two R V groups may together form a ring system and / or two R 6 groups may together form a ring system;

[0134] x 1 、y 1 are independently selected from 0 or 1, where when x 1 or y 1 is 0, then the corresponding group E 1 is absent; provided that x 1 +y 1 = 1 or 2;

[0135] c, f are the same or different, each time they appear, and represent 0, 1, 2, 3 or 4;

[0136] d and e each independently represent 0, 1, 2, or 3 each time they appear;

[0137] If x 1 = 0, then g represents 0, 1, 2, or 3; or if x 1 = 1, then g represents 0, 1, or 2;

[0138] If y 1 = 0, then h represents 0, 1, 2, 3, or 4; or if y 1 = 1, then h represents 0, 1, 2, or 3;

[0139] If x = 0, then k represents 0, 1, 2, 3, or 4; or if x = 1, then k represents 0, 1, 2, or 3;

[0140] If y = 0, then l represents 0, 1, 2, or 3; or if y = 1, then l represents 0, 1, or 2;

[0141] s each independently represents 0, 1, 2, 3, or 4 each time it appears; and

[0142] u represents 0, 1, or 2;

[0143] And wherein the symbols and designations R Z , K, E, R, Ar, x, and y have the same meanings as described above.

[0144] Preferably, K is Ar 10 , and Ar 10 is selected from aromatic ring systems having 6 to 40, preferably 6 to 30, more preferably 6 to 18 aromatic ring atoms, or heteroaromatic ring systems having 5 to 40, preferably 6 to 30, more preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more R groups.

[0145] Preferably, M is an aromatic ring system having 6 to 40 aromatic ring atoms, or a heteroaromatic ring system having 5 to 40, preferably 6 to 30, more preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more R groups.

[0146] Preferably, Ar 5 each independently is an aromatic ring system having 6 to 30, preferably 6 to 18 aromatic ring atoms, or a heteroaromatic ring system having 5 to 30, preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more R groups each time it appears.

[0147] Examples of such heteroaromatic compounds are described below:

[0148]

[0149]

[0150]

[0151] According to another preferred embodiment, the compound to be deuterated is an aromatic amine, wherein the aromatic amine contains one, two or three groups selected from aromatic or heteroaromatic ring systems. More preferably, the compound to be deuterated is an aromatic amine containing three aromatic or heteroaromatic ring systems, the aromatic or heteroaromatic ring systems being selected from aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R R substituted, where R R has the same definition as above.

[0152] Even more preferably, the compound to be deuterated is an aromatic amine selected from the compounds of formula (A):

[0153]

[0154] wherein:

[0155] A 1 is the same or different in each case and is H, an alkyl group having 1 to 20 carbon atoms and which may be substituted by one or more R 1 groups, or Ar 1 ;

[0156] Ar 1 is the same or different in each case and is an aromatic ring system having 6 to 60 aromatic ring atoms and which may be substituted by one or more R 1 groups, or a heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R 1 groups; Ar 1 and / or A 1 groups may be bonded to each other via R 1 groups;

[0157] R 1 is the same or different in each case and is selected from H, D, F, C(=O)R 2 , CN, Si(R 2 )3, P(=O)(R 2 )2, OR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more R 1The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R 2 groups; and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R 2 C=CR 2 -, -C≡C-, Si(R 2 )2, C=O, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, P(=O)(R 2 ), -O-, -S-, SO or SO2;

[0158] R 2 is the same or different in each case and is selected from H, D, F, CN, an alkyl group having 1 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R 2 groups may be linked to each other and may form a ring; and the alkyl groups, the aromatic ring systems and the heteroaromatic ring systems mentioned may be substituted by F or CN.

[0159] Particularly preferably, the compound to be deuterated is selected from the compounds of one of the formulas (A-I) to (A-IX):

[0160]

[0161]

[0162]

[0163] wherein one or more R 1 groups may be bonded to any of the indicated unsubstituted positions, and:

[0164] V is the same or different in each case and is CR 1 or N;

[0165] E 10 is the same or different in each case and is a single bond, O, S, C(R 1 )2, Si(R 1 )2, PR 1 , C(R 1 )2-C(R 1 )2 or CR 1 =CR 1 , preferably O, S, C(R 1 )2 or Si(R 1 )2;

[0166] E 20 Identical or different in each case and is O, S, C(R 1 )2, Si(R 1 )2, PR 1 , NR 1 , C(R 1 )2-C(R 1 )2 or CR 1 =CR 1 , preferably O, S, C(R 1 )2 or Si(R 1 )2;

[0167] Ar 2 is an aromatic ring system having 6 to 20 aromatic ring atoms and may be substituted by one or more R 1 groups, or a heteroaromatic ring system having 5 to 20 aromatic ring atoms and may be substituted by one or more R 1 groups;

[0168] n, p, q are identical or different and each is 0 or 1; and

[0169] Ar 1 , R 1 are as defined above.

[0170] Preferred aromatic amine compounds are hole transport materials, which can be used in hole transport, hole injection or electron blocking layers, such as indeno[1,2-b]fluoreneamine derivatives (e.g., according to WO 06 / 122630 or WO 06 / 100896), amine derivatives disclosed in EP 1661888, hexazatriphenylene derivatives (e.g., according to WO 01 / 049806), amine derivatives having a fused aromatic system (e.g., according to US 5,061,569), amine derivatives disclosed in WO 95 / 09147, monobenzoindeno[1,2-b]fluoreneamine (e.g., according to WO 08 / 006449), dibenzoindeno[1,2-b]fluoreneamine (e.g., according to WO 07 / 140847), spirobifluoreneamine (e.g., according to WO2012 / 034627 or WO2013 / 120577), fluoreneamine (e.g., according to WO 2014 / 015937, WO 2014 / 015938 and WO2014 / 015935), spirodibenzopyranamine (e.g., according to WO 2013 / 083216) and dihydroacridine derivatives (e.g., according to WO 2012 / 150001).

