[go: up one dir, main page]

WO2025132547A1 - Procédé mécanochimique de deutération de composés organiques - Google Patents

Procédé mécanochimique de deutération de composés organiques Download PDF

Info

Publication number
WO2025132547A1
WO2025132547A1 PCT/EP2024/087052 EP2024087052W WO2025132547A1 WO 2025132547 A1 WO2025132547 A1 WO 2025132547A1 EP 2024087052 W EP2024087052 W EP 2024087052W WO 2025132547 A1 WO2025132547 A1 WO 2025132547A1
Authority
WO
WIPO (PCT)
Prior art keywords
deuterated
atoms
aromatic
compound
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/087052
Other languages
English (en)
Inventor
Nico FLECK
Marcel BUERGER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of WO2025132547A1 publication Critical patent/WO2025132547A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/001—Acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/002—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled

Definitions

  • the present invention relates to a method for deuterating an organic compound, and to deuterated compounds obtained by said method.
  • Deuterium ( 2 H) is one of the two stable isotopes of hydrogen (besides protium, 1 H) and has a natural abundance of approximately 0.0156% (0.0312% by mass) of all the naturally occurring hydrogen in the oceans.
  • Deuterated compounds in which the level of deuterium is intentionally enriched, are known.
  • deuterated aromatic compounds have often been used in studies of the course of chemical reactions or conversions in metabolism.
  • Deuterated aromatic compounds are also used as starting materials for pharmaceutical compounds or markers.
  • deuterated organic or metallorganic compounds in electronic devices. More particularly, the use of deuterated organic or metallorganic compounds in organic electroluminescent devices (OLEDs) can drastically improve the OLEDs performances in terms of efficiency and lifetime as disclosed, for example, in WO 2010/099534, WO 2011/050888 or J. Phys. Chem. C 2007, 111 , 3490-3494.
  • electronic devices are understood to mean organic electronic devices, which contain organic semiconductor materials as functional materials.
  • the electronic devices stand for organic electroluminescent (EL) devices such as organic light emitting diodes (OLEDs).
  • EL organic electroluminescent
  • OLEDs organic light emitting diodes
  • organic electroluminescent (EL) devices are understood to mean electronic devices containing spaced electrodes which are separated by one or more layers that comprise organic compounds, which form the so-called organic light emitting structure, and emit light when a voltage is applied.
  • organic layer any layer of an organic electronic device which comprises one or more organic compounds as functional materials will also be called “organic layer”.
  • a higher deuteration degree than in nature can be achieved by reacting building blocks together, where at least one of the building blocks has been enriched with deuterium beforehand via a deuteration method (as described in WO 2011/050888), or by deuterating a compound via a deuteration method once it has been synthesized (as described in WO 2010/099534).
  • deuteration methods for the synthesis of deuterated compounds can be quite challenging, time-consuming and also costly.
  • the practical realization of deuterating an organic compound essentially relies on two approaches that represent the state of the art:
  • acid- catalyzed processes using a deuterated aromatic solvent e.g. benzene-d 6 or toluene-d 8
  • deuterium source as described, for example, in WO 2011/053334.
  • Such processes suffer from the intrinsic drawback of high costs for the deuterium source, since deuterium is commercially enriched as D2O, and all other deuterated solvents are obtained upstream.
  • deuteration methods that can overcome at least some of the above-outlined drawbacks for forming various deuterated compounds that can be used in OLEDs, but also for forming deuterated building blocks that can be used in the synthesis of deuterated compounds.
  • deuteration methods that can be performed under mild conditions and still result in high deuteration degree and process efficiency.
  • Mechanochemistry in general refers to a way of promoting chemical reactions or chemical transformations by utilizing mechanical force and/or mechanical energy, and without the need for bulk dissolution of reactants.
  • This art of chemical synthesis relies especially on methods which apply mechanical force, for example frictional, shear and/or impact force, including, but not limited to, (ball)-milling, extruding, grinding, vibration or acoustic mixing, and combinations thereof.
