Process for preparation of organic compounds for deuterization

Abstract

The invention relates to a preparation method of an organic compound for deuterization, which comprises the following steps: preparing a liquid composition, the liquid composition comprises the organic compound, at least one heterogeneous metal catalyst, at least one deuterium source, and as a solvent at least one aliphatic heterocompound and optionally at least one aliphatic hydrocarbon.

Description

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

[0002] Deuterium is an isotope of hydrogen that occurs naturally at a ratio of 0.015%. Deuterated compounds with high ratios of deuterium are known, and deuterated aromatic compounds are often used to study chemical reaction processes or metabolic transformations.

[0003] Deuterated aromatic compounds are used as starting materials or labels for pharmaceutical compounds.

[0004] Electronic devices containing organic semiconductors, organometallic semiconductors and / or polymer semiconductors are becoming increasingly important and are used in many commercial products for reasons of their cost and performance. Examples which may be mentioned here are organic charge transport materials in copiers (e.g. triarylamine hole transporters), organic light emitting diodes or polymer light emitting diodes (OLED or PLED) in display devices or organic photoreceptors in copiers. Organic solar cells (O-SCs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic integrated circuits (O-ICs), organic light amplifiers and organic laser diodes (O-lasers) are at an advanced stage of development and are likely to become very important in the future.

[0005] For the purposes of the present invention, an electronic device is an organic electronic device containing an organic semiconductor material as functional material. In particular, the electronic device represents an electroluminescent device, such as an OLED.

[0006] The structure of an OLED in which organic compounds are used as functional materials is known to the person skilled in the art from the prior art. In general, an OLED refers to an electronic device which has one or more layers comprising organic compounds and emits light when a voltage is applied.

[0007] In electronic devices, and in particular in OLEDs, there is an urgent need to improve performance data, in particular lifetime, efficiency and operating voltage. So far, no satisfactory solutions have been found for these aspects.

[0008] Electronic devices generally comprise a cathode, an anode and at least one functional layer, preferably a light-emitting layer. In addition to these layers, they may also comprise further layers, for example in each case 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] Hole transport layers and electron transport layers have a significant impact on the performance data of electronic devices.

[0010] Recently, it has been found that the exchange of hydrogen atoms in organic electronic devices can increase the lifetime of organic electronic devices. This may be due to the fact that CD bonds are slightly stronger than CH bonds, thereby suppressing certain decomposition reactions.

[0011] For the preparation of deuterated compounds, it is advantageous if the deuteration is not carried out until late in the preparation process, particularly in the case of compounds for electronic devices, since deuteration is generally a very expensive step.

[0012] Thus, a precursor of a compound for use in an electronic device, an intermediate of such a compound, or the compound for use in an electronic device itself may be deuterated.

[0013] Typically, the undeuterated compound is treated with a deuterated acid such as D2SO4 or D3PO4 for several hours to obtain the deuterated compound.

[0014] The undeuterated compound can also be reacted in a deuterated solvent in the presence of a Lewis acid such as aluminum trichloride.

[0015] Other methods use high temperatures and voltage or radiation.

[0016] Still other methods use D2 gas, D2O or deuterated solvents such as C6D6 and metal catalysts.

[0017] However, this reaction is usually very slow and unreliable. In addition, deuterium sources such as C6D6 or d8-toluene are very expensive and poorly available.

[0018] JP 2020070291 describes a method for preparing a deuterated compound in an aliphatic hydrocarbon having more than 6 carbon atoms, a deuterium source and a metal catalyst as a solvent. However, an alcohol is additionally used as an additive. In addition, it is also difficult to simply remove the decalin used. The obtained compound is difficult to purify.

[0019] WO 2016073425 A2 describes a method for deuterating a compound in D2O at high pressure and temperature, optionally using a solvent.

[0020] KR 2020094033 A describes deuteration in D2O in the presence of a reducing agent, optionally using 1,4-dioxane.

[0021] An object of the present invention is to provide a method for preparing a deuterated compound, which method has a high conversion rate and a high yield and can economically use a deuterium source.

[0022] The object is achieved by a method for preparing a deuterated organic compound, the method comprising the following steps:

[0023] a) preparing a liquid composition comprising at least one organic compound; at least one heterogeneous metal catalyst; at least one deuterium source; and as solvent at least one aliphatic heterocompound, preferably an acyclic aliphatic ether or a cyclic aliphatic ether and / or an acyclic aliphatic amine or a cyclic aliphatic amine, and optionally at least one aliphatic hydrocarbon;

[0024] b) heating the composition and deuterating the organic compound.

[0025] Deuteration in the sense of the present invention means that during the reaction some or all hydrogen atoms are exchanged with deuterium (D). In deuterated compounds, deuterium is present more frequently than in natural abundance, greater than 100 times. In the case of percentage data, the data refers to the ratio of deuterium in a particular compound to the sum of protons and deuterium.

[0026] In step a), a liquid composition is prepared, which comprises an 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.

[0027] For this purpose, the individual components are mixed. The organic compound may be dissolved in the composition and / or be in partially dispersed form.

[0028] The heterogeneous metal catalyst is preferably selected from the group consisting of platinum, palladium, rhodium, ruthenium, nickel, cobalt, oxides thereof and combinations thereof, preferably platinum or palladium and / or oxides thereof.

[0029] Preferably, the metal of the at least one metal catalyst is in an oxidation state of 0 to 2, preferably 0. Preferably, the at least one metal catalyst is in the form of an elemental metal and / or a metal oxide, preferably as an elemental metal.

[0030] The metal catalyst preferably comprises at least one heterogeneous metal catalyst. The metal of the metal catalyst is preferably in the form of a metal, preferably in the form of a metal applied to a solid phase insoluble in the composition. The solid phase can be a suitable material, for example carbon such as activated carbon or carbon black, silicate, molecular sieve or polymer. The solid phase is stable under the reaction conditions. Carbon is preferably used as a solid phase. Such catalysts are, for example, referred to as Pd / C or Pt / C.