[0171] Still according to a preferred embodiment of the present invention, the compound to be deuterated comprises an organometallic compound. Preferably, the organometallic compound contains metal atoms selected from copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium. More preferably, it is a compound containing iridium or platinum and having at least one heteroaromatic ring system. Preferably, it is a compound suitable as a phosphorescent compound (= triplet emitter). Examples of such compounds can be found in applications WO 00 / 70655, WO2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO05 / 033244, WO 05 / 019373, US2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2018 / 011186 and WO 2018 / 041769, WO 2019 / 020538, WO 2018 / 178001, WO 2019 / 115423 or WO 2019 / 158453. Generally, all phosphorescent complexes as used in phosphorescent OLEDs according to the prior art and known to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art can use additional phosphorescent complexes without creative work.

[0172] Preferably, the organometallic compound is a metal chelate complex, especially a metal chelate complex having at least one heteroaromatic ring system as a chelating ligand of the metal. Preferably, at least one heteroaromatic ring system is bonded to the metal via at least one nitrogen atom and via at least one carbon atom. Preferably, these atoms are each part of an aryl group or a heteroaryl group, which are connected via at least a single bond. Examples of such compounds are 2-phenylpyridine or similar compounds in which the above aryl group or heteroaryl group is connected via a single bond.

[0173] Preferably, in the H-D exchange carried out by metal catalysis or acid catalysis, the ratio of the hydrogen atoms of the organic compound to the deuterium of the deuterium source is at least 1:1.5, preferably 1:1.5 to 1:1000, preferably 1:2 to 1:500, particularly preferably 1:5 to 1:200. A ratio of 1:5 to 1:100 is particularly preferred.

[0174] The present invention also relates to a deuterated compound obtained by the deuteration method as described above.

[0175] The deuterated compound according to the present invention is suitable for electronic devices, particularly organic light-emitting diodes (OLEDs). Depending on the substitution, these compounds can be used for different functions and layers.

[0176] An electronic device in the sense of the present invention is a device comprising at least one layer containing at least one organic compound. The assembly may also contain inorganic materials or layers consisting entirely of inorganic materials.

[0177] The electronic device is preferably selected from organic light-emitting diodes (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic electroluminescent devices, but preferably organic light-emitting diodes (OLEDs).

[0178] The device is particularly preferably an organic light-emitting diode comprising a cathode, an anode, and at least one light-emitting layer, wherein at least one organic layer contains at least one deuterated compound according to the present invention, and the organic layer may be a light-emitting layer, a hole-transporting layer, an electron-transporting layer, a hole-blocking layer, an electron-blocking layer, or another functional layer.

[0179] In addition to the cathode, anode, light-emitting layer, hole-transporting layer, electron-transporting layer, hole-blocking layer, and electron-blocking layer, the organic light-emitting diode may further comprise additional layers, such as selected from hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers, charge-generation layers, and / or organic or inorganic p / n junctions. Similarly, an intermediate layer may be inserted between two light-emitting layers, which, for example, has an exciton-blocking function. However, it should be noted that not all of these layers must be present.

[0180] The organic electroluminescent device may comprise a light-emitting layer, or it may comprise a plurality of light-emitting layers. If there are a plurality of light-emitting layers, these light-emitting layers preferably have a plurality of emission peaks in total between 380 nm and 750 nm, such that white light is emitted overall, that is, different light-emitting compounds capable of fluorescing or phosphorescing are used in the light-emitting layers. In particular, a system with three light-emitting layers is preferred, wherein the three layers exhibit blue, green, and orange or red emission (the main structure is described, for example, in WO 2005 / 011013). The organic electroluminescent device according to the present invention may also be a tandem OLED, particularly an OLED that emits white light.

[0181] According to a preferred embodiment, the organic electroluminescent device comprises a hole-transporting layer, the hole-transporting layer comprising at least one deuterated hole-transporting material selected from deuterated aromatic amines obtained by the method according to the present invention.

[0182] According to a preferred embodiment, the organic electroluminescent device comprises an organic layer, preferably a light-emitting layer, the organic layer comprising at least one host or matrix material selected from deuterated aromatic or heteroaromatic compounds obtained by the method according to the present invention.

[0183] According to a preferred embodiment, the organic electroluminescent device comprises a light-emitting layer, the light-emitting layer comprising at least one phosphorescent emitter selected from deuterated organometallic compounds obtained by the method according to the present invention.

[0184] According to a preferred embodiment, the organic electroluminescent device comprises a light-emitting layer, the light-emitting layer comprising at least one fluorescent emitter selected from deuterated compounds comprising an aromatic ring system, a heteroaromatic ring system, or an aromatic amine obtained by the method according to the present invention.

[0185] In addition, the deuterated compounds according to the present invention may also be used in an electron-transporting layer and / or a hole-blocking layer and / or a hole-transporting layer and / or an exciton-blocking layer.

[0186] The term "phosphorescent compound" typically refers to a compound in which light emission occurs through a spin-forbidden transition, such as a transition from an excited triplet state or a state with a higher spin quantum number such as a quintet state.

[0187] When the deuterated compound is used as a hole-transporting material in a hole-transporting layer, a hole-injecting layer or an electron-blocking layer, the compound can be used as a pure material, i.e., in a 100% proportion in the hole-transporting layer, or it can be used in combination with one or more other compounds. In a preferred embodiment, the organic layer containing the deuterated compound further contains one or more p-type dopants. The p-type dopants used according to the present invention are preferably those organic electron acceptor compounds that are capable of oxidizing one or more of the other compounds in the mixture.

[0188] The deuterated compound can also be used in the light-emitting layer as a host (= matrix material) in combination with one or more light-emitting compounds, preferably phosphorescent compounds.

[0189] In this case, for a fluorescent light-emitting layer, the proportion of the matrix material in the light-emitting layer is between 50.0% by volume and 99.9% by volume, preferably between 80.0% by volume and 99.5% by volume, particularly preferably between 92.0% by volume and 99.5% by volume, and for a phosphorescent light-emitting layer, the proportion of the matrix material in the light-emitting layer is between 85.0% by volume and 97.0% by volume.

