Process for preparing deuterated organic compounds

Abstract

The present invention relates to a process for preparing a deuterated organic compound, comprising the following steps: preparing a liquid composition comprising the organic compound, at least one heterogeneous metal catalyst, at least one deuterium source, and at least one aliphatic hetero compound, and optionally at least one aliphatic hydrocarbon, as a solvent.

Description

[0001] Process for the preparation of deuterated organic compounds

[0002] The present invention relates to a process for the preparation of deuterated organic compounds and deuterated compounds prepared by this process.

[0003] Deuterium is an isotope of hydrogen and has a natural occurrence of 0.015%. Deuterated compounds with high deuterium content are known, and deuterated aromatic compounds have frequently been used in studies of the course of chemical reactions or metabolic processes.

[0004] Deuterated aromatic compounds are used as starting materials for pharmaceutical compounds or markers.

[0005] Electronic devices containing organic, organometallic, and / or polymeric semiconductors are becoming increasingly important. Due to their cost and performance, these semiconductors are used in many commercial products. Examples include organic-based charge transport materials (e.g., triarylamine-based hole transporters) in copiers, organic or polymeric light-emitting diodes (OLEDs or PLEDs) in display devices, and organic photoreceptors in copiers. Organic solar cells (O-SCs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic switching elements (O-ICs), organic optical amplifiers, and organic laser diodes (O-lasers) are at an advanced stage of development and have the potential to become highly important in the future.

[0006] Electronic devices within the meaning of this invention are understood to be organic electronic devices that contain organic semiconductor materials as functional materials. In particular, these electronic devices represent electroluminescent devices such as OLEDs. The structure of OLEDs in which organic compounds are used as functional materials is known to those skilled in the art. In general, OLEDs are understood to be electronic devices that have one or more layers comprising organic compounds and that emit light when a voltage is applied.

[0007] In electronic devices, especially OLEDs, there is a great need to improve performance, particularly lifetime, efficiency, and operating voltage. No satisfactory solution has yet been found for these aspects.

[0008] Electronic devices typically comprise a cathode, an anode, and at least one functional, preferably emissive, layer. In addition to these layers, they may contain further layers, for example, one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers, and / or charge-generation layers.

[0009] The hole transport layers and electron transport layers have a major influence on the performance of electronic devices.

[0010] Recently, it was discovered that replacing a hydrogen atom in an organic electronic device increases the lifetime of the device. This may be due to the fact that the C–D bond is slightly stronger than a C–H bond, thus suppressing certain decomposition reactions.

[0011] For the production of deuterated compounds, it is advantageous to perform deuteration late in the manufacturing process, especially for compounds for electronic devices, since deuteration is generally a very costly step. Therefore, precursors for compounds for electronic devices, intermediates of such compounds, or the compounds for electronic devices themselves can be deuterated.

[0012] Typically, undeuterated compounds are treated with deuterated acids such as D2SO4 or D3PO4 for several hours to obtain deuterated compounds.

[0013] It is also possible to react the undeuterated compound in a deuterated solvent in the presence of a Lewis acid such as aluminum trichloride.

[0014] Other methods use high temperatures and electrical voltage or radiation.

[0015] Still other methods use D2 gas, D2O or a deuterated solvent such as CeDe and a metallic catalyst.

[0016] However, the conversion is often very slow and unreliable. Furthermore, deuterium sources such as CeDe or d8-toluene are very expensive and difficult to obtain.

[0017] JP2020070291 describes a process for producing deuterated compounds in an aliphatic hydrocarbon with more than 6 carbon atoms as a solvent, a deuterium source, and a metal catalyst. However, an alcohol is also used as an additive. The decalin used is also difficult to remove, and the resulting compounds are difficult to purify.

[0018] WO2016073425A2 describes a process for deuterating compounds at high pressure and temperature in D2O, optionally with solvent.

[0019] KR2020094033A describes deuteration in D2O, optionally with 1,4-dioxane in the presence of a reducing agent. The object of the present invention is to provide a process for the preparation of deuterated compounds with a high conversion rate and high yield, while economically using the deuterium source.

[0020] The object is achieved by a process for producing a deuterated organic compound comprising the following steps: a) preparing a liquid composition comprising at least one organic compound, at least one heterogeneous metal catalyst, at least one deuterium source, and at least one aliphatic heterocompound, preferably acyclic aliphatic or cyclic aliphatic ethers and / or acyclic aliphatic or cyclic aliphatic amines, and optionally at least one aliphatic hydrocarbon, as solvent; b) heating the composition to deuterate the organic compound.

[0021] Deuteration, as defined in the invention, means that some or all of the hydrogen atoms are exchanged for deuterium (D) during the reaction. In a deuterated compound, deuterium is more than 100 times more abundant than its natural abundance. Percentages given refer to the ratio of deuterium to the sum of protons and deuterium for a given compound.

[0022] In step a), a liquid composition comprising the organic compound, at least one heterogeneous metal catalyst, at least one deuterium source, and at least one aliphatic ether, and optionally at least one aliphatic hydrocarbon, as solvent is prepared.

[0023] For this purpose, the individual components are mixed. The organic compound can be dissolved and / or partially dispersed in the composition. The heterogeneous metal catalyst is preferably selected from the group comprising platinum, palladium, rhodium, ruthenium, nickel, cobalt, oxides thereof, and combinations thereof, preferably platinum or palladium and / or oxides thereof.

[0024] Preferably, the metal of at least one metal catalyst is in the oxidation state 0 to 2, preferably 0. Preferably, at least one metal catalyst is present as elemental metal and / or metal oxide, preferably as elemental metal.

[0025] The metal catalyst preferably comprises at least one heterogeneous metal catalyst. The metal of the metal catalyst is preferably present as a metal, preferably applied to a solid phase that is insoluble in the composition. The solid phase can be a suitable material, for example, carbon such as activated carbon or carbon black, silicates, molecular sieves, or polymers. The solid phase is stable under the reaction conditions. Carbon is preferably used as the solid phase. Such catalysts are referred to, for example, as Pd / C or Pt / C.