[0031] Preferred metal catalysts are platinum, palladium or mixtures of platinum and palladium, particularly preferably as metal, especially preferably as a heterogeneous catalyst.

[0032] At least one metal catalyst is preferably selected from: platinum / carbon (Pt / C), palladium / carbon (Pd / C) or a mixture of Pt / C and Pd / C. In the case of a mixture, a mixture of Pt / C and Pd / C in a weight ratio of 10: 1 to 1: 2, preferably 7: 1 to 1: 1, in particular 5: 1 to 1: 1 is preferred.

[0033] The metal content on carbon of the metal catalyst is preferably from 1% to 10% by weight, in particular from 3% to 7% by weight, particularly preferably 5% by weight.

[0034] 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. In the case of greater amounts of catalyst, generally fewer by-products are formed.

[0035] The organic compound preferably dissolves in the composition, in particular under the conditions in step b). This means that the organic compound dissolves in the composition after warming.

[0036] The organic compound is preferably an aromatic or heteroaromatic compound, in particular a hydrocarbon compound, or an organometallic compound. Preferably, it is a compound having at least one aromatic or heteroaromatic ring system. The compound or a precursor of such a compound is particularly preferably used in electronic devices, in particular OLEDs.

[0037] Aromatic ring systems in the sense of the present invention contain 6 to 60 C atoms, preferably 6 to 40 C atoms in the ring system. Heteroaromatic ring systems in the sense of the present invention contain 1 to 60 C atoms, preferably 1 to 40 C atoms, and at least one heteroatom in the ring system, provided 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 in the sense of the present invention is a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be connected via non-aromatic units (preferably less than 10% of non-H atoms), for example, via C, N or O atoms or carbonyl groups. This also refers to systems in which two or more aryl or heteroaryl groups are directly connected to each other, for example biphenyl, terphenyl, bipyridine or phenylpyridine. Thus, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene etc. are also intended to be aromatic ring systems in the sense of the present invention, as are systems in which two or more aryl groups are linked, for example, via linear or cyclic alkyl groups or via silyl groups. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups and groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example biphenyl, terphenyl, quaterphenyl or bipyridine, and fluorene or spirobifluorene. In the case of linked heteroaromatic ring systems, ring systems with N-atom-linked aryl or heteroaryl groups are particularly preferred.

[0038] An aryl group in the sense of the present invention contains 6 to 40 C atoms; a heteroaryl group in the sense of the present invention contains 5 to 40 C atoms and at least one heteroatom, provided 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 mean a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused (annulated) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic rings which are linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.

[0039] The electron-rich heteroaromatic ring system is characterized in that it is a heteroaromatic ring system that does not contain any electron-deficient heteroaryl groups. The electron-deficient heteroaryl group is a six-membered heteroaryl ring group with at least one nitrogen atom or a five-membered heteroaryl ring group with at least two heteroatoms, one of which is a nitrogen atom, and the other is an oxygen, sulfur or substituted nitrogen atom, wherein in each case other aryl or heteroaryl groups can also be fused to these groups. In contrast, the electron-rich heteroaryl group is a five-membered heteroaryl ring group with just one heteroatom selected from oxygen, sulfur or substituted nitrogen and other aryl groups and / or other electron-rich five-membered heteroaryl ring groups can be fused thereto. Therefore, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. The electron-rich heteroaryl group is also referred to as an electron-rich heteroaromatic group.

[0040] An electron-deficient heteroaromatic ring system is characterized in that it contains at least one electron-deficient heteroaryl group, particularly preferably no electron-rich heteroaryl groups are present.

[0041] The organic compound may contain one or more aliphatic hydrocarbon groups, or alkyl, alkenyl or alkynyl groups. In addition, it may be substituted by another group such as F, CN, Cl, Br, I, alkoxy or thioalkyl groups. It is important here that these groups do not react under the reaction conditions.

[0042] For the purposes of the present invention, the term alkyl group is used as a generic term for straight or branched alkyl groups and cyclic alkyl groups. Similarly, the term alkenyl group or alkynyl group is used as a generic term for straight or branched alkenyl or alkynyl groups and cyclic alkenyl or alkynyl groups.

[0043] For the purposes of the present invention, aliphatic hydrocarbon radicals or alkyl radicals or alkenyl or alkynyl radicals which may contain 1 to 40 C atoms and in which further individual non-adjacent CH2 groups may be substituted by O, C=O, (C=O)O are preferably the following radicals: 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, 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-hexan-1-yl, 1,1-dimethyl-n-heptan-1-yl, 1,1-dimethyl-n-octan-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-hexyl, 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-diethyl- 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, 1-(n-octyl)-cyclohex-1-yl and 1-(n-decyl)-cyclohex-1-yl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, cyclooctadienyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. Alkoxy groups having 1 to 40 C atoms are preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.Thioalkyl radicals having 1 to 40 C atoms are in particular 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. Generally, the alkyl, alkoxy or thioalkyl group according to the present invention can be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the above groups; in addition, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN or NO2, preferably by F, Cl or CN, particularly preferably by F or CN.

[0044] An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, which may in each case also be substituted by the abovementioned radicals or hydrocarbon radicals and which may be attached to the aromatic or heteroaromatic ring system via any desired position is in particular a radical derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, lettuce, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, cis- or trans-indolocarbazole, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, 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, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthymidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, Benzoxazole, naphthoxazole, anthraoxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazaterphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescein ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole oxadiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 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, indolizine and benzothiadiazole or radicals derived from combinations of these systems, in particular which are linked to one another via single bonds and / or N atoms.

[0045] For the purposes of this specification, the statement that two or more radicals can form a ring system with one another means in particular that the two radicals are connected to one another via a chemical bond and formally eliminate two hydrogen atoms. This is illustrated by the following scheme:

[0046] .