[0190] Thus, for a fluorescent light-emitting layer, the proportion of the light-emitting compound is between 0.1% by volume and 50.0% by volume, preferably between 0.5% by volume and 20.0% by volume, particularly preferably between 0.5% by volume and 8.0% by volume, and for a phosphorescent light-emitting layer, the proportion of the light-emitting compound is between 3.0% by volume and 15.0% by volume.

[0191] Examples of the fluorescent emitters are aromatic anthrylamines, aromatic anthryldiamines, aromatic pyrenylamines, aromatic pyrenyldiamines, aromatic perylenylamines or aromatic perylenydiamines. Aromatic anthrylamines are considered to be compounds in which one diarylamino group is preferably directly bonded to the anthracene group at the 9-position. Aromatic anthryldiamines are considered to be compounds in which two diarylamino groups are preferably directly bonded to the anthracene group at the 9,10-positions. Aromatic pyrenylamines, pyrenyldiamines, perylenylamines or perylenydiamines are defined in a similar manner, where the diarylamino group is preferably bonded to pyrene at the 1-position or at the 1,6-positions. Further preferred emitters are, for example, indeno[1,2-b]fluoreneamines or indeno[1,2-b]fluorenediamines according to WO 2006 / 108497 or WO2006 / 122630; benzoindeno[1,2-b]fluoreneamines or benzoindeno[1,2-b]fluorenediamines according to WO 2008 / 006449; and dibenzoindeno[1,2-b]fluoreneamines or dibenzoindeno[1,2-b]fluorenediamines according to WO 2007 / 140847; and indeno[1,2-b]fluorene derivatives containing fused aryl groups disclosed in WO2010 / 012328. Even more preferred emitters are benzoanthracene derivatives as disclosed in WO2015 / 158409, anthracene derivatives as disclosed in WO 2017 / 036573, fluorene dimers linked via heteroaryl groups as in WO2016 / 150544 or phen azine derivatives as disclosed in WO 2017 / 028940 and WO 2017 / 028941. Also preferred are pyrene arylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871. Also preferred are benzoindeno[1,2-b]fluoreneamines disclosed in WO 2014 / 037077, benzo[1,2-b]fluoreneamines disclosed in WO 2014 / 106522 and indeno[1,2-b]fluorene disclosed in WO 2014 / 111269 or WO 2017 / 036574, WO 2018 / 007421. Also preferred are emitters containing dibenzofuran or indeno[1,2-b]dibenzofuran moieties as disclosed in WO 2018 / 095888, WO 2018 / 095940, WO 2019 / 076789, WO 2019 / 170572. Also preferred are boron derivatives as disclosed, for example, in WO 2015 / 102118, CN108409769, CN107266484, WO2017195669 or US2018069182.

[0192] Examples of suitable host materials for fluorescent compounds include materials of various substance classes. Preferred host materials are selected from the following classes: oligoarylenes (e.g., 2,2’,7,7’-tetraphenylspirobifluorene according to EP 676461, or dinaphthylanthracene), in particular oligoarylenes having fused aromatic groups; oligoarylene vinylene (e.g., DPVBi or spiro-DPVBi according to EP 676461); polypod metal complexes (e.g., according to WO 2004 / 081017); hole-conducting compounds (e.g., according to WO 2004 / 058911); electron-conducting compounds, especially ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO 2005 / 084081 and WO 2005 / 084082); atropisomers (e.g., according to WO 2006 / 048268); boronic acid derivatives (e.g., according to WO 2006 / 117052); or benzanthracenes (e.g., according to WO 2008 / 145239). Particularly preferred host materials are selected from the following classes: oligoarylenes including naphthalene, anthracene, benzanthracene and / or pyrene, or atropisomers of these compounds; oligoarylene vinylene; ketones; phosphine oxides; and sulfoxides. Very particularly preferred host materials are selected from the following classes: oligoarylenes including anthracene, benzanthracene, benzophenanthrene and / or pyrene, or atropisomers of these compounds. In the context of the present invention, oligoarylenes are to be understood as compounds in which at least three aryl or arylene groups are linked together. Further preferred are the anthracene derivatives disclosed in WO 2006 / 097208, WO 2006 / 131192, WO 2007 / 065550, WO 2007 / 110129, WO 2007 / 065678, WO 2008 / 145239, WO 2009 / 100925, WO 2011 / 054442 and EP 1553154, the anthracene derivatives disclosed in EP 1749809, EP 1905754 and US2012 / 0187826, the pyrene compounds disclosed in WO 2015 / 158409, the benzanthracenylanthracene compounds disclosed in WO2017 / 025165, and the phenanthrylanthracene disclosed in WO 2017 / 036573.

[0193] Examples of the host materials for the phosphorescent emitters are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, such as according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines; carbazole derivatives, such as CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives according to WO 2005 / 039246, US2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; indolocarbazole derivatives, such as according to WO 2007 / 063754 or WO 2008 / 056746; indacarbazole derivatives, such as according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, such as according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar host materials, such as according to WO2007 / 137725; silanes, such as according to WO 2005 / 111172; borazoles or borates, such as according to WO 2006 / 117052; triazine derivatives, such as according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877; zinc complexes, such as according to EP 652273 or WO2009 / 062578; siladiazoles or silatetrazoles derivatives, such as according to WO 2010 / 054729; phosphadiazoles derivatives, such as according to WO 2010 / 054730; bridged carbazole derivatives, such as according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; terphenylidene derivatives, such as according to WO 2012 / 048781; lactams, such as according to WO 2011 / 116865 or WO 2011 / 137951; or dibenzofuran derivatives, such as according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO2017 / 148565. Also, another phosphorescent emitter having an emission wavelength shorter than that of the actual emitter may be present as a co-host in the mixture or a compound that does not participate or does not participate to a large extent in charge transport may be used, such as described in WO 2010 / 108579.

[0194] In addition to the deuterated compounds, suitable charge transport materials, such as those that can be used in the hole injection or hole transport layer or electron blocking layer or electron transport layer of the electronic device, are, for example, those mentioned in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953 - 1010, or other materials used in these layers according to the prior art.