[0026] Preferred metal catalysts are platinum, palladium or mixtures of platinum and palladium, particularly preferably as metal, particularly preferably as heterogeneous catalyst.

[0027] Preferably, the at least one metal catalyst is selected from platinum on carbon (Pt / C), palladium on carbon (Pd / C), or a mixture of Pt / C and Pd / C. In the case of a mixture, a mixture of 10:1 to 1:2 of Pt / C to Pd / C, preferably 7:1 to 1:1, in particular 5:1 to 1:1, measured by weight, is preferred.

[0028] The content of metal on the carbon of the metal catalyst is preferably 1 to 10 wt.%, in particular 3 to 7 wt.%, particularly preferably 5 wt.%.

[0029] The molar ratio of organic compound to catalyst is preferably from 2:1 to 100:1, in particular from 2:1 to 70:1, preferably from 2:1 to 30:1. With a higher amount of catalyst, fewer by-products are generally formed.

[0030] The organic compound is preferably dissolved in the composition, in particular dissolved under the conditions in step b). This means that the organic compound is dissolved in the composition after heating.

[0031] The organic compound is preferably an aromatic or heteroaromatic compound, in particular a hydrocarbon compound, or an organometallic compound. This is preferably a compound with at least one aromatic or heteroaromatic ring system. The compound is particularly preferably suitable for use in an electronic device, in particular an OLED, or a precursor of such a compound.

[0032] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 1 to 60 C atoms, preferably 1 to 40 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be linked by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C, N or O atom or carbonyl group. This also includes systems in which two or more aryl or heteroaryl groups are directly linked to one another, such as:Biphenyl, terphenyl, bipyridine, or phenylpyridine. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also to be understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a linear or cyclic alkyl group or by a silyl group. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups, as well as groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example biphenyl, terphenyl, quaterphenyl, or bipyridine, as well as fluorene or spirobifluorene. Among the linked heteroaromatic ring systems, ring systems with aryl or heteroaryl groups linked to nitrogen atoms are particularly preferred.

[0033] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 5 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as an aromatic ring system.

[0034] An electron-rich heteroaromatic ring system is characterized by the fact that it is a heteroaromatic ring system that contains no electron-deficient heteroaryl groups. An electron-deficient heteroaryl group is a six-membered ring heteroaryl group with at least one nitrogen atom or a five-membered ring heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other oxygen, sulfur, or a substituted nitrogen atom, to which further aryl or heteroaryl groups may be fused. In contrast, electron-rich heteroaryl groups are five-membered ring heteroaryl groups with exactly one heteroatom selected from oxygen, sulfur, or substituted nitrogen, to which further aryl groups and / or further electron-rich five-membered ring heteroaryl groups may be fused.Examples of electron-rich heteroaryl groups include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, and indenocarbazole. An electron-rich heteroaryl group is also called an electron-rich heteroaromatic radical.

[0035] An electron-poor heteroaromatic ring system is characterized in that it contains at least one electron-poor heteroaryl group, and particularly preferably no electron-rich heteroaryl groups.

[0036] The organic compound may contain one or more aliphatic hydrocarbon radicals, or alkyl, alkenyl, or alkynyl groups. It may also be substituted with other groups such as F, CN, Cl, Br, I, alkoxy, or thioalkyl groups. It is important that these groups do not react under the reaction conditions.

[0037] In the context of the present invention, the term "alkyl group" is used as a generic term for both linear or branched alkyl groups and cyclic alkyl groups. Analogously, the terms "alkenyl group" and "alkynyl group" are used as generic terms for both linear or branched alkenyl or alkynyl groups, as well as for cyclic alkenyl or alkynyl groups.

[0038] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 40 C atoms and in which individual non-adjacent CH2 groups may also be substituted by O, C=O, (C=O)O, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, cyclooctyl, 2-ethylhexyl, 1-bicyclo[2,2,2]octyl, 2-bicyclo[2,2,2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-Dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1 -yl, 1,1-dimethyl-n-hept-1 -yl, 1,1-dimethyl-n-oct-1 -yl, 1,1-dimethyl-n-dec-1 -yl, 1, 1 -Dimethyl-n-dodec-1 -yl, 1 ,1 -Dimethyl-n-tetradec-1 - yl, 1 ,1 -Dimethyl-n-hexadec-1 -yl, 1 ,1 -Dimethyl-n-octadec-1 -yl, 1 ,1 -Diethyl- n-hex-1 -yl, 1 , 1 -Diethyl-n-hept-1 -yl, 1 , 1 -Diethyl-n-oct-1 -yl, 1 , 1 -Diethyl-n- dec-1 -yl, 1 ,1 -Diethyl-n-dodec-1 -yl, 1 ,1 -Diethyl-n-tetradec-1 -yl, 1 ,1 - Diethyln-n-hexadec-1 -yl, 1 , 1 -Diethyl-n-octadec-1 -yl, 1 -(n-Propyl)-cyclohex- 1 -yl, 1 -(n-Butyl)-cyclohex-1 -yl, 1 -(n-Hexyl)-cyclohex-1 -yl, l -(n-Octyl)- cyclohex-1 -yl und 1 -(n-Decyl)-cyclohex-1 -yl, Ethenyl, Propenyl, Butenyl, Pentenyl, Cyclopentenyl, Hexenyl, Cyclohexenyl, Heptenyl, Cycloheptenyl, Octenyl, Cyclooctenyl, Cyclooctadienyl, Ethinyl, Propinyl, Butinyl, Pentinyl, Hexinyl, Heptinyl oder Octinyl verstanden. Unter einer Alkoxygruppe mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n-Hexoxy, Cyclohexyloxy, n-Heptoxy, Cyclo- heptyloxy, n-Octyloxy, Cyclooctyloxy,2-Ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group with 1 to 40 carbon atoms includes, in particular, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethynylthio, Propynylthio, Butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic,where one or more non-adjacent CH2 groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, particularly preferably F or CN.