[0047] Furthermore, the above expression also means that, in the case where one of the two groups represents hydrogen, the second group is bonded at the position where the hydrogen atom is bonded, thereby forming a ring. This is illustrated by the following scheme:

[0048] .

[0049] In the case of organometallic compounds, these are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds such as iridium or platinum, particularly preferably platinum compounds, which have at least one heteroaromatic ring system. Preference is given to compounds that are suitable as phosphorescent compounds (=triplet emitters). Examples of such compounds can be found in the applications cited for phosphorescent compounds.

[0050] These compounds are preferably metal chelate complexes, particularly metal chelate complexes having at least one heteroaromatic ring system as a chelate ligand of the metal. Preferably at least one heteroaromatic ring system bonded to the metal via at least one nitrogen atom and via at least one carbon atom. These atoms are preferably at least part of an aryl group or heteroaryl group connected via a single bond in each case. Examples of compounds of this type are 2-phenylpyridine or similar compounds wherein the above-mentioned aryl group or heteroaryl group is connected via a single bond.

[0051] The deuterium source is preferably selected from heavy water, D2O, d6-benzene or d8-toluene, preferably heavy water or D2O, particularly preferably D2O. In particular, heavy water or D2O is a cheaper deuterium source than other compounds.

[0052] Heavy water is understood to mean water in which 50 mol %, preferably at least 70 mol %, particularly preferably at least 80 mol % and in particular at least 90% or 99% of all hydrogen atoms have been replaced by deuterium.

[0053] The solvent is particularly useful for increasing the solubility of the organic compound in the composition.

[0054] Surprisingly, it has been found that solvents, in particular at least one aliphatic heterocompound and optionally at least one aliphatic hydrocarbon, can promote deuteration.

[0055] The aliphatic heterocompound is preferably an aliphatic solvent having at least one heteroatom, preferably selected from N and / or O, and having a boiling point (measured at atmospheric pressure) above 75° C., in particular above 80° C. Preference is given to acyclic or cyclic aliphatic ethers and / or acyclic or cyclic aliphatic amines, particular preference to cyclic aliphatic ethers and / or cyclic aliphatic amines.

[0056] Ethers are understood to mean compounds containing at least one oxygen atom bonded to two aliphatic hydrocarbon groups as defined above, which may also form a ring with one another.

[0057] Aliphatic ethers here refer to monoethers, diethers or triethers.

[0058] The solvent is preferably a linear or cyclic ether having 4 to 18 carbon atoms and 1 to 4 oxygen atoms, preferably a linear or cyclic ether having 4 to 12 carbon atoms and 1 to 3 oxygen atoms, and particularly a linear or cyclic ether having 4 to 8 carbon atoms and 1 or 2 oxygen atoms.

[0059] The solvent is preferably a cyclic aliphatic heterocompound having 4 to 18 carbon atoms, 1 to 4 heteroatoms in each case selected from nitrogen atoms or oxygen atoms. The solvent is particularly preferably a cyclic aliphatic heterocompound having 4 to 12 carbon atoms, 1 to 2 heteroatoms in each case selected from nitrogen atoms or oxygen atoms, very particularly preferably a cyclic aliphatic heterocompound having 4 to 12 carbon atoms, 1 to 2 heteroatoms in each case selected from nitrogen atoms or oxygen atoms, wherein the compound contains at least one six-membered ring.

[0060] 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.

[0061] The cyclic amines which may also contain an oxygen atom are selected, for example, from piperidine, morpholine, pyrrolidine, in particular piperidine or morpholine.

[0062] The optional aliphatic hydrocarbons are preferably aliphatic hydrocarbons having a boiling point (measured at atmospheric pressure) above 75° C., in particular above 80° C. The aliphatic hydrocarbons are preferably cycloalkanes, preferably aliphatic hydrocarbons having at least one ring with 6 aliphatic carbon atoms. Particular preference is given to cyclohexane, methylcyclohexane, methylcyclopentane or condensed cycloalkanes such as decalin. Preference is given to cyclohexane, methylcyclopentane and decalin, in particular cyclohexane. Decalin may be in the form of cis-isomers or trans-isomers or a mixture of isomers.

[0063] It is also possible to use mixtures of solvents, in particular mixtures of at least one aliphatic heterocompound and at least one aliphatic hydrocarbon.

[0064] The volume ratio of the aliphatic hydrocarbon and the aliphatic hetero compound may be selected according to the organic compound, for example, from 100:1 to 1:100, particularly 30:1 to 1:30.

[0065] Therefore, other solvents may also be added in an amount of up to 40% by volume, in particular 0% to 30% by volume, based on aliphatic hetero compounds. This may be, for example, a cycloalkane, in particular a solvent having at least one ring with 6 aliphatic carbon atoms. Particularly preferred are cyclohexane, methylcyclohexane, methylcyclopentane or fused cycloalkanes such as decalin. Preferred are cyclohexane, methylcyclopentane and decalin, in particular cyclohexane. Here, decalin may be in the form of a cis-isomer or a trans-isomer or a mixture of isomers.

[0066] In another embodiment, at least one aliphatic hydrocarbon is present in excess by volume relative to at least one aliphatic heterocompound. In a preferred embodiment, the ratio of hydrocarbon to aliphatic heterocompound 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.

[0067] In a preferred embodiment, the solvent comprises a mixture of at least one cyclic aliphatic heterocompound and at least one cycloalkane. Preferably, the mixture comprises a cycloalkane having at least one ring with 6 aliphatic carbon atoms, particularly preferably cyclohexane, methylcyclohexane or a fused cycloalkane such as decalin, and at least one cyclic aliphatic heterocompound having 4 to 12 carbon atoms and 1 to 2 heteroatoms selected in each case from nitrogen atoms or oxygen atoms, wherein the compound contains at least one six-membered ring. Examples thereof are 1,4-dioxane, tetrahydropyran, piperidine or morpholine.