[0195] Preferably, the OLED comprises two or more different hole transport layers. In this context, the deuterated compounds obtained by the method of the present invention can be used in one or more or all of the hole transport layers. Materials particularly preferred for use in the hole transport layer of the OLED include indeno[1,2 - b]fluoreneamine derivatives (e.g., according to WO 06 / 122630 or WO 06 / 100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g., according to WO 01 / 049806), amine derivatives having fused aromatic compounds (e.g., according to US 5,061,569), amine derivatives disclosed in WO 95 / 09147, monobenzylindeno[1,2 - b]fluoreneamine (e.g., according to WO 08 / 006449), dibenzylindeno[1,2 - b]fluoreneamine (e.g., according to WO 07 / 140847), spirobifluoreneamine (e.g., according to WO 2012 / 034627 or WO 2013 / 120577), fluoreneamine (e.g., according to WO2014 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), spirodibenzopyranamine (e.g., according to WO 2013 / 083216), dihydroacridine derivatives (e.g., according to WO 2012 / 150001), spirodibenzofuran and spirodibenzothiophene (e.g., according to WO 2015 / 022051, WO 2016 / 102048 and WO 2016 / 131521), phenanthrene diarylamine (e.g., according to WO 2015 / 131976), spirotribenzotropone (e.g., according to WO 2016 / 087017), spirobifluorene having a m - phenylenediamine group (e.g., according to WO 2016 / 078738), spirobisacridine (e.g., according to WO 2015 / 158411), xanthene diarylamine (e.g., according to WO 2014 / 072017), and 9,10 - dihydroanthracene spirocyclic compounds having a diarylamino group according to WO 2015 / 086108.

[0196] Particularly preferred hole-transporting materials are spirobifluorene compounds substituted by diarylamino groups at the 4-position as hole-transporting compounds, in particular those compounds claimed and disclosed in WO 2013 / 120577, and spirobifluorene compounds substituted by diarylamino groups at the 2-position as hole-transporting compounds, in particular those compounds claimed and disclosed in WO 2012 / 034627.

[0197] Suitable materials for the electron-transporting layer are all materials used as electron-transporting materials in the electron-transporting layer according to the prior art. Particularly suitable are aluminum complexes such as Alq3; zirconium complexes such as Zrq4; lithium complexes such as Liq; benzimidazole derivatives; triazine derivatives; pyrimidine derivatives; pyridine derivatives; pyrazine derivatives; quinoxaline derivatives; quinoline derivatives; diazole derivatives; aromatic ketones; lactams; boranes; phosphadiazole derivatives and phosphine oxide derivatives. Further suitable materials include derivatives of the above-mentioned compounds as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975 and WO 2010 / 072300.

[0198] All of the above-mentioned materials, all of which are suitable as OLED materials, can be deuterated by the method according to the present invention.

[0199] The deuterated materials can be used alone in a layer or in combination with one or more deuterated or non-deuterated materials. Thus, another aspect of the present invention is a composition comprising a deuterated compound obtained by the method as defined above and at least one additional compound.

[0200] Preferred cathodes for the electronic component are metals with a low work function, metal alloys of different metals (such as alkaline earth metals, alkali metals, main group metals or lanthanide elements (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.)) or multilayer structures. Also suitable are alloys of alkali metals or alkaline earth metals and silver, such as an alloy of magnesium and silver. In the multilayer structure, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can be used, and usually combinations of metals such as Ca / Ag, Mg / Ag or Ba / Ag are used. It can also be advantageous to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of suitable materials are alkali metal or alkaline earth metal fluorides, as well as corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). For this purpose, lithium quinolate (LiQ) can also be used. The layer thickness of the layer is preferably between 0.5 nm and 5 nm.

[0201] Preferred anodes are materials with a high work function. Preferably, the anode has a work function higher than 4.5 eV relative to vacuum. First, metals with a high redox potential (such as Ag, Pt, or Au) are suitable for this purpose. Second, metal / metal oxide electrodes (e.g., Al / Ni / NiO x , Al / PtO x ) can also be preferred. For some applications, at least one electrode must be transparent or partially transparent to allow irradiation of the organic material (organic solar cell) or light emission (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). Additionally preferred are conductive doped organic materials, especially conductive doped polymers. Further, the anode can also consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0202] The device is structured, provided with contact connections, and finally sealed to exclude the harmful effects of water and air.

[0203] In the other layers of the organic electroluminescent device, all materials commonly used in the prior art can be used. Thus, a person skilled in the art can use all known materials for organic electroluminescent devices in combination with the deuterated compounds without creative effort. Additionally, the above compounds, especially aromatic or heteroaromatic compounds, can be deuterated by the method according to the present invention, particularly improving their lifetime.

[0204] Preferably, the organic electroluminescent device comprises one or more layers deposited by a sublimation method. In this method, the material is applied by vapor deposition in a vacuum sublimation system at an initial pressure below 10 -5 mbar, preferably below 10 -6 mbar. However, the initial pressure can also be even lower, for example, below 10 -7 mbar.

[0205] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated by the OVPD (organic vapor deposition) method or by carrier gas sublimation. In this method, the material is applied at a pressure between 10 -5 mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, where the material is applied directly through a nozzle and thus structured.

[0206] Further preferred is an organic electroluminescent device comprising one or more layers which are fabricated from a solution, such as by spin coating, or by any printing method such as screen printing, flexographic printing, offset printing, LITI (light-induced thermal imaging, thermal transfer printing), inkjet printing or nozzle printing. For this purpose, soluble compounds are required, for example, which can be obtained by suitable substitution.

[0207] Hybrid methods are also feasible, where, for example, one or more layers are applied from a solution and one or more additional layers are vapor deposited.

[0208] These methods are generally known to those skilled in the art and can be applied by the skilled person to an organic electroluminescent device comprising the compounds of the invention without creative effort. Examples

[0209] The compound is subjected to the deuteration method described below. The degree of deuteration of the compound is determined by quantitative 1 1H-NMR. The duration and temperature of each deuteration process are determined in such a way that the highest possible degree of deuteration is achieved without formation of impurities: a trade-off is made between a high degree of deuteration and a low impurity content.