[0039] An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, preferably 5 - 40 aromatic ring atoms, which may also be substituted by the above-mentioned radicals or a hydrocarbon radical and which may be linked to the aromatic or heteroaromatic ring via any desired positions, is understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, Truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,Indol, Isoindol, Carba- zol, Pyridin, Chinolin, Isochinolin, Acridin, Phenanthridin, Benzo-5,6-chino- lin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimi- dazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benz- oxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2- Thiazol, 1 ,3-Thiazol, Benzothiazol, Pyridazin, Hexaazatriphenylen, Benzo- pyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1 ,5-Diazaanthracen, 2,7- Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diaza- pyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Pheno- thiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenan- throlin, 1 ,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4- Oxadiazol, 1 ,2,5-Oxadiazol, 1 ,3,4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thia- diazol, 1 ,2,5-Thiadiazol, 1 ,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4-Triazin, 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 groups derived from combinations of these systems, which are linked to one another in particular via single bonds and / or N atoms.

[0040] For the purposes of this description, the phrase "two or more residues can form a ring system" is understood to mean, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0041] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0042] In the case of an organometallic compound, it is preferably a compound comprising copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, indium, palladium, platinum, silver, gold, or europium, in particular compounds such as indium or platinum, particularly preferably platinum, which have at least one heteroaromatic ring system. Compounds suitable as phosphorescent compounds (= triplet emitters) are preferred. Examples of such compounds can be found in the cited applications for phosphorescent compounds.

[0043] These compounds are preferably metal chelate complexes, in particular with at least one heteroaromatic ring system as a chelate ligand for the metal. Preference is given to at least one heteroaromatic ring system that binds to the metal via at least one nitrogen atom and at least one carbon atom. These atoms are preferably each part of an aryl group or heteroaryl group, which are linked via at least one single bond. Examples of such a compound are 2-phenylpyridine or analogous compounds in which the aforementioned aryl groups or heteroaryl groups are linked via a single bond. The deuterium source is preferably selected from heavy water, D2O, d6-benzene, or d8-toluene, preferably heavy water or D2O, particularly preferably D2O. Heavy water or D2O, in particular, are a more favorable deuterium source than the other compounds.

[0044] Heavy water is understood to mean water in which 50 mol% of all hydrogen atoms are exchanged for deuterium, preferably at least 70 mol%, particularly preferably at least 80 mol%, in particular at least 90% or 99%.

[0045] The solvent serves in particular to increase the solubility of the organic compound in the composition.

[0046] Surprisingly, it was found that the solvent, in particular at least one aliphatic hetero compound, and optionally at least one aliphatic hydrocarbon, promotes deuteration.

[0047] The aliphatic heterocompound is preferably an aliphatic solvent with a boiling point above 75°C and at least one heteroatom, preferably selected from N and / or O, in particular above 80°C (measured at atmospheric pressure). Preference is given to acyclic aliphatic or cyclic aliphatic ethers and / or acyclic aliphatic or cyclic aliphatic amines; particularly preferred are cyclic aliphatic ethers and / or cyclic aliphatic amines.

[0048] An ether is understood to mean a compound which comprises at least one oxygen atom to which two aliphatic hydrocarbon radicals as defined above are bonded, which can also form a ring with each other.

[0049] Aliphatic ethers are understood to be monoethers, diethers or triethers.

[0050] Preferably, the solvent is a linear or cyclic ether having 4 to 18 carbon atoms and 1 to 4 oxygen atoms, preferred are ethers having 4 to 12 carbon atoms and 1 to 3 oxygen atoms, in particular 4 to 8 carbon atoms and 1 or 2 oxygen atoms.

[0051] The solvent is preferably a cyclic aliphatic heterocompound having 4 to 18 carbon atoms and 1 to 4 heteroatoms, each selected from nitrogen or oxygen. The solvent is particularly preferably a cyclic aliphatic heterocompound having 4 to 12 carbon atoms and 1 to 2 heteroatoms, each selected from nitrogen or oxygen. Very particularly preferably, the solvent is a cyclic aliphatic heterocompound having 4 to 12 carbon atoms and 1 to 2 heteroatoms, each selected from nitrogen or oxygen, wherein the compound comprises at least one six-membered ring.

[0052] Examples of such solvents are cyclic ethers such as 1,4-dioxane, tetrahydropyran (THP), tetrahydrofuran, 2-methyltetrahydrofuran, 2,2-dimethyltetrahydrofuran; aliphatic monoethers such as tert-butyl methyl ether, tert-butyl ethyl ether, tert-amyl methyl ether, dibutyl ether; aliphatic diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-di-tert-butoxyethane, diethylene glycol diethyl ether and diethylene glycol dibutyl ether. Particularly preferred are cyclic ethers such as 1,4-dioxane, tetrahydropyran, tetrahydrofuran, in particular 1,4-dioxane or tetrahydropyran and aliphatic monoethers such as tert-butyl methyl ether, tert-amyl methyl ether,

[0053] Cyclic amines, which may also comprise oxygen atoms, are selected, for example, from piperidine, morpholine, pyrrolidine, in particular piperidine or morpholine.

[0054] The optional aliphatic hydrocarbon is preferably an aliphatic hydrocarbon with a boiling point above 75°C, especially above 80°C (measured at atmospheric pressure). The aliphatic hydrocarbon is preferably a cycloalkane, preferably an aliphatic hydrocarbon with at least one ring containing 6 aliphatic carbon atoms. Particular preference is given to cyclohexane, methylcyclohexane, methylcyclopentane, or fused cycloalkanes such as decalin. Preference is given to cyclohexane, methylcyclopentane, and decalin, especially cyclohexane. The decalin can be present as a cis or trans isomer or as a mixture of isomers.

[0055] Mixtures of solvents may also be used, in particular mixtures of at least one aliphatic hetero compound and at least one aliphatic hydrocarbon.

[0056] The ratio of aliphatic hydrocarbon and aliphatic hetero compound by volume can be selected depending on the organic compound, for example from 100:1 to 1:100, in particular 30:1 to 1:30.