  • the present invention therefore provides a method for deuterating an organic compound, the method comprising the following steps:
  • composition (b) subjecting the composition to a mechanochemical treatment in the presence of a catalyst.
  • Deuteration of an organic compound means the substitution of at least one hydrogen atom that is bound to a carbon atom of an organic compound with a deuterium atom, which substitution is also referred to herein as “H-D exchange”. Accordingly, the terms “H-D exchange method” and “deuteration method” both are understood to mean methods which aim at substituting at least one hydrogen atom in a compound with a deuterium atom to obtain a deuterated compound.
  • deuterated compound corresponds to a compound, in which at least one hydrogen atom is replaced by a deuterium atom and in which the abundance of deuterium at each deuterated position of the compound is higher than the natural abundance of deuterium, which is about 0.015%.
  • a compound/precursor has to undergo a deuterium enrichment via a deuteration method.
  • a “deuterated compound” is indeed a mixture of various isotopomers, but the singular term is applied for the sake of conciseness.
  • the deuteration degree corresponds to the number of deuterium atoms in a compound based on the total number of deuterium atoms and protium atoms in the compound in %, as follows:
  • ND is the number of deuterium atoms in the compound
  • Np is the number of deuterium and protium atoms in the compound.
  • the deuteration degree can be determined or measured by 1 H-NMR or gas chromatography-mass spectrometry (GC-MS), or high-performance liquid chromatography-mass spectrometry (HPLC-MS), which are all standard methods known to a person skilled in the art.
  • GC-MS gas chromatography-mass spectrometry
  • HPLC-MS high-performance liquid chromatography-mass spectrometry
  • hydrogen should be understood to design the protium isotope of hydrogen, which accounts for more than 99.98% of the natural occurring hydrogen in the oceans.
  • “mechanochemical treatment” should be understood to mean conduction of a chemical reaction, here, deuteration via H-D exchange, in a setup, where mechanical energy is dissipated on the reaction mixture as the predominant, but not necessarily the only, form of energy input.
  • Typical examples of methods capable of providing a setup, where mechanical energy is dissipated on the reaction mixture include, without being limited thereto, milling such as ball milling, grinding, extruding, mixing such as vibrational mixing or resonance acoustic mixing, and the like, which methods apply mechanical force such as frictional, shear and/or impact force on the reactants.
  • mechanochemical device should be understood to mean any device, apparatus or equipment capable of conducting such mechanochemical treatment by generating mechanical force and/or energy to be dissipated on the reaction mixture.
  • Typical devices in this sense include, without being limited thereto, milling devices such as ball, shaker, roller or planetary mills, extruders, mixing devices such as (resonance) acoustic mixers or vibrational mixers, grinding devices, and the like.
  • Providing the composition in step a) preferably comprises mixing of the individual components, i.e. , the organic compound to be deuterated, the deuterium source, etc.
  • the mixing can be carried out in any feasible way known to a person skilled in the art.
  • the organic compound may be dissolved or partially dispersed in the composition, which may be due to the fact that deuterium source used is liquid, or because a solvent may be additionally added.
  • the composition is preferably provided in the form of a solution or a suspension, more preferably in the form of a suspension, in particular in case the organic compounds has low solubility in common solvents and/or the deuterium source.
  • the mechanochemical approach applied in the present invention advantageously does not require for bulk dissolution of reactants and therefore allows for reduced amounts of solvents and renders high temperatures to boost the solubility unnecessary.
  • a deuterium source which is able to provide one or more deuterium atoms for hydrogen substitution has to be provided in the composition.
  • the deuterium source is preferably selected from deuterated hydrocarbons, deuterated ethers, deuterated chlorocarbons, deuterated aprotic compounds, and deuterated protic compounds.