[0210] Example 1:

[0211] Example 1 is a method according to the invention comprising steps 1.1) and 1.2) as defined below.

[0212]

[0213] Step 1.1) A suspension of compound A (500 g, 0.89 mol) and cyclohexane (27.95 L) is prepared in an autoclave. Pt-C catalyst (200.0 g) and D2O (2.66 L) are added. The autoclave is sealed and degassed with N2. The reaction mixture is stirred at 120 °C and 4.0 bar for 24 hours and then cooled. After phase separation, the catalyst is washed with THF. The combined organic fractions are concentrated and filtered through basic AlO x The remaining clear solution is concentrated in vacuo and the residue is recrystallized from THF / cyclohexane (424 g, 98.9% purity determined by HPLC, degree of deuteration 56%).

[0214] Step 1.2) Under an inert atmosphere, the product obtained in Step 1.1) (9.2 g, deuteration degree 56%) was dissolved in toluene-d8 (110 mL). At 0 °C, trifluoromethanesulfonic acid (14 mL) was added dropwise. After 5 hours at 0 °C, a small amount of D2O (37 mL) was added dropwise (this step is optional. If H2O is used to quench the solution, the deuteration degree of the obtained product will be slightly reduced). The addition is strongly exothermic, and the temperature was controlled to a maximum of 15 °C. At 15 °C, an aqueous NaOH solution (50 mL, 20 wt%) was added dropwise. The organic layer was separated and washed with brine and distilled H2O. The solvent was removed under reduced pressure. The crude product was purified by short column chromatography (toluene, basic AlO x )), recrystallization (toluene), and sublimation to obtain the purified product (6.6 g, 99.96% purity determined by HPLC, deuteration degree 90%).

[0215] Example 2:

[0216] Example 2 is a method according to the invention comprising Steps 2.1) and 2.2) as defined below.

[0217]

[0218] Step 2.1) A suspension of compound B (500 g, 0.79 mol), cyclohexane (23.3 L), and 1,4-di ane (1.47 L) was prepared in an autoclave. A Pt / Pd-C catalyst (375 g, 4:1) and D2O (2.75 L) were added. The autoclave was sealed and degassed with N2. The reaction mixture was stirred at 120 °C and 4.6 bar for 20 hours and then cooled. After phase separation, the catalyst was washed with THF. The combined organic fractions were concentrated and filtered through basic AlO x . The remaining clear solution was concentrated in vacuo, and the residue was recrystallized from toluene / acetonitrile and toluene / ethanol (338 g, 99.96% purity determined by HPLC, deuteration degree 41%).

[0219] Step 2.2) Under an inert atmosphere, the product obtained from Step 2.1) (5.0 g, deuteration degree 41%) was dissolved in toluene-d8 (63 mL). At 10 °C, trifluoromethanesulfonic acid (6.6 mL) was added dropwise. After 23 hours at 20 °C, the temperature was lowered to 7 °C and a small amount of D2O (9.4 mL) was added dropwise (this step is optional. If H2O is used to quench the solution, the deuteration degree of the obtained product will be slightly reduced). The addition is strongly exothermic, and the temperature was controlled to a maximum of 15 °C. At 15 °C, an aqueous NaOH solution (50 mL, 20 wt%) was added dropwise. The organic layer was separated, washed with brine and distilled H2O and dried over Na2SO4. After filtration, the solvent was removed under reduced pressure. A crude product in the form of an off-white solid was obtained. (5.0 g, 99.7% purity determined by HPLC, deuteration degree 84%).

[0220] Comparative Example 3:

[0221] Comparative Example 3 is a comparative method including Step 3.1) and Step 3.2) described below.

[0222]

[0223] Step 3.1) A suspension of Compound A (500 g, 0.89 mol) and cyclohexane (27.95 L) was prepared in an autoclave. Pt-C catalyst (200.0 g) and D2O (2.66 L) were added. The autoclave was sealed and degassed with N2. The reaction mixture was stirred at 120 °C and 4.0 bar for 24 hours and then cooled. After phase separation, the catalyst was washed with THF. The combined organic fractions were concentrated and filtered through basic AlO x The remaining clear solution was concentrated in vacuo, and the residue was recrystallized from THF / cyclohexane (424 g, 98.9% purity determined by HPLC, deuteration degree 56%).

[0224] Step 3.2) A suspension of the product obtained from Step 3.1) (1.0 g, 1.78 mol) and cyclohexane (43.0 g) was prepared in an autoclave. Pt-C catalyst (0.40 g) and D2O (6.0 g) were added. The autoclave was sealed and degassed with N2. The reaction mixture was stirred at 120 °C and 4.0 bar for 20 hours and then cooled. After phase separation, the catalyst was washed with THF. The combined organic fractions were concentrated and filtered through basic AlO x The remaining clear solution was concentrated in vacuo to obtain the product (deuteration degree 67%).

[0225] Comparative Example 4:

[0226] Comparative Example 4 is a comparative method including Step 4.1) and Step 4.2) described below.

[0227]

[0228] Step 4.1) Dissolve compound A (5.0 g) in toluene-d8 (63 mL) under an inert atmosphere. At 10 °C, add dropwise trifluoromethanesulfonic acid (7.8 mL). After 5 hours at 0 °C, add dropwise a small amount of D2O (20.9 mL) (this step is optional; if H2O is used to quench the solution, the degree of deuteration of the obtained product will be slightly reduced). The addition is strongly exothermic, and the temperature is controlled to a maximum of 15 °C. At 15 °C, add dropwise an aqueous NaOH solution (50 mL, 20 wt%). Separate the organic layer, wash it with brine and distilled H2O, and dry it over Na2SO4. After filtration, remove the solvent under reduced pressure. Obtain a crude product as an off-white solid. (4.7 g, 99.9% purity determined by HPLC, degree of deuteration 52%).