[0057] Thus, up to 40 vol.% of a further solvent, in particular 0 to 30 vol.%, can be added, based on the aliphatic hetero compound(s). These can be, for example, cycloalkanes, in particular a solvent having at least one ring with 6 aliphatic carbon atoms. Particular preference is given to cyclohexane, methylcyclohexane, methylcyclopentane, or fused cycloalkanes such as decalin. Preference is given to cyclohexane, methylcyclopentane, and decalin, especially cyclohexane. The decalin can be present as a cis or trans isomer or as a mixture of isomers.

[0058] In a further embodiment, the at least one aliphatic hydrocarbon is present in excess by volume over the at least one aliphatic hetero compound. In a preferred embodiment, the ratio of hydrocarbon to aliphatic hetero compound, measured by volume, is at least 1.05:1, preferably at least 1.1:1, in particular 1.1:1 to 50:1, very particularly 1.1:1 to 30:1.

[0059] In a preferred embodiment, the solvent comprises a mixture of at least one cyclic aliphatic

[0060] Heterocompound and at least one cycloalkane. Preferred is a mixture comprising cycloalkanes having at least one ring with 6 aliphatic carbon atoms, particularly preferably cyclohexane, methylcyclohexane, or fused cycloalkanes such as decalin, and at least one cyclic aliphatic heterocompound having 4 to 12 carbon atoms, 1 to 2 heteroatoms each selected from nitrogen or oxygen, wherein the compound comprises at least one six-membered ring. Examples include 1,4-dioxane, tetrahydropyran, piperidine, or morpholine.

[0061] In a preferred embodiment, in the case of a mixture, the solvent is a mixture comprising cyclohexane, methylcyclohexane and / or decalin, with at least one cyclic ether selected from 1,4-dioxane and / or tetrahydropyran.

[0062] The solvent is preferably non-deuterated. Preferably, the deuterium source, in particular D2O, is the only deuterated compound in the composition.

[0063] The composition preferably does not comprise any aliphatic alcohols, especially those with 1 to 10 carbon atoms. The composition preferably does not comprise any aliphatic alcohols. The composition preferably does not comprise any organic compounds containing hydroxyl groups.

[0064] It is known from the prior art that deuteration is favored in the presence of aliphatic alcohols with 1 to 10 carbon atoms. Surprisingly, it was found that reaction with the pretreated metal catalyst in the presence of an aliphatic hetero compound improves deuteration.

[0065] In the composition, the ratio of 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. The aliphatic solvent, the aliphatic hetero compound and the optional aliphatic hydrocarbon are used in an amount such that the organic compound dissolves at least partially; measured in volume, preferably in a deuterium source:solvent ratio of 2:1 to 1:50, preferably 1:1 to 1:30, in particular 1:1.5 to 1:30, very particularly 1:1.5 to 1:15. The ideal amount depends on the solubility of the compound.

[0066] The improved solubility of the compounds in the solvent used can, in particular, increase the space yield. The process according to the invention makes it possible to carry out the process at higher concentrations.

[0067] Surprisingly, it was found that the composition of the solvent can be particularly advantageous for certain classes of compounds.

[0068] The use of at least one aliphatic heterocompound as part of the solvent leads to significantly improved deuteration rates with virtually no byproducts, especially for organic compounds, especially aromatic or heteroaromatic compounds containing at least one NH function, compared to pure aliphatic hydrocarbons as solvents. This is especially true when the aliphatic heterocompound is used in excess, especially as the sole solvent.

[0069] Surprisingly, it was found that when the aliphatic hetero compound, preferably the cyclic ether, is used as the sole solvent, complete conversion can be achieved, ie no undeuterated reactant is detectable.

[0070] This embodiment is therefore particularly suitable for intermediates in OLED production that contain such free NH functions. NH functions include both NH groups and NH2 groups. These can be, for example, primary or secondary amines and carbazole compounds or carbazole derivatives.

[0071] In step b) the composition is heated, resulting in deuteration.

[0072] The reaction can be carried out with pressure equalization with the ambient temperature, i.e., in an open or closed vessel. In the latter case, the autogenous pressure can cause a pressure increase due to heating. Carrying out the reaction with pressure equalization can also involve heating under reflux conditions. Step b) is therefore preferably carried out at a pressure of 1 bar or more, preferably below 6 bar.

[0073] The reaction is preferably not carried out in the presence of additional reactive gases such as H2 or D2. The reaction is preferably carried out in an inert atmosphere such as nitrogen or argon. Inert means that the gas or gas mixture does not react under the process conditions.

[0074] Preferably, the composition is not heated by microwaves.

[0075] It may be necessary to degas the composition prior to implementation. This can be achieved, for example, by repeatedly exposing it to the reaction atmosphere.

[0076] In step b), the reaction is carried out with heating. The heating can take place at a temperature of at least 40°C, in particular at least 70°C, in particular at least 100°C. The temperature is preferably up to 250°C, in particular up to 160°C. Particularly preferably from 70°C to 200°C, in particular from 70°C to 160°C. In a preferred embodiment, the temperature is from 100°C to 160°C, in particular from 115°C to 160°C. The reaction is preferably not carried out under supercritical conditions. Depending on the reaction regime, the reaction can also be carried out under reflux. The solvent can then be selected accordingly so that the desired reaction temperature is reached.

[0077] The inventive process is preferably carried out until a deuteration of at least 20%, in particular 30%, is achieved. This figure refers to the degree of deuteration of the highest mass peak of the product mixture.

[0078] In addition to deuteration, the formation of byproducts is also of great importance in the process. Especially when applied to complex compounds, a lower formation of byproducts can be more advantageous than the highest possible deuteration. This is also due to the fact that not all protons in a compound are equally accessible.

[0079] Depending on the byproducts, it may also be more advantageous if complete conversion is achieved, so that at least no reactant is detectable. This is especially the case if the byproducts are easy to separate.

[0080] The process is preferably carried out until a conversion of at least 90% (measured by HPLC) is achieved. This means that a maximum of 10% of reactant remains. A conversion of at least 95% is preferred.

[0081] The reaction is preferably carried out for 1 to 200 hours, especially for 10 to 100 hours.