  • the deuterium source is selected from deuterium oxide (D2O), deuterated benzenes (benzene-dn), particularly benzene-de, deuterated toluenes (toluene-dn), particularly toluene- ds and toluene-ds, deuterated xylenes (xylene-dn), particularly xylene-dw, deuterated dimethyl sulfoxide (DMSO-dn), particularly DMSO-de, deuterated acetones (acetone-dn), particularly acetone-de, deuterated alcohols, preferably CD3OD and EtOH-dn, and CDCI3, and mixtures thereof.
  • D2O deuterium oxide
  • benzene-dn deuterated benzenes
  • benzene-dn deuterated toluenes
  • toluene-dn particularly toluene- ds and toluene-ds
  • the deuterium source is selected from D2O, deuterated benzenes (benzene-d n ), deuterated toluenes (toluene-d n ), deuterated xylenes (xylene- d n ), CD3OD and EtOH-dn, and mixtures thereof.
  • the deuterium source is deuterium oxide (D2O) due to its comparably low costs.
  • Deuterium oxide in the sense of the invention also refers to heavy water.
  • the deuterium source has a deuterium enrichment of more than 10 mol%, preferably more than 50 mol%, more preferably more than 70 mol%, and most preferably more than 90 mol%, in order to increase the H-D exchange rate.
  • a deuterium enrichment of more than 10 mol% is understood to mean that more than 10 mol% of all hydrogen atoms are substituted by deuterium, and so on.
  • the deuterium source is selected from deuterated hydrocarbon solvents, deuterated ether solvents, deuterated chlorocarbon solvents, deuterated aprotic solvents, and deuterated protic solvents, for example deuterium oxide, deuterated benzenes, deuterated toluenes, deuterated xylenes, deuterated dimethyl sulfoxide, deuterated acetones, deuterated alcohols, and CDCh, having a deuterium enrichment of more than 10 mol%, preferably more than 50 mol%, more preferably more than 70 mol%, and most preferably more than 90 mol%.
  • deuterated hydrocarbon solvents for example deuterium oxide, deuterated benzenes, deuterated toluenes, deuterated xylenes, deuterated dimethyl sulfoxide, deuterated acetones, deuterated alcohols, and CDCh, having a deuterium enrichment of more than 10 mol%, preferably more
  • the amount of the deuterium source may depend on the type of organic compound and its amount in the composition.
  • the amount of the deuterium source in the composition provided in step a) is from 1 to 98 weight percent (“wt.%”), more preferably 1 to 95 wt.%, even more preferably 1 to 75 wt.%, even more preferably 1 to 65 wt.%, even more preferably 1 to 55 wt.%, still more preferably 1 to 45 wt.%, still more preferably 1 to 35 wt.%, particularly preferably 1 to 25 wt.%, more particularly preferably 1 to 15 wt.% and most preferably 1 to 5 wt.%, each based on a total weight of the deuterium source and the organic compound in the composition.
  • the mechanochemical treatment in step b) is not limited, as long as it is capable of conducting the deuteration of the organic compound via H-D exchange in a setup, where mechanical energy is dissipated on the composition as the predominant, but not necessarily the only, form of energy input.
  • any method known by a person skilled in the art that applies mechanical force, such as frictional, shear and/or impact force, to thereby provide a setup where mechanical energy is dissipated on the composition may be employed as desired.
  • Exemplary methods for conducting the mechanochemical treatment in step b) include, but are not limited to, milling, such as ball-milling, grinding, extruding, or mixing, such as vibrational mixing or (resonance) acoustic mixing, of the composition in order to apply mechanical force and/or energy.
  • Devices for carrying out such mechanochemical treatment, which generate mechanical force and/or energy to be dissipated on the composition are known to a person skilled in the art and include, for example, milling devices such as ball, shaker, roller and planetary mills, extruders, mixing devices such as (resonance) acoustic mixers or vibrational mixers, grinding devices such as manual grinders, without being limited thereto.
  • the mechanochemical treatment of the composition for conducting the deuteration of the organic compound may allow for reducing the amount of solvent and may render high temperatures to boost the solubility of the organic compound and high reaction temperatures, which may increase the formation of side reactions, unnecessary, but high conversation and H-D exchange rates and fast reaction rates may nevertheless be achieved.