[0229] Step 4.2) Dissolve the product obtained from Step 4.1) (4.7 g) in toluene-d8 (57 mL) under an inert atmosphere. At 10 °C, add dropwise trifluoromethanesulfonic acid (7.0 mL). After 5 hours at 0 °C, add dropwise a small amount of D2O (18.7 mL) (this step is optional; if H2O is used to quench the solution, the degree of deuteration of the obtained product will be slightly reduced). The addition is strongly exothermic, and the temperature is controlled to a maximum of 15 °C. At 15 °C, add dropwise an aqueous NaOH solution (50 mL, 20 wt%). Separate the organic layer, wash it with brine and distilled H2O, and dry it over Na2SO4. After filtration, remove the solvent under reduced pressure. Obtain a crude product as an off-white solid. (4.1 g, 99.9% purity determined by HPLC, degree of deuteration 52%).

[0230] Comparative Example 5

[0231] Comparative Example 5 is a comparative method including Steps 5.1) and 5.2) described below.

[0232]

[0233] Step 5.1) Prepare a suspension of compound B (500 g, 1.53 mol), cyclohexane (23.3 L), and 1,4-di ane (1.47 L) in an autoclave. Add a Pt / Pd-C catalyst (375 g, 4:1) and D2O (2.75 L). Seal the autoclave and degas it with N2. Stir the reaction mixture at 120 °C and 4.6 bar for 20 hours, then cool. After phase separation, wash the catalyst with THF. Concentrate the combined organic fractions and pass them through basic AlO xFiltration. The remaining clarified solution was concentrated in vacuo, and the residue was recrystallized from toluene / acetonitrile and toluene / ethanol (338 g, 99.96% purity determined by HPLC, deuteration degree 41%).

[0234] Step 5.2) A suspension of the product obtained in Step 5.1) (1 g, 0.79 mol), cyclohexane (68 mL) and 1,4-dioxane (1 mL) was prepared in an autoclave. Pt / Pd-C catalyst (750 mg, 4:1) and D2O (10 mL) were added. The autoclave was sealed and degassed with N2. The reaction mixture was stirred at 120 °C and 4.6 bar for 20 h and then cooled. After phase separation, the catalyst was washed with THF. The combined organic fractions were concentrated and filtered through basic AlO. The remaining clarified solution was concentrated in vacuo to obtain the product (deuteration degree 62%). x Filtration. The remaining clarified solution was concentrated in vacuo to obtain the product (deuteration degree 62%).

[0235] Comparative Example 6

[0236] Comparative Example 6 is a comparative method including Step 6.1) and Step 6.2) described below.

[0237]

[0238] Step 6.1) Compound B (5.0 g) was dissolved in toluene-d8 (67 mL) under an inert atmosphere. At 10 °C, trifluoromethanesulfonic acid (6.9 mL) was added dropwise. After 20 h at 20 °C, a small amount of D2O (9.9 mL) was added dropwise (this step is optional; if H2O is used to quench the solution, the deuteration degree of the obtained product will be slightly reduced). The addition is strongly exothermic, and the temperature was controlled to a maximum of 15 °C. At 15 °C, an aqueous NaOH solution (50 mL, 20 wt%) was added dropwise. The organic layer was separated, washed with brine and distilled H2O and dried over Na2SO4. After filtration, the solvent was removed under reduced pressure. The crude product was obtained as an off-white solid. (5.2 g, 99.9% purity determined by HPLC, deuteration degree 64%).

[0239] Step 6.2) Under an inert atmosphere, dissolve the product obtained from Step 6.1) (5.2 g) in toluene-d8 (68 mL). At 10 °C, add dropwise trifluoromethanesulfonic acid (7.1 mL). After 17 hours at 20 °C, add dropwise a small amount of D2O (10.2 mL) (this step is optional; if H2O is used to quench the solution, the degree of deuteration of the obtained product will be slightly reduced). The addition is strongly exothermic, and the temperature is controlled to a maximum of 15 °C. At 15 °C, add dropwise an aqueous NaOH solution (50 mL, 20 wt%). Separate the organic layer, wash it with brine and distilled H2O, and dry it over Na2SO4. After filtration, remove the solvent under reduced pressure. Obtain a crude product as an off-white solid. (4.6 g, 99.9% purity determined by HPLC, degree of deuteration 76%).

Claims

1. A method for preparing a deuterated compound, the method comprising the following steps in the following order: (a) Performing a first deuteration reaction of a compound by an H-D exchange method to form a first deuterated compound having a deuteration degree x; (b) Performing a second deuteration reaction of the first deuterated compound by an H-D exchange method to form a second deuterated compound having a deuteration degree y; wherein the H-D exchange method in steps (a) and (b) is selected from H-D exchange catalyzed by an acid and H-D exchange catalyzed by a metal; wherein if the H-D exchange method in step (a) is H-D exchange catalyzed by a metal, then the H-D exchange method in step (b) is H-D exchange catalyzed by an acid, or if the H-D exchange method in step (a) is H-D exchange catalyzed by an acid, then the H-D exchange method in step (b) is H-D exchange catalyzed by a metal, and wherein after step (b), the deuteration degrees x and y satisfy the following condition (Equation 1): y≥1.3x (Equation 1).

2. The method according to claim 1, wherein The H-D exchange method in step (a) is H-D exchange catalyzed by a metal, and the H-D exchange method in step (b) is H-D exchange catalyzed by an acid.

3. The method according to claim 1 or 2, characterized in that The H-D exchange method in step (a) is H-D exchange catalyzed by an acid, and the H-D exchange method in step (b) is H-D exchange catalyzed by a metal.

4. The method according to one or more of the preceding claims, characterized in that The H-D exchange catalyzed by a metal is H-D exchange catalyzed by heterogeneous metal catalysis.

5. The method according to one or more of the preceding claims, characterized in that The H-D exchange catalyzed by a metal comprises the following steps in the following order: MC-1) Mixing a compound or a first deuterated compound, a solvent, a metal catalyst, and a deuterium source; MC-2) Heating to cause a reaction.