[0068] In a preferred embodiment, in the case of a mixture, the solvent is a mixture comprising cyclohexane, methylcyclohexane and / or decalin, and at least one cyclic ether selected from 1,4-dioxane and / or tetrahydropyran.

[0069] The solvent is preferably not deuterated. The deuterium source, especially D2O, is preferably the only deuterated compound of the composition.

[0070] The composition preferably does not contain any aliphatic alcohols, in particular aliphatic alcohols having 1 to 10 carbon atoms, the composition preferably does not contain any aliphatic alcohols.The composition preferably does not contain any organic compounds having hydroxyl groups.

[0071] It is known from the prior art that deuteration is promoted in the presence of aliphatic alcohols having 1 to 10 carbon atoms. Surprisingly, it has been found that reaction with a pretreated metal catalyst in the presence of aliphatic heterocompounds improves the deuteration.

[0072] The ratio of hydrogen atoms of the organic compound to deuterium of the deuterium source in the composition 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.

[0073] The amount of aliphatic solvent, aliphatic hetero compound and optionally aliphatic hydrocarbon is such that the organic compound is at least partially dissolved; preferably the deuterium source: solvent ratio measured by volume is 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.

[0074] Improved solubility of the compounds in the solvents used can in particular increase the spatial yield.The process according to the invention enables the process to be carried out at higher concentrations.

[0075] Surprisingly, it has been found that the composition of the solvent can be particularly advantageous for certain classes of compounds.

[0076] The use of at least one aliphatic heterocompound as part of the solvent, especially in the case of organic compounds, especially aromatic or heteroaromatic compounds containing at least one NH function, leads to a significantly improved degree of deuteration, with virtually no by-products compared to pure aliphatic hydrocarbons as solvent. This is especially true if the aliphatic heterocompound is used as excess solvent, especially as the sole solvent.

[0077] Surprisingly, it has been found that when using aliphatic heterocompounds, preferably cyclic ethers, as the sole solvent, a complete conversion can be achieved, ie no undeuterated starting material can be detected.

[0078] Therefore, this embodiment is particularly suitable for intermediates for the production of OLEDs containing such free NH functional groups. Here, NH functional groups refer to NH groups and NH2 groups. They can be, for example, primary or secondary amines and carbazole compounds or carbazole derivatives.

[0079] In step b), the composition is heated to allow deuteration to occur.

[0080] The reaction can be carried out in equilibrium with the ambient pressure, i.e. in an open container or in a closed container. In the latter case, the autogenous pressure may cause a pressure increase due to the heating. The expression of pressure equilibrium may also refer to heating under reflux conditions. Therefore, step b) is preferably carried out at a pressure of 1 bar or more. Preferably less than 6 bar.

[0081] The reaction is preferably carried out in the absence of other 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.

[0082] The composition is preferably not warmed by microwaves.

[0083] It may be necessary to degas the composition before this step. This can be done, for example, by applying the reactive atmosphere several times.

[0084] In step b), the reaction is carried out under heating. Heating can be carried out at a temperature of at least 40° C., in particular at least 70° C., in particular at least 100° C. The temperature is preferably at most 250° C., in particular at most 160° C. Particularly preferably 70° C. to 200° C., in particular 70° C. to 160° C. In a preferred embodiment, the temperature is 100° C. to 160° C., in particular 115° C. to 160° C. The reaction is preferably not carried out under supercritical conditions.

[0085] Depending on the way the reaction is carried out, the reaction can also be carried out under reflux. The solvent can then be selected accordingly to achieve the desired reaction temperature.

[0086] The process according to the invention 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.

[0087] In addition to the deuteration, the formation of by-products during the process is also very important. Especially when applied to complex compounds, less by-product formation can be more favorable than the highest possible deuteration. This is due in particular to the fact that not all protons in a compound are equally accessible.

[0088] Depending on the by-product, it may be more advantageous if a complete conversion is achieved and thus at least no starting material is detected any more. This is particularly the case if the by-product is easy to separate off.

[0089] The process is preferably continued until a conversion of at least 90% (measured using HPLC) is achieved. This means that a maximum of 10% of the starting material is still present. Preferably the conversion is at least 95%.

[0090] The reaction is preferably carried out for 1 hour to 200 hours, particularly 10 hours to 100 hours.

[0091] The reaction is particularly preferably continued until a degree of deuteration of at least 20% and less than 15% by-products, preferably at least 25% and less than 10% by-products, in particular at least 30% and less than 10% by-products is achieved.

[0092] In a preferred embodiment, the reaction is continued until the degree of deuteration of the by-products is greater than 30% and the by-products are less than 5%, in particular the degree of deuteration is greater than 30% and the by-products are less than 4%, preferably the by-products are less than 2%.

[0093] After cooling and optional pressure equalization, the deuterated compound is preferably isolated using known techniques. This may include extraction, precipitation, filtration, distillation, chromatography or similar methods.

[0094] In one embodiment of the invention, the composition comprises at least one additive for improving deuteration and / or reducing by-products. At least one additive is preferably selected from: alkylamines, preferably alkylamines containing alkyl groups having 1 to 40 C atoms, wherein individual 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, the metal salts and / or metal oxides are selected from salts or oxides of palladium, platinum, rhodium, ruthenium, silver, gold, copper, nickel or cobalt, wherein salts or oxides of silver or palladium, in particular salts or oxides of Pd(II) are preferred. In the case of 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. Carboxylates such as Pd(OAc)2, Ag(OAc) or Pd(OPiv)2 are particularly preferred.

[0095] Preferred alkylamines are alkylamines with at least two, preferably three, alkyl groups, in particular alkyl groups with 1 to 40 C atoms, wherein individual non-adjacent CH2 groups may be replaced by O and at least two alkyl groups may 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. Preference is given to alkylamines containing three alkyl groups with 1 to 5 C atoms (tertiary amines) and alkylamines containing three alkyl groups, two of which form a ring, wherein the ring may contain O atoms.