  • the mechanochemical treatment in step b) comprises milling, in particular ball-milling, grinding, extruding, or mixing, in particular vibrational mixing or (resonance) acoustic mixing, or a combination of one or more thereof, of the composition provided in step a), and more preferably comprises milling or mixing, or a combination thereof, and particularly preferably comprises ball-mixing or (resonance) acoustic mixing, or a combination thereof.
  • the conditions at which those methods are carried out for the mechanochemical treating can be selected by a person skilled in the art without difficulties based on general technical knowledge, and may vary depending on the method applied.
  • the mechanochemical treatment in step b) is carried out using a mechanochemical device, which is configured to generate mechanical force and/or energy to be dissipated on the composition, the mechanochemical device being more preferably selected from milling devices such as ball mills, shaker mills, roller mills or planetary mills, extruders, mixing devices such as resonance acoustic mixers or vibrational mixers, and grinding devices, and a combination of one or more thereof.
  • the duration of the mechanochemical treatment in step b) is not particularly limited, as long as sufficient energy to promote chemical synthesis is created, and may be set as desired mainly depending on the method and/or device employed.
  • mechanochemical treatment in step b) it may be preferable according to an embodiment of the invention to carry out mechanochemical treatment in step b) for at least 30 minutes, more preferably for at least 1 h.
  • a duration of the mechanochemical treatment of 48 h or less may be preferably, more preferably 24 h or less. Therefore, in a particularly preferred embodiment the mechanochemical treatment in step b) is carried out for a period of 30 min to 48 h, even more preferably 1 h to 24 h, which is an optimum range in view of conversation rates and process efficiency.
  • the mechanochemical treatment in step b) comprises milling, in particular ball-milling, grinding, extruding, or mixing, in particular vibrational mixing or (resonance) acoustic mixing, or a combination of one or more thereof, for at least 30 minutes, preferably for at least 1 h, and preferably for 48 h or less, more preferably 24 h or less.
  • the method according to the invention advantageously does not necessarily require any heating, for example, to dissolve the organic material and/or to initiate and promote the H-D exchange, which in particular means that the method of the invention, and in particular the mechanochemical treatment, can be carried out at relatively low temperatures, in particular ambient (room) temperature (23 ⁇ 2 °C). Therefore, in a preferred embodiment the method for deuterating an organic compound according to the invention does not comprise any step of heating the composition, preferably not any heating step at all. However, moderate heating in order to further increase conversation and H-D exchange rates and the reaction time may nevertheless be applied.
  • the mechanochemical treatment in step b) is carried out under a controlled temperature in the range of 20°C to 120°C, more preferably 20°C to 80°C, even more preferably 20°C to 60°C.
  • a controlled temperature in the range of 20°C to 120°C, more preferably 20°C to 80°C, even more preferably 20°C to 60°C.
  • the mechanochemical treatment in step b) comprises milling, in particular ballmilling, grinding, extruding, or mixing, in particular vibrational mixing or (resonance) acoustic mixing, or a combination of one or more thereof, under a controlled temperature in the range of 20°C to 120°C, more preferably 20°C to 80°C, even more preferably 20°C to 60°C.
  • the mechanochemical treatment in step b) is carried out under a condition of pressure of 1 bar or more, more preferably in the range of 1 bar to 5 bar, in order to further increase conversation and H-D exchange rates while preventing side reactions and formation of unwanted side products.
  • the mechanochemical treatment in step b) comprises milling, in particular ball-milling, grinding, extruding, or mixing, in particular vibrational mixing or (resonance) acoustic mixing, or a combination of one or more thereof, under conditions of pressure of 1 bar or more, more preferably in the range of 1 bar to 5 bar.
  • Each of the above conditions for the mechanochemical treatment i.e. time, temperature and pressure, may be selected by a person skilled in the art as desired within the above-defined ranges, depending on, for example, the method and/or mechanochemical device employed for mechanochemically treating the composition, or the organic compound to be deuterated.