6. The method according to claim 5, wherein The deuterium source in step MC-1) comprises one of the following deuterium sources: D2O, deuterated benzene, deuterated toluene, deuterated xylene, CDCl3, CD3OD, and mixtures thereof.

7. The method according to claim 5 or 6, characterized in that The metal catalyst in step MC-1) comprises platinum, palladium, rhodium, ruthenium, nickel, cobalt, their oxides, their complexes, and combinations thereof.

8. The method according to one or more of claims 5 to 7, characterized in that The solvent in step MC-1) comprises a solvent selected from aromatic solvents, ethers, alcohols, alkanes, cycloalkanes, acids, amides, esters, or mixtures thereof.

9. The method according to one or more of claims 5 to 8, characterized in that Step MC-2) is carried out at a temperature between 40 °C and 250 °C.

10. The method according to one or more of claims 5 to 9, characterized in that Step MC-2) occurs under an inert gas.

11. The method according to one or more of the preceding claims, characterized in that The H-D exchange catalyzed by an acid is selected from H-D exchange catalyzed by homogeneous acid catalysis.

12. The method according to one or more of the preceding claims, characterized in that The H-D exchange catalyzed by an acid comprises the following steps in the following order: AC-1) Mixing a compound or a first deuterated compound with a deuterated solvent; AC-2) Treating the reaction mixture of step AC-1) with an acid catalyst having a pKa of 0 or lower in water.

13. The method according to claim 12, wherein The acid catalyst has a pKa of -5 or lower in water.

14. The method according to claim 12 or 13, characterized in that The deuterated solvent is a deuterated aromatic solvent.

15. The method according to one or more of claims 12 to 14, characterized in that The deuterated solvent comprises a solvent selected from deuterated benzene, deuterated toluene, deuterated xylene, CDCl3, CD3OD, and mixtures thereof.

16. The method according to one or more of claims 12 to 15, characterized in that The acid catalyst is H2SO4, D2SO4, CF3CO2H, CF3CO2D, CH3SO3H, CH3SO3D, C6H6SO3H, C6H6SO3D, CF3SO3H, CF3SO3D, FSO3H, FSO3D, and mixtures thereof.

17. The method according to one or more of claims 12 to 16, characterized in that The deuterated solvent used in the H-D exchange by acid catalysis is re-enriched with deuterium by introducing the deuterated solvent into the reaction mixture of the H-D exchange by metal catalysis.

18. The method according to one or more of the preceding claims, characterized in that The compound to be deuterated contains an aromatic ring system, a heteroaromatic ring system, an aromatic amine, or an organometallic compound.

19. The method according to claim 18, wherein The compound to be deuterated is an aromatic ring system selected from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, bibenzylidene, terphenyl, terbenzylidene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indeno[1,2-b]fluorene, triphenylene, isotriphenylene, spirotriphenylene, spiroisotriphenylene, and combinations of these groups, and the aromatic ring system may be substituted by one or more groups R R wherein R R which, each time it occurs, independently represents H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, N(R')₂, N(Ar)₂, NO₂, Si(R')₃, B(OR')₂, OSO₂R', a straight-chain alkyl, alkoxy or thioalkyl group having from 1 to 40 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having from 3 to 40 C atoms, each of said groups being optionally substituted by one or more groups R', where in each case one or more non-adjacent CH₂ groups may be replaced by R'C═CR', C≡C, Si(R')₂, Ge(R')₂, Sn(R')₂, C═O, C═S, C═Se, P(═O)(R'), SO, SO₂, O, S or CONR', and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, said aromatic or heteroaromatic ring system being optionally substituted by one or more groups R' in each case, or an aryloxy group having from 5 to 60 aromatic ring atoms, said aryloxy group being optionally substituted by one or more groups R'; where two groups R R may together form an aliphatic or aromatic ring system which is optionally substituted by one or more groups R'; Ar is, each occurrence being the same or different, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case also be substituted by one or more groups R'; R' is, each occurrence being the same or different, H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S, and where one or more H atoms may be replaced by D, F, Cl, Br, or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.

20. The method according to claim 18, wherein The compound to be deuterated is a heteroaromatic ring system selected from the following substances: dibenzofuran, dibenzothiophene, carbazole, indolocarbazole, indeno[1,2-b]carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzoquinoline, phenothiazine, phen azine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, phen azine, phenothiazine and combinations of these groups, and the heteroaromatic ring system may be substituted by one or more groups R R wherein R R has the same definition as in claim 19.

21. The method according to claim 18, wherein The compound to be deuterated is a heteroaromatic ring system selected from the compounds of formula (h-1) or (h-2): wherein: K is Ar 10 or -L 1 -N(Ar)2; Z is C-R Z ; or two adjacent groups Z together form a fused ring; R Z identical or different in each case and selected from H, D, F, Cl, Br, I, N(Ar)2, N(R)2, OAr, SAr, CN, NO2, OR, SR, COOR, C(=O)N(R)2, Si(R)3, B(OR)2, C(=O)R, P(=O)(R)2, S(=O)R, S(=O)2R, OSO2R, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R groups, where one or more non-adjacent CH2 groups may be replaced by Si(R)2, C=O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and which may in each case be substituted by one or more R groups; L 1 is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and being optionally substituted by one or more R groups; Ar 10 is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, said aromatic ring system or heteroaromatic ring system being optionally substituted by one or more R groups; R Z Identical or different in each case, and is H, D, F, Cl, Br, I, N(Ar)2, N(R)2, OAr, SAr, CN, NO2, OR, SR, COOR, C(=O)N(R)2, Si(R)3, B(OR)2, C(=O)R, P(=O)(R)2, S(=O)R, S(=O)2R, OSO2R, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R groups, where one or more non-adjacent CH2 groups may be replaced by Si(R)2, C=O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system, the aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case being substitutable by one or more R groups; simultaneously, two R Z groups may also together form a ring system; E is, independently at each occurrence, a single bond or the group C(R 0 )2; R 0 independently selected, each time it appears, from a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, which groups may in each case be substituted by one or more R' groups; R is, each occurrence being the same or different, H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar)2, S(=O)Ar, S(=O)2Ar, N(R')2, N(Ar)2, NO2, Si(R')3, B(OR')2, OSO2R', a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 C atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 C atoms, each of which groups may be substituted by one or more groups R', where in each case one or more non-adjacent CH2 groups may be replaced by R'C=CR', C≡C, Si(R')2, Ge(R')2, Sn(R')2, C=O, C=S, C=Se, P(=O)(R'), SO, SO2, O, S, or CONR', and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more groups R', or an aryloxy group having 5 to 60 aromatic ring atoms, which aryloxy group may be substituted by one or more groups R'; where two groups R may together form an aliphatic or aromatic ring system which may be substituted by one or more groups R'. Ar is, each time it occurs, the same or different and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case also be substituted by one or more groups R'; R' is, each time it occurs, the same or different and represents H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S, and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms; x, y are independently selected from 0 or 1, where when x or y is 0, the corresponding group E is absent; and x + y = 1 or 2.