[0096] Examples of such amines are triethylamine, dimethylethylamine, diethylmethylamine, diisopropylethylamine, of which triethylamine is preferred. Examples of cyclic amines are morpholine derivatives, in particular morpholine, piperidine, 2,2,6,6-tetramethylpiperidine, N-alkylmorpholines such as N-methylmorpholine, N-ethylmorpholine, N-propylmorpholine. The amine used is preferably soluble in the composition.

[0097] The above-mentioned metal salts are particularly preferred.

[0098] Surprisingly, it has been found that, in particular, alkylamines, silver salts and / or palladium salts can promote deuteration and reduce the formation of by-products. This can allow the reaction to be carried out for a longer time or at a higher temperature. The use of additives may depend on the compound to be deuterated.

[0099] Depending on the reaction mode and the organic compound, the additive can be used in different amounts. Preferably, 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.

[0100] In one embodiment of the present invention, the composition does not contain any reducing agent, in particular does not contain any NaBD4.

[0101] In a preferred embodiment, the composition comprises: at least one aromatic or heteroaromatic compound, platinum / carbon and / or palladium / 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, and the metal salts and / or metal oxides are selected from salts or oxides of palladium, platinum, rhodium, ruthenium, silver, gold, copper, nickel or cobalt.

[0102] In a preferred embodiment, the composition consists of at least one aromatic or heteroaromatic compound, platinum / carbon and / or palladium / 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, and the metal salts and / or metal oxides are selected from salts or oxides of palladium, platinum, rhodium, ruthenium, silver, gold, copper, nickel or cobalt.

[0103] In one embodiment of the present invention, at least one heterogeneous metal catalyst is treated prior to being added to the composition, wherein the treatment comprises drying of the metal catalyst.

[0104] In one embodiment of the present invention, the heterogeneous metal catalyst is water-wet prior to drying, wherein the water content (by Karl Fischer) is at least 10%.

[0105] 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 at reduced pressure, in particular below 100 mbar. Drying is preferably continued until the water content (by Karl Fischer method) is less than 5% by weight, preferably less than 2% by weight, preferably less than 1%.

[0106] Particularly preferably, drying is carried out at 50° C. to 70° C. at less than 50 mbar, in particular at 50° C. to 70° C. at less than 30 mbar, very particularly preferably at 55° C. to 75° C. at 1 mbar to 30 mbar. Drying is preferably carried out for at least 24 hours, in particular for at least 48 hours. Preferably, drying is carried out for 24 hours to 96 hours, in particular for 48 hours to 96 hours.

[0107] The treatment is preferably carried out under air or an inert gas such as nitrogen or argon. No activation with hydrogen or deuterium gases takes place.

[0108] Metal catalysts are often stored in moist form. Surprisingly, it has now been found that pre-drying, in particular when using D2O as deuterium source, significantly improves the activity of the catalyst.

[0109] The pretreated metal catalyst can be used in the next step without additional treatment.

[0110] The deuterated compounds according to the invention are suitable for use in electronic devices, in particular in organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds can be used in a variety of functions and layers.

[0111] An electronic component in the sense of the present invention is a component which contains at least one layer which comprises at least one organic compound. The component may also contain inorganic materials or may also contain layers which consist completely of inorganic materials.

[0112] The electronic device is preferably selected from: organic electroluminescent device (OLED), organic integrated circuit (O-IC), organic field effect transistor (O-FET), organic thin film transistor (OTFT), organic light emitting transistor (OLET), organic solar cell (OSC), dye-sensitized organic solar cell (DSSC), organic optical detector, organic photoreceptor, organic field quenching device (OFQD), light emitting electrochemical cell (LEC), organic laser diode (O-laser) and organic plasma light emitting device, but preferably an organic electroluminescent device (OLED).

[0113] 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 can be an emitting layer, a hole transport layer, an electron transport layer, a hole blocking layer, an electron blocking layer or another functional layer, and the at least one organic layer comprises at least one deuterated compound according to the invention. The layers depend on the substitution of the compound.

[0114] In addition to these layers, the organic electroluminescent device may also include other layers, such as 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. Similarly, an intermediate layer having, for example, an exciton blocking function may be introduced between two light-emitting layers. However, it should be noted that each of these layers does not necessarily have to be present.

[0115] The organic electroluminescent device can contain a luminescent layer, or it can contain multiple luminescent layers. If there are multiple luminescent layers, they preferably have multiple luminescent peaks between 380 nm and 750 nm in total, so that the overall result is white luminescence, that is, a variety of luminescent compounds that can fluoresce or phosphoresce are used in the luminescent layer. Particularly preferably, there is a system with three luminescent layers, wherein the three layers show blue, green and orange or red luminescence (basic structure is described in, for example, WO 2005 / 011013). The organic electroluminescent device according to the present invention can also be a tandem OLED, especially for white luminescent OLED.

[0116] An organic electroluminescent device may comprise one or more phosphorescent emitters.

[0117] The organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers, at least one of which comprises at least one deuterated compound. In addition, the deuterated compound according to the invention may also be used in an electron transport layer and / or a hole blocking layer and / or a hole transport layer and / or an exciton blocking layer.

[0118] The term "phosphorescent compound" generally refers to a compound in which light emission occurs via a spin-forbidden transition, for example from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0119] Suitable phosphorescent compounds (=triplet emitters) are in particular compounds which emit light under suitable excitation, 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 comprising transition metals or lanthanides are preferably regarded as phosphorescent compounds, in particular if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper. In the context of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent emitting compounds.

[0120] Examples of the above-mentioned luminophores can be found in 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、WO2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO2014 / 094961、WO 2014 / 094960、WO 2015 / 036074、WO 2015 / 104045、WO 2015 / 117718、WO2016 / 015815、WO 2016 / 124304、WO 2017 / 032439、WO 2018 / 011186、WO 2018 / 041769、WO2019 / 020538、WO 2018 / 178001, WO 2019 / 115423 and WO 2019 / 158453. In general, all phosphorescent complexes known to the person skilled in the art for phosphorescent OLEDs and in the field of organic electroluminescence according to the prior art are suitable, and the person skilled in the art can use other phosphorescent complexes without inventive effort. Surprisingly, it has been found that such compounds can be deuterated using the method according to the invention.