[0082] Particularly preferably, the reaction is carried out until a degree of deuteration of at least 20% with less than 15% by-products is reached, preferably of at least 25% with less than 10% by-products, in particular of at least 30% with less than 10%. In a preferred embodiment, the reaction is carried out until the by-products have a deuteration of more than 30% and by-products of less than 5%, in particular a deuteration of more than 30% and by-products of less than 4%, preferably by-products of less than 2%.

[0083] After cooling and, if necessary, pressure equalization, the deuterated compound is preferably isolated using known techniques. This may include extraction, precipitation, filtration, distillation, chromatography, or similar processes.

[0084] In one embodiment of the invention, the composition 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 with alkyl groups having 1 to 40 C atoms, where individual non-adjacent CH2 groups may be substituted by O and at least two alkyl groups may 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, with salts or oxides of silver or palladium, in particular Pd(II), being preferred. In the case of salts, these can be, for example, chlorides, bromides, iodides, nitrates, sulfates, carboxylic acid salts such as acetates, propionates, and pivalates, such as Pd(OAc)2, Ag(OAc), or Pd(OPiv)2. Particularly preferred are carboxylic acid salts such as Pd(OAc)2, Ag(OAc) or Pd(OPiv)2.

[0085] Preferred alkylamines are alkylamines having at least two, preferably three alkyl groups, in particular having 1 to 40 C atoms, where individual non-adjacent CH2 groups may be substituted by O and at least two alkyl groups may form a ring. Preferred alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-Hexyl, 2-Hexyl, 3-Hexyl, neo-Hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl. Preferred are alkylamines with three alkyl groups (tertiary amines) with 1 to 5 C atoms, as well as alkylamines with three alkyl groups, where two alkyl groups form a ring, where the ring may contain an O atom.

[0086] Examples of such amines are triethylamine, dimethylethylamine, diethylmethylamine, and diisopropylethylamine, with triethylamine being preferred. Examples of cyclic amines are morpholine derivatives, especially morpholine, piperidine, 2,2,6,6-tetramethylpiperidine, and N-alkylmorpholines such as N-methylmorpholine, N-ethylmorpholine, and N-propylmorpholine.

[0087] Preferably, the amine used is soluble in the composition.

[0088] The aforementioned metal salts are particularly preferred.

[0089] Surprisingly, it has been found that alkylamines, silver salts, and / or palladium salts, in particular, promote deuteration and reduce the formation of byproducts. This may make it possible to conduct the reaction for longer or at higher temperatures. The use of additives may depend on the compound to be deuterated.

[0090] The additives can be used in varying amounts depending on the reaction procedure and the organic compound. 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, in particular 1:2 to 1:30.

[0091] In one embodiment of the invention, the composition does not comprise a reducing agent, in particular no NaBÜ4.

[0092] In a preferred embodiment, the composition comprises at least one aromatic or heteroaromatic compound, platinum on carbon and / or palladium on carbon, D2O, and at least one aliphatic cyclic ether, preferably 1,4-dioxane and / or tetrahydropyran, and / or at least one aliphatic cyclic amine, preferably piperidine; and optionally at least one aliphatic cycloalkane, preferably cyclohexane, decalin, methylcyclohexane and / or methylcyclopentane, and optionally at least one additive, wherein the additive is selected from alkylamines, metal salts and / or metal oxides selected from salts or oxides of palladium, platinum, rhodium, ruthenium, silver, gold, copper, nickel or cobalt.

[0093] In a preferred embodiment, the composition consists of at least one aromatic or heteroaromatic compound, platinum on carbon and / or palladium on carbon, D2O, and at least one aliphatic cyclic ether, preferably 1,4-dioxane and / or tetrahydropyran, and / or at least one aliphatic cyclic amine, preferably piperidine; and optionally at least one aliphatic cycloalkane, preferably cyclohexane, methylcyclohexane and / or methylcyclopentane, and optionally at least one additive, wherein the additive is selected from alkylamines, metal salts and / or metal oxides selected from salts or oxides of palladium, platinum, rhodium, ruthenium, silver, gold, copper, nickel or cobalt.

[0094] In one embodiment of the invention, the at least one heterogeneous metal catalyst is treated prior to addition to the composition, said treatment comprising drying the metal catalyst.

[0095] In one embodiment of the invention, the heterogeneous metal catalyst is water-moist before drying, with the water content being at least 10% (according to Karl Fischer).

[0096] The heterogeneous metal catalyst is dried. This is preferably carried out at elevated temperature, in particular at 20°C to 200°C, preferably at 20 to 100°C, particularly preferably under reduced pressure, in particular below 100 mbar. Drying is preferably carried out until the water content is below 5% by weight, preferably 2% by weight (according to Karl Fischer), preferably below 1%.

[0097] Drying at 50°C to 70°C at less than 50 mbar is particularly preferred, in particular 50°C to 70°C at less than 30 mbar, and very particularly preferably at 55°C to 75°C at 1 to 30 mbar. Drying is preferably carried out for at least 24 hours, in particular at least 48 hours. Drying between 24 and 96 hours, in particular 48 to 96 hours, is preferred.

[0098] The treatment is preferably carried out under air or an inert gas such as nitrogen or argon. No activation with hydrogen or deuterium gas takes place.

[0099] Metal catalysts in particular are often stored in moist water.

[0100] Surprisingly, it has now been found that prior drying, especially when using D2O as deuterium source, significantly improves the activity of the catalyst.

[0101] The pretreated metal catalyst can be used in the next step without further treatment.

[0102] The deuterated compounds according to the invention are suitable for use in an electronic device, in particular in an organic electroluminescent device (OLED). Depending on the substitution, the compounds can be used in different functions and layers.

[0103] An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers composed entirely of inorganic materials.

[0104] The electronic device is preferably selected from the group consisting of organic electroluminescent devices (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 quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon emitting devices, but preferably organic electroluminescent devices (OLEDs).

[0105] The device is particularly preferably an organic electroluminescent device comprising a cathode, an anode, and at least one emitting layer, wherein at least one organic layer, which may be an emitting layer, hole-transport layer, electron-transport layer, hole-blocking layer, electron-blocking layer, or another functional layer, comprises at least one deuterated compound according to the invention. The layer depends on the substitution of the compound.