22. The method according to claim 21, wherein The compound to be deuterated is a heteroaromatic ring system of a compound selected from compounds of formula (h-1-1) to (h-1-3) and (h-2-1) to (h-2-2), where the symbols and designations have the following meanings: M is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which aromatic ring system or heteroaromatic ring system may be substituted by one or more R groups; E 1 is independently, at each occurrence, a single bond or a group C(R 0 )2; wherein R 0 has the same meaning as in claim 21; Ar 5 which, each time it appears, is the same or different and is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, said aromatic ring system or heteroaromatic ring system being optionally substituted by one or more R groups; R T 、R V 、R 6 which are the same or different in each case and are selected from H, D, F, Cl, Br, I, N(Ar)2, N(R)2, OAr, SAr, CN, NO2, OR, SR, COOR, C(=O)N(R)2, Si(R)3, B(OR)2, C(=O)R, P(=O)(R)2, S(=O)R, S(=O)2R, OSO2R, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R groups, where one or more non-adjacent CH2 groups may be replaced by Si(R)2, C=O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system, the aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and being in each case substitutable by one or more R groups; simultaneously, two R T groups may together form a ring system, two R V groups may together form a ring system and / or two R 6 groups may together form a ring system; x 1 and y 1 are independently selected from 0 or 1, wherein when x 1 or y 1 is 0, the corresponding group E 1 does not exist; provided that x 1 + y 1 = 1 or 2; c, f are, each time they occur, the same or different and represent 0, 1, 2, 3 or 4; d, e are, each time they occur, the same or different and represent 0, 1, 2 or 3; If x 1 = 0, then g represents 0, 1, 2, or 3; or if x 1 = 1, then g represents 0, 1, or 2; If y 1 = 0, then h represents 0, 1, 2, 3, or 4; or if y 1 = 1, then h represents 0, 1, 2, or 3; If x = 0, then k represents 0, 1, 2, 3 or 4; or if x = 1, then k represents 0, 1, 2 or 3; If y = 0, then l represents 0, 1, 2 or 3; or if y = 1, then l represents 0, 1 or 2; s is, each time it occurs, the same or different and represents 0, 1, 2, 3 or 4; and u represents 0, 1 or 2; and in which the symbols and designations R Z , K, E, R, Ar, x and y have the same meanings as in claim 21.

23. The method according to claim 18, wherein The compound to be deuterated is an aromatic amine of a compound selected from compounds of formula (A): where: A 1 which are the same or different in each case and are H, an alkyl group having from 1 to 20 carbon atoms and which may be substituted by one or more R 1 groups, or Ar 1 ; Ar 1 which are the same or different in each case and are an aromatic ring system having from 6 to 60 aromatic ring atoms and which may be substituted by one or more R 1 groups, or a heteroaromatic ring system having from 5 to 60 aromatic ring atoms and which may be substituted by one or more R 1 groups; Ar 1 and / or A 1 groups may here be bonded to one another via R 1 groups; R 1 identical or different in each case and selected from H, D, F, C(=O)R 2 , CN, Si(R 2 )3, P(=O)(R 2 )2, OR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more R 1 groups may be linked to each other and may form a ring; where the alkyl, alkoxy, alkenyl, and alkynyl groups mentioned and the aromatic ring system and heteroaromatic ring system mentioned may each be substituted by one or more R 2 groups; and where one or more CH2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups mentioned may be replaced by -R 2 C=CR 2 -, -C≡C-, Si(R 2 )2, C=O, C=NR 2 , -C(=O)O-, -C(=O)NR 2 (-), P(=O)(R 2 )-, -O-, -S-, SO or SO2; R 2 identical or different in each case and selected from H, D, F, CN, an alkyl group having 1 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more R 2 groups may be linked to one another and may form a ring; and where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN.

24. The method according to claim 23, wherein The aromatic amine compound is selected from compounds of one of formula (A-I) to (A-IX): One or more of R 1 groups may be bonded to any of the unsubstituted positions shown, and: V is the same or different in each case and is CR 1 or N; E 10 identical or different in each case and is a single bond, O, S, C(R 1 )2, Si(R 1 )2, PR 1 , C(R 1 )2-C(R 1 )2 or CR 1 =CR 1 ; E 20 the same or different in each case and is O, S, C(R 1 )2, Si(R 1 )2, PR 1 , NR 1 , C(R 1 )2-C(R 1 )2 or CR 1 =CR 1 ; Ar 2 is an aromatic ring system having 6 to 20 aromatic ring atoms and which may be substituted by one or more R 1 groups, or a heteroaromatic ring system having 5 to 20 aromatic ring atoms and which may be substituted by one or more R 1 groups; n, p, q are the same or different and each is 0 or 1; and Ar 1 and R 1 are as defined in claim 23.

25. A deuterated compound, which deuterated compound is obtained by the method according to one or more of claims 1 to 24.

26. A composition, which composition comprises a deuterated compound obtained by the method according to one or more of claims 1 to 24 and other compounds.

27. An electronic device, which electronic device comprises a deuterated compound obtained by the method according to one or more of claims 1 to 24.

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