[0121] 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 hole transport layer in a proportion of 100%, or it can be used in combination with one or more other compounds. In a preferred embodiment, the organic layer comprising the deuterated compound then additionally comprises one or more p-type dopants. The p-type dopant used according to the invention is preferably an organic electron acceptor compound capable of oxidizing one or more other compounds in the mixture.

[0122] 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.

[0123] Particularly preferred p-type dopants are quinodimethane compounds, azaindenofluorenediones, azaphenylidenes, azaterphenylidenes, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of the third main group, 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. It is also preferred to use transition metal oxides as dopants, preferably oxides of rhenium, molybdenum and tungsten, particularly preferably Re2O7, MoO3, WO3 and ReO3.

[0124] The p-type dopant is preferably present in the p-doped layer in a substantially uniform distribution. This can be achieved, for example, by co-evaporating the p-type dopant and the hole transport material matrix.

[0125] The deuterated compounds can also be used as matrix materials in an emitting layer in combination with one or more emitting compounds, preferably phosphorescent compounds.

[0126] In this case, the proportion of the matrix material in the emitting layer is between 50.0% and 99.9% by volume, preferably between 80.0% and 99.5% by volume, particularly preferably between 92.0% and 99.5% by volume, for a fluorescent emitting layer, and between 85.0% and 97.0% by volume for a phosphorescent emitting layer.

[0127] Accordingly, the proportion of the emitting compound is between 0.1% and 50.0% by volume, preferably between 0.5% and 20.0% by volume, particularly preferably between 0.5% and 8.0% by volume for a fluorescent emitting layer, and between 3.0% and 15.0% by volume for a phosphorescent emitting layer.

[0128] The light-emitting layer of the organic electroluminescent device may also comprise a system containing a plurality of matrix materials (mixed matrix system) and / or a plurality of light-emitting compounds. Also in this case, the light-emitting compounds are usually those compounds having a smaller proportion in the system, and the matrix materials are usually those compounds having a larger proportion in the system. However, in individual cases, the proportion of individual matrix materials in the system may be less than the proportion of individual light-emitting compounds.

[0129] Preferred fluorescent luminescent compounds are selected from arylamines. For the purposes of the present invention, arylamines or aromatic amines refer to compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably a fused ring system with at least 14 aromatic ring atoms. Preferred examples of these ring systems are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic leucophyllamines or aromatic leucophyllamines. Aromatic anthraceneamines refer to compounds in which one diarylamino group is directly bonded to anthracene groups, preferably directly bonded at the 9 position. Aromatic anthracenediamines refer to compounds in which two diarylamino groups are directly bonded to anthracene groups, preferably directly bonded at the 9,10 positions. Aromatic pyreneamines, pyrenediamines, leucophyllamines and leucophyllamines are similarly defined, wherein the diarylamino groups are preferably bonded to pyrene at the 1 position or the 1,6 position. Other preferred emitting compounds are indenofluorenamine or indenofluorenediamine, for example according to WO 2006 / 108497 or WO 2006 / 122630, for example benzoindenofluorenamine or benzoindenofluorenediamine, for example according to WO 2008 / 006449, and for example dibenzoindenofluorenamine or dibenzoindenofluorenediamine, for example according to WO 2007 / 140847, and indenofluorene derivatives containing fused aryl groups disclosed in WO 2010 / 012328. Preference is also given to the pyrenarylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871. Likewise preferred are the benzoindenofluoreneamines disclosed in WO 2014 / 037077, the benzofluoreneamines disclosed in WO 2014 / 106522, the extended benzoindenofluorenes disclosed in WO 2014 / 111269 and WO 2017 / 036574, the phenoxazines disclosed in WO 2017 / 028940 and WO 2017 / 028941, and the fluorene derivatives bonded to furan units or thiophene units disclosed in WO 2016 / 150544.

[0130] For fluorescent compounds, useful matrix materials preferably include materials from a variety of substance classes. Preferred matrix materials are selected from the following classes: oligoaryls (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461, or dinaphthylanthracene), in particular oligoaryls with annulated aromatic groups, oligoarylidenevinylene (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 and the like (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 benzanthracene (e.g. according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the class of oligoarylene groups comprising naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylene vinylene groups, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the class of oligoarylene groups comprising anthracene, benzanthracene, triphenylene and / or pyrene or atropisomers of these compounds. For the purposes of the present invention, an oligoarylene group is a compound in which at least three aryl or arylene groups are linked to one another. Additionally preferred are anthracene derivatives disclosed in WO 2006 / 097208, WO 2006 / 131192, WO 2007 / 065550, WO 2007 / 110129, WO 2007 / 065678, WO2008 / 145239, WO 2009 / 100925, WO 2011 / 054442 and EP 1553154, pyrene compounds disclosed in EP1749809, EP 1905754 and US 2012 / 0187826, benzanthrylanthracene compounds disclosed in WO 2015 / 158409, indenobenzofurans disclosed in WO 2017 / 025165, and phenanthrenthracene disclosed in WO 2017 / 036573.

[0131] For phosphorescent compounds, preferred matrix materials are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines; carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746; indenocarbazole derivatives, for example according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials, for example according to WO 2007 / 137725; silanes, for example according to WO 2005 / 111172; borazolidines or boric acid esters, for example according to WO 2006 / 117052; triazine derivatives, for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877; zinc complexes, for example according to EP652273 or WO 2009 / 062578; siladiazacyclopentane or siladiazacyclopentane derivatives, for example according to WO 2010 / 054729; phosphodiazacyclopentane derivatives, for example according to WO 2010 / 054730; bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; terphenylidene derivatives, for example according to WO 2012 / 048781; lactams, for example according to WO 2011 / 116865 or WO 2011 / 137951; or dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565. Other phosphorescent emitters emitting at a shorter wavelength than the actual emitter, or compounds which do not participate in charge transport or do not participate to a significant extent, as described, for example, in WO 2010 / 108579, may likewise be present in the mixture as co-hosts.