[0106] In addition to these layers, the organic electroluminescent device may contain further layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers, and / or organic or inorganic p / n junctions. Interlayers, which, for example, have an exciton blocking function, may also be introduced between two emitting layers. It should be noted, however, that not all of these layers are necessarily present.

[0107] The organic electroluminescent device can contain one emitting layer or it can contain multiple emitting layers. If multiple emitting layers are present, these preferably have a total of multiple emission maxima between 380 nm and 750 nm, resulting in overall white emission, i.e., different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Particular preference is given to systems with three emitting layers, with the three layers exhibiting blue, green, and orange or red emission (the basic structure is described, for example, in WO 2005 / 011013). The organic electroluminescent device according to the invention can also be a tandem OLED, in particular for white-emitting OLEDs.

[0108] The organic electroluminescent device may comprise one or more phosphorescent emitters.

[0109] The organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers, with at least one layer containing at least one deuterated compound. Furthermore, the deuterated compound according to the invention can also be used in an electron-transport layer and / or in a hole-blocking layer and / or in a hole-transporting layer and / or in an exciton-blocking layer.

[0110] The term "phosphorescent compound" typically refers to compounds in which the emission of light occurs through a spin-forbidden transition, e.g., a transition from an excited triplet state or a state with a higher spin quantum number, e.g., a quintet state.

[0111] Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds which, upon suitable excitation, emit light, preferably in the visible range, and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. All luminescent complexes with transition metals or lanthanides are preferably considered as phosphorescent compounds, in particular if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, indium, palladium, platinum, silver, gold, or europium, in particular compounds containing indium, platinum, or copper. For the purposes of the present invention, all luminescent indium, platinum, or copper complexes are considered to be phosphorescent emitting compounds.Examples of the emitters described above can be found in the applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 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, WO 2018 / 041769, WO 2019 / 020538, WO 2018 / 178001, WO 2019 / 115423, and WO 2019 / 158453. In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without inventive step.Surprisingly, it was found that such compounds can be deuterated using the method according to the invention.

[0112] If the deuterated compound is used as a hole-transport material in a hole-transport layer, a hole-injection layer, or an electron-blocking layer, the compound can be used as a pure material, i.e., in a 100% proportion, in the hole-transport 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 then additionally contains one or more p-dopants. P-dopants used according to the present invention are preferably those organic electron-accepting compounds capable of oxidizing one or more of the other compounds in the mixture.

[0113] Particularly preferred embodiments of p-dopants are the compounds disclosed in WO 2011 / 073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009 / 003455, WO 2010 / 094378, WO 2011 / 120709, US 2010 / 0096600, WO 2012 / 095143 and DE 102012209523.

[0114] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenylenes, azatriphenylenes, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of main group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a bonding site. Transition metal oxides are also preferably used as dopants, preferably oxides of rhenium, molybdenum, and tungsten, particularly preferably Re2O3, MoO5, WO3, and ReO5.

[0115] The p-type dopants are preferably present in a substantially homogeneous distribution throughout the p-doped layers. This can be achieved, for example, by coevaporation of the p-type dopant and the hole-transport material matrix.

[0116] The deuterated compound can also be used in an emitting layer as a matrix material in combination with one or more emitting compounds, preferably phosphorescent compounds.

[0117] In this case, the proportion of matrix material in the emitting layer is between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.%, particularly preferably between 92.0 and 99.5 vol.% for fluorescent emitting layers and between 85.0 and 97.0 vol.% for phosphorescent emitting layers.

[0118] Accordingly, the proportion of the emitting compound is between 0.1 and 50.0 vol. %, preferably between 0.5 and 20.0 vol. %, particularly preferably between 0.5 and 8.0 vol. % for fluorescent emitting layers and between 3.0 and 15.0 vol. % for phosphorescent emitting layers. An emitting layer of an organic electroluminescent device can also comprise systems that contain a plurality of matrix materials (mixed matrix systems) and / or a plurality of emitting compounds. In this case, too, the emitting compounds are generally those that have the smaller proportion in the system and the matrix materials are those that have the larger proportion in the system. In individual cases, however, the proportion of an individual matrix material in the system can be lower than the proportion of an individual emitting compound.

[0119] Preferred fluorescent-emitting compounds are selected from the class of arylamines. For the purposes of the present invention, an arylamine or an aromatic amine is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably having at least 14 aromatic ring atoms. Preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in position 9.An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in positions 9 and 10. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, in which the diarylamino groups are preferably bonded to the pyrene in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or fluorenediamines, for example according to WO 2006 / 108497 or WO 2006 / 122630, benzoindenofluorenamines or benzofluorenediamines, for example according to WO 2008 / 006449, and dibenzoindenofluorenamines or diamines, for example according to WO 2007 / 140847, as well as the indenofluorene derivatives with fused aryl groups disclosed in WO 2010 / 012328. Also preferred are the pyrenearylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871.Also preferred are the benzoindenofluorenamines disclosed in WO 2014 / 037077, the benzoindenofluorenamines disclosed in WO 2014 / 106522, the extended benzoindenofluorenes disclosed in WO 2014 / 111269 and in WO 2017 / 036574, the phenoxazines disclosed in WO 2017 / 028940 and in WO 2017 / 028941 and the fluorine derivatives bonded to furan units or to thiophene units disclosed in WO 2016 / 150544.

[0120] Useful matrix materials, preferably for fluorescent compounds, include materials from different substance classes. Preferred matrix materials are selected from the classes of oligoaryls (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoaryls with fused aromatic groups, oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g. according to WO 2004 / 081017), hole-conducting compounds (e.g. according to WO 2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides etc. (for example according to WO 2005 / 084081 and WO 2005 / 084082), atropisomers (for example according to WO 2006 / 048268), boronic acid derivatives (for example according to WO 2006 / 117052) or the benzanthracenes (for example according to WO 2008 / 145239).Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene, and / or pyrene, or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene, and / or pyrene, or atropisomers of these compounds. For the purposes of the present invention, an oligoarylene is understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.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 pyrene compounds disclosed in EP 1749809, EP 1905754 and US 2012 / 0187826, the benzanthracenylanthracene compounds disclosed in WO 2015 / 158409, the indenobenzofurans disclosed in WO 2017 / 025165 and the pyrene compounds disclosed in WO 2017 / 036573 disclosed phenanthrylanthracenes.