[0132] In addition to deuterated compounds, suitable charge transport materials that can be used in hole injection layers or hole transport layers or electron blocking layers or electron transport layers of electronic components are, for example, the compounds cited in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials for use in these layers according to the prior art.

[0133] The OLED preferably comprises two or more different hole-transporting layers. In this case, the deuterated compound can be used for one or more or all of the hole-transporting layers. Other compounds which are preferably used in the hole-transporting layer of the OLED are, in particular, indenofluoreneamine derivatives (for example according to WO 06 / 122630 or WO 06 / 100896), amine derivatives as disclosed in EP 1661888, hexaazaterphenylidene derivatives (for example according to WO 01 / 049806), amine derivatives containing an annulated aromatic ring (for example according to US Pat. No. 5,061,569), amine derivatives as disclosed in WO 95 / 09147, monobenzoindenofluoreneamine (for example according to WO 08 / 006449), dibenzoindenofluoreneamine (for example according to WO 07 / 140847), spirobifluoreneamine (for example according to WO 2012 / 034627 or WO 2013 / 120577), fluoreneamine (for example according to WO 2014 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), spirobibenzopyranamines (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), phenanthryl diarylamines (for example according to WO 2015 / 131976), spirotribenzotropolones (for example according to WO 2016 / 087017), spirobifluorenes containing meta-phenylenediamine groups (for example according to WO 2016 / 078738), spirobiacridines (for example according to WO 2015 / 158411), xanthene diarylamines (for example according to WO 2014 / 072017), and 9,10-dihydroanthracene spiro compounds containing a diarylamino group according to WO 2015 / 086108.

[0134] Very particular preference is given to using spirobifluorenes substituted in the 4-position by a diarylamino group as hole-transporting compounds, in particular those compounds claimed and disclosed in WO 2013 / 120577, and spirobifluorenes substituted in the 2-position by a diarylamino group as hole-transporting compounds, in particular those compounds claimed and disclosed in WO 2012 / 034627.

[0135] The materials that can be used for the electron transport layer are all materials used as electron transport materials in the electron transport layer according to the prior art. 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, phosphodiazocyclopentane derivatives, and phosphine oxide derivatives. Other suitable materials are derivatives of the above compounds disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0136] The preferred cathode of the electronic component is a metal with a low work function, a metal alloy or a multilayer structure, wherein the metal alloy or multilayer structure comprises a variety of metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alkali metals or alkaline earth metals and silver alloys, such as alloys of magnesium and silver are also suitable. In the case of a multilayer structure, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, are also used, wherein combinations of metals, such as Ca / Ag, Mg / Ag or Ba / Ag are generally used. It is also 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, and corresponding oxides or carbonates (e.g. LiF, Li2O 、 BaF2, MgO, NaF, CsF, Cs2CO3, etc.). For this purpose, lithium quinolate (LiQ) can also be used. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0137] Preferred anodes are materials with a high work function. The anode preferably has a work function greater than 4.5 eV relative to vacuum. Suitable for this purpose are firstly metals with a high redox potential, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (such as Al / Ni / NiO x 、Al / PtO x). For some applications, at least one of the electrodes must be transparent or translucent in order to enable illumination of the organic material (organic solar cells) or luminescence (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive doped organic materials, in particular conductive doped polymers, are also preferred. In addition, the anode can also consist of two or more layers, for example an ITO inner layer and an outer layer of a metal oxide, the metal oxide being preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0138] The device is structured accordingly (depending on the application), provided with contacts and finally sealed to exclude harmful influences due to water and air.

[0139] In the other layers of the organic electroluminescent device, all materials commonly used according to the prior art can be used. The person skilled in the art will therefore be able to use all materials known for organic electroluminescent devices in combination with deuterated compounds without inventive effort. In addition, the above-mentioned compounds, in particular aromatic or heteroaromatic compounds, can be deuterated using the method according to the invention, in particular to improve their lifetime.

[0140] Furthermore, preference is given to an organic electroluminescent device, characterized in that one or more layers are coated by means of a sublimation method, wherein the sublimation reaction is carried out in a vacuum sublimation unit at temperatures below 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, the initial pressure can also be even lower, for example below 10 -7 millibar.

[0141] Likewise preferred is an organic electroluminescent device, characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation, wherein at 10 -5 The material is applied at a pressure of between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thereby structured.

[0142] Furthermore, preference is given to an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin coating, or by any desired printing method, for example screen printing, flexographic printing, offset printing, LITI (light-induced thermal imaging), inkjet printing or nozzle printing. For this purpose, it is necessary to obtain soluble compounds, for example by suitable substitution.

[0143] Furthermore, hybrid processes are possible in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

[0144] These processes are generally known to the person skilled in the art and can be applied without inventive step to organic electroluminescent devices which contain the compounds according to the invention.

[0145] In particular, electronic devices containing one or more deuterated compounds may be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications (eg, light therapy).

[0146] The deuterated compound and the organic electroluminescent device according to the present invention are distinguished by having one or more of the following characteristics:

[0147] 1. The compounds according to the invention cause longevity.

[0148] 2. The compounds according to the invention lead to high efficiencies, in particular high EQEs.

[0149] 3. The compounds according to the invention lead to low operating voltages.

[0150] The present invention is explained in more detail by the following examples, but it is not intended to be limited thereby. Those skilled in the art will be able to use the description to implement the present invention within the entire scope disclosed, and will be able to prepare other deuterated compounds and use them in electronic devices without inventive effort, or use the method according to the present invention. Example

[0151] Unless otherwise stated, the following syntheses were carried out in dry solvents under a protective gas atmosphere. Solvents and reagents can be obtained, for example, from Sigma-ALDRICH or ABCR. The corresponding numbers in square brackets or the numbers shown for individual compounds refer to the CAS numbers of compounds known from the literature.

[0152] Compounds used:

[0153]

[0154] Materials used:

[0155] Deuterium oxide - D2O: Sigma Aldrich (≥99.5 atomic % D)

[0156] Dioxane- Dioxane: MerckMillipore (≥99.5%)

[0157] Tetrahydropyran - THP: Sigma Aldrich (≥98.5%)

[0158] 2-Methyltetrahydrofuran- MTHF: Sigma Aldrich (≥98.5%)

[0159] 2,2-Dimethyltetrahydrofuran - DMTHF: Sigma Aldrich (≥98.5%)

[0160] Methyl tert-butyl ether - MTBE: MerckMillipore (≥99.5%)

[0161] Tert-Amyl Methyl Ether - TAME: MerckMillipore (≥99.5%)

[0162] 1,2-Di-tert-butoxyethane - DTBOE: Alfa Chemistry (> 95%)

[0163] Piperidine-Pip: MerckMillipore (≥99.0%)

[0164] 2,2,6,6-Tetramethylpiperidine - TMPip: Sigma Aldrich (≥98.5%)

[0165] Morpholine-Morph: MerckMillipore (≥99.0%)

[0166] Cyclohexane-Cy: MerckMillipore (≥99.5%)

[0167] Palladium / Carbon - Pd / C: 5 wt% Pd; Evonic Operations GmbH

[0168] Platinum / Carbon - Pt / C: 5 wt% Pt; Evonic Operations GmbH

[0169] Rhodium / Carbon - Rh / C: 5 wt% Rh; Evonic Operations GmbH

[0170] Nickel / Carbon - Ni / C: 5 wt% Ni; Evonic Operations GmbH

[0171] Drying of catalyst:

[0172] The water-wet catalysts (Pd / C and Pt / C) were dried in a vacuum drying cabinet at 60° C. and 20 mbar for 7 days. The water content according to Karl Fischer method was about 1%.

[0173] Overview of the steps:

[0174] Performance of reactions in autoclaves at inherent pressure

[0175] Compound V, D2O, solvent (Lömi), catalyst Kat.1, optional catalyst Kat.2 and additive Add.1 are charged into a stirred autoclave, rendered inert by injecting and discharging 5 bar of nitrogen twice, degassed by injecting and discharging 30 bar of nitrogen once and stirred at the specified temperature T for the specified reaction time R at 1000 rpm using a pitched blade stirrer. The exact batch quantities are as follows. The stirred autoclave is allowed to cool, the reaction mixture is removed while still warm (about 50° C.-80° C.), the catalyst is filtered off and any aqueous phase present is separated off. The catalyst is washed with a warm (about 50° C.-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 to dryness in a rotary evaporator under reduced pressure (p about 20 mbar, T about 60° C.).

[0176] Batch materials and reaction conditions:

[0177]

[0178] result:

[0179]

[0180] Batch materials and reaction conditions:

[0181]

[0182] result:

[0183]

[0184] Batch materials and reaction conditions:

[0185]

[0186] result:

[0187]

[0188] Batch materials and reaction conditions:

[0189]

[0190] result:

[0191]

[0192] Batch materials and reaction conditions:

[0193]

[0194] result:

[0195]

[0196] Batch materials and reaction conditions:

[0197]

[0198] result:

[0199]

[0200] Batch materials and reaction conditions:

[0201]

[0202] result:

[0203]

[0204] Batch materials and reaction conditions:

[0205]

[0206] result:

[0207]

[0208] Experiments in pure 1,4-dioxane, THP or MTBE

[0209] The experiments were performed as described above.

[0210] Batch materials and reaction conditions:

[0211]

[0212] result:

[0213]

[0214] Batch materials and reaction conditions:

[0215]

[0216] result:

[0217]

[0218] For compounds V2 containing an NH function, complete conversion occurred in pure 1,4-dioxane or THP or MTBE, which was not achieved in mixtures of cyclohexane and 1,4-dioxane.

Claims

1. A method for preparing a deuterated organic compound, the method 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 an acyclic or cyclic aliphatic ether and / or an acyclic or cyclic aliphatic amine, and optionally at least one aliphatic hydrocarbon as solvent; b) heating the composition and deuterating the organic compound.

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

3. The process according to one or more of claims 1 or 2, wherein the organic compound is an aromatic or heteroaromatic compound or an organometallic compound.

4. The process according to one or more of claims 1 to 3, wherein the organic compound is an aromatic or heteroaromatic compound or an organometallic compound containing at least one NH function.

5. The 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. The process according to one or more of claims 1 to 5, wherein the solvent is an aliphatic solvent having a boiling point above 75°C.

7. The 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. The method according to one or more of claims 1 to 7, wherein the ratio by volume of deuterium source to solvent is from 2:1 to 1:

50.

9. The method according to one or more of claims 1 to 8, wherein: In step b), the mixture is heated to a temperature of at least 40°C, preferably at least 70°C.

10. The method according to one or more of claims 1 to 9, wherein: In step b), the mixture is heated to a temperature of at most 200°C, preferably at most 160°C.

11. The method according to one or more of claims 1 to 10, wherein step b) is carried out under pressure equilibrium with the ambient pressure or without pressure equilibrium.

12. The 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. The process according to one of claims 1 to 12, wherein the solvent comprises at least one cycloaliphatic ether and / or at least one cycloaliphatic amine, and optionally at least one aliphatic hydrocarbon.

14. The process according to 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.

15. The method according to one of claims 1 to 14, wherein at least one heterogeneous metal catalyst is treated before being added to the composition, wherein the treatment comprises drying of the metal catalyst.

16. The method according to claim 15, wherein the drying is continued until the water content (by Karl Fischer method) is less than 5% by weight.

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