[0121] Preferred matrix materials for phosphorescent compounds are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, e.g. B. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronic esters, e.g. according to WO 2006 / 117052, triazine derivatives, e.g. B. according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g.according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, e.g. according to WO 2012 / 048781, lactams, e.g. according to WO 2011 / 116865 or WO 2011 / 137951, or dibenzofuran derivatives, e.g. B. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565. Likewise, a further phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host, or a compound that does not participate, or does not participate to a significant extent, in charge transport, as described, for example, in WO 2010 / 108579.

[0122] Suitable charge transport materials, such as those which can be used in the hole injection or hole transport layer or in the electron barrier layer or in the electron transport layer of the electronic component, are, in addition to the deuterated compounds, for example those mentioned in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art.

[0123] Preferably, the OLED comprises two or more different hole-transporting layers. The deuterated compound can be used in one or more or all of the hole-transporting layers. Further compounds which are preferably used in hole-transporting layers of OLEDs are, in particular, indenofluorenamine derivatives (e.g. according to WO 06 / 122630 or WO 06 / 100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. according to WO 01 / 049806), amine derivatives with fused aromatics (for example according to US 5,061,569), the amine derivatives disclosed in WO 95 / 09147, monobenzoindenofluorenamines (for example according to WO 08 / 006449), dibenzoindenofluorenamines (for example according to WO 07 / 140847), spirobifluorenamines (for example according to WO 2012 / 034627 or WO 2013 / 120577), fluorenamines (for example according to WO 2014 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), spirodibenzopyranamines (for example according to WO 2013 / 083216),Dihydroacridine derivatives (for example according to WO 2012 / 150001 ), spirodibenzofurans and spirodibenzothiophenes (for example according to WO 2015 / 022051 , WO 2016 / 102048 and WO 2016 / 131521 ), phenanthrenediarylamines (for example according to WO 2015 / 131976), spirotribenzotropolones (for example according to WO 2016 / 087017), spirobifluorenes with meta-phenyldiamine groups (for example according to WO 2016 / 078738), spirobisacridines (for example according to WO 2015 / 158411 ), xanthenediarylamines (for example according to WO 2014 / 072017), and 9,10-dihydroanthracene spiro compounds with diarylamino groups according to WO 2015 / 086108.,

[0124] Very particular preference is given to the use of spirobifluorenes substituted by diarylamino groups in the 4-position as hole-transporting compounds, in particular the use of those compounds claimed and disclosed in WO 2013 / 120577, and the use of spirobifluorenes substituted by diarylamino groups in the 2-position as hole-transporting compounds, in particular the use of those compounds claimed and disclosed in WO 2012 / 034627.

[0125] All materials that are used in the prior art as electron-transport materials in the electron-transport layer can be used as materials for the electron-transport layer. Particularly suitable are aluminum complexes, e.g., Alq3; zirconium complexes, e.g., Zrq4; lithium complexes, e.g., Liq; benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. Other suitable materials are derivatives of the aforementioned compounds, as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0126] Preferred cathodes of the electronic component are metals with low work functions, metal alloys, or multilayer structures made of different metals, e.g., alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys of an alkali or alkaline earth metal and silver, e.g., an alloy of magnesium and silver. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function can also be used, e.g., Ag or Al, with combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, generally being used. It can also be advantageous to introduce a thin intermediate layer made of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Examples of suitable materials include alkali or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The layer thickness is preferably between 0.5 and 5 nm. Preferred anodes are materials with a high work function. Preferably, the anode has a work function of more than 4.5 eV against vacuum. Metals with a high redox potential, e.g., Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiOx, Al / PtOx) may also be preferred. For some applications, at least one of the electrodes must be transparent or semi-transparent to enable irradiation of the organic material (organic solar cell) or the emission of light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides.Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Further preferred are conductively doped organic materials, especially conductively doped polymers. Furthermore, 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.

[0127] The device is structured, contacted and finally sealed accordingly (depending on the application) to exclude harmful influences from water and air.

[0128] In the further layers of the organic electroluminescent device, any materials commonly used in the prior art can be used. Therefore, the skilled person can use any materials known for organic electroluminescent devices in combination with the deuterated compounds without inventive step. The aforementioned compounds, in particular aromatic or heteroaromatic compounds, can also be deuterated using the method according to the invention, particularly to improve their lifetime.

[0129] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0130] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0131] Also preferred is an organic electroluminescent device characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

[0132] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are deposited by vapor deposition.

[0133] These processes are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices containing the compounds according to the invention.

[0134] In particular, the electronic devices containing one or more deuterated compounds can be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications (e.g., light therapy). The deuterated compounds and the organic electroluminescent devices according to the invention are characterized by one or more of the following properties:

[0135] 1 . The compounds according to the invention lead to long lifetimes.

[0136] 2. The compounds according to the invention lead to high efficiencies, in particular to a high EQE.

[0137] 3. The compounds according to the invention result in low operating voltages.

[0138] The invention is further illustrated by the following examples, without intending to limit it. From these descriptions, those skilled in the art can practice the invention within the entire disclosed scope and, without inventive step, prepare further deuterated compounds and use them in electronic devices or apply the inventive method.

[0139] Examples:

[0140] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased from Sigma-Aldrich or ABCR, for example. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the known compounds.

[0141] Connections used:

[0142]

[0143] Materials used:

[0144] Deuteriumoxid - D2O: Sigma Aldrich (>99.9 atom%D) Dioxan - Dioxan: MerckMillipore (>99.5%)

[0145] Tetrahydropyran - THP: Sigma Aldrich (>98.5%) 2-Methyltetrahydrofuran - MTHF: Sigma Aldrich (>98.5%)

[0146] 2.2-Dimethyltetrahydrofuran - DMTHF: Sigma Aldrich (>98.5%)

[0147] Methyl-tert-butylether - MTBE: MerckMillipore (>99.5%) tert-Amyl-methylether - TAME: MerckMillipore (>99.5%)

[0148] 1 .2-Di-tert-butoxyethan - DTBOE: Alfa Chemistry (> 95 %) Piperidin - Pip: MerckMillipore (>99.0%)

[0149] 2,2,6,6-Tetramethylpiperidin - TMPip: Sigma Aldrich (>98.5%) Morphilin - Morph: MerckMillipore (>99.0%)

[0150] Cyclohexan - Cy: MerckMillipore (>99.5%)

[0151] Palladium / Coal - Pd / C; 5 wt.% Pd; Evonic Operations GmbH Platinum / Coal - Pt / C: 5 wt.% Pt; Evonic Operations GmbH Rhodium / Coal - Pt / C: 5 wt.% Pt; Evonic Operations GmbH Nickel / Coal - Pt / C: 5 wt.% Pt; Evonic Operations GmbH

[0152] Drying the catalysts:

[0153] The water-moist catalysts (Pd / C and Pt / C) were dried for 3 days at 60 °C and 20 mbar in a vacuum drying oven. Water content according to Karl Fischer was approximately 1%.

[0154] General description: Reaction in an autoclave under autogenous pressure

[0155] A stirred autoclave is charged with compound V, DO, a solvent (Lömi), a catalyst Cat. 1, optionally a catalyst Cat. 2, and an additive Add. 1. It is rendered inert by twice injecting and releasing 5 bar of nitrogen, degassed by once injecting and releasing 30 bar of nitrogen, and stirred for the specified reaction time R at the specified temperature T using an inclined blade stirrer at 1000 rpm. The exact batch quantities are shown below. The stirred autoclave is allowed to cool, the still warm (approx. 50 - 80 °C) reaction mixture is removed, the catalyst is filtered off, and the aqueous phase, if present, is separated off. The catalyst is rinsed with a warm (approx. 50 - 80 °C) organic solvent, such as THF, dioxane, THP, ethyl acetate, dichloromethane, etc., until it no longer contains any product. The combined organic phases are evaporated under reduced pressure on a rotary evaporator (p approx. 20 mbar, T approx.60 °C) to dryness.

[0156] Approach and reaction conditions:

[0157] Result:

[0158]

[0159] Approach and reaction conditions:

[0160] Result:

[0161] Approach and reaction conditions:

[0162] Result:

[0163] Approach and reaction conditions:

[0164] Result:

[0165] Approach and reaction conditions:

[0166] Result:

[0167] Approach and reaction conditions:

[0168] Result:

[0169] Approach and reaction conditions:

[0170] Result:

[0171] Approach and reaction conditions:

[0172] Result:

[0173] Tests in pure 1,4-dioxane or THP or MTBE

[0174] The experiments were carried out as described above.

[0175] Approach and reaction conditions:

[0176] Result:

[0177] Approach and reaction conditions:

[0178] Result:

[0179] For the compound V2 with an NH function, complete conversion is achieved in pure 1,4-dioxane or THP or MTBE, which was not achieved in mixtures of cyclohexane with 1,4-dioxane.

Claims

Patent claims 1. A process for the preparation of a deuterated organic compound comprising the following steps: a) Preparing a liquid composition comprising at least one organic compound, at least one heterogeneous metal catalyst, at least one deuterium source, and at least one aliphatic heterocompound, preferably acyclic aliphatic or cyclic aliphatic ethers and / or acyclic aliphatic or cyclic aliphatic amines, and optionally at least one aliphatic hydrocarbon, as a solvent. b) Heating the composition with deuteration of the organic compound.

2. The method of claim 1, wherein the heterogeneous metal catalyst is selected from the group comprising platinum, palladium, rhodium, ruthenium, nickel, cobalt, oxides thereof and combinations thereof.

3. A method according to one or more of claims 1 or 2, wherein the organic compound is an aromatic or heteroaromatic compound or a metal-organic compound.

4. A method according to one or more of claims 1 to 3, wherein the organic compound is an aromatic or heteroaromatic compound or a metal-organic compound comprising at least one NH function.

5. Method according to one or more of claims 1 to 4, wherein the deuterium source is selected from heavy water, D2O, d6-benzene or d8-toluene, preferably heavy water or D2O.

6. A method according to one or more of claims 1 to 5, wherein the solvent is an aliphatic solvent with a boiling point above 75 °C.

7. Method according to one or more of claims 1 to 6, wherein the ratio of hydrogen atoms of the organic compound to deuterium of the deuterium source is at least 1 :1.

5.

8. Method according to one or more of claims 1 to 7, wherein the ratio of deuterium source to solvent, measured in volume, is from 2:1 to 1:

50.

9. Method according to one or more of claims 1 to 8, wherein in step b) the temperature is heated to at least 40 °C, preferably at least 70 °C.

10. Method according to one or more of claims 1 to 9, wherein in step b) heating is carried out to a temperature of up to 200 °C, preferably up to 160 °C.

11. Method according to one or more of claims 1 to 10, wherein step b) is carried out with or without pressure equalization with the environment.

12. A method according to one or more of claims 1 to 11, wherein the composition comprises at least one additive selected from alkylamines, metal salts and / or metal oxides selected from salts or oxides of palladium, platinum, rhodium, ruthenium, silver, gold, copper, nickel or cobalt.

13. A method according to any one of claims 1 to 12, wherein the solvent comprises at least one cyclic aliphatic ether and / or at least one cyclic aliphatic amine, and optionally at least one aliphatic hydrocarbon.

14. A method according to any one of claims 1 to 12, wherein the solvent comprises at least one acyclic aliphatic ether and / or at least one acyclic aliphatic amine, and optionally at least one aliphatic hydrocarbon. A method according to any one of claims 1 to 14, wherein the at least one heterogeneous metal catalyst is treated before being added to the composition, wherein this treatment comprises drying the metal catalyst. A method according to claim 15, wherein the drying is carried out to a water content of less than 5 wt% (according to Karl Fischer).

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