  • the mechanochemical device to be employed for the mechanochemical treatment in step b) may be equipped with temperature and/or pressure control capabilities.
  • the mechanochemical treatment of the composition in step b) is conducted in the presence of a catalyst.
  • the catalyst is preferably a metal catalyst, and more preferably comprises or is selected from platinum, palladium, rhodium, ruthenium, iridium, nickel, cobalt, oxides thereof, complexes thereof, or a combination of one or more thereof. Even more preferably, the metal catalyst comprises or is selected from platinum, palladium, oxides thereof, complexes thereof, or combinations thereof, and most preferably comprises or is selected from platinum, platinum oxides or platinum complexes.
  • the catalyst may part of the mechanochemical device itself which is employed to carry out the mechanochemical treating.
  • the catalyst may bear the catalyst either in the form of a coating (for example, milling balls or jars surface-coated with platinum) or by being made of the catalyst material (for example solid platinum milling balls or jars).
  • the catalyst is added to the composition as a separate component, preferably in solid form, and more preferably before the composition is subjected to the mechanochemical treatment.
  • the timing of the addition of the catalyst is not critical, as long as it is ensured that the mechanochemical treatment of the composition is conducted in the presence of the catalyst.
  • the catalyst is either employed in pure form, including oxides, complexes, blends thereof, for example, a powder or the like of the respective metal or metal oxide, or deposited on an inert solid support phase, that is, a solid phase that is stable under the conditions of the mechanochemical treatment and preferably is not soluble in the composition.
  • the solid phase may be any suitable material.
  • the inert solid support phase are, without being limited thereto, carbons such as activated carbon or carbon black, aluminium oxides, titanium oxides, silicon oxides, silicates, or polymers. Particularly preferably, the inert solid phase is selected form carbons. Depositing the catalyst on an inert solid support phase provides the possibility of tuning the properties of the catalyst and, therefore, is preferable according to the present invention.
  • the catalyst is selected from platinum on carbon (Pt/C), palladium on carbon (Pd/C), platinum(IV) oxide on carbon (PtC /C), palladium(ll) hydroxide on carbon (Pd(OH)2/C), palladium ⁇ I) chloride on carbon (PdCl2/C), or a combination thereof.
  • a preferred catalyst combination is a combination of Pt/C and Pd/C, preferably a mixture of 10:1 to 1 :2 of Pt/C to Pd/C, more preferably 7:1 to 1 :1 , especially 5:1 to 1 :1 , measured by weight.
  • the catalyst is selected from Pt/C and PtO 2 /C.
  • the content of the metal on the carbon of the catalyst according to this embodiment is preferably 1 to 15% by weight, for example 5% by weight, or 10 % by weight, based on the total weight of the catalyst.
  • the molar ratio of the catalyst (that is, the metal catalyst, omitting the solid support phase of the catalyst if present) to the compound to be deuterated is preferably from 1 :100 to 1 :1 , more preferably from 1 :70 to 1 :2, especially from 1 :30 to 1 :2. With a higher amount of catalyst, a higher reaction rate is observed, however, the costs increase concomitantly.
  • Catalysts in particular metal catalysts, are often stored in a water-moist state.
  • the catalyst is dried before being used and added to the composition in order to remove water (H2O) that may compromise deuteration. Drying of the catalyst may be carried out at a temperature of 20 °C to 200 °C and for a period of at least 12 hours, preferably at reduced pressure, in particular below 100 mbar, and further preferably under inert gas such as nitrogen or argon.
  • the catalyst in another embodiment of the invention, in particular if the catalyst has been stored in a deuterated liquid, in particular D2O, the catalyst is not dried before being used, but preferably the catalyst is employed and added to the composition in its wetted or moist state, because the deuterated liquid advantageously may act as a deuterium source.
  • the deuterated liquid wetting the catalyst may either be the only deuterium source provided in the composition in step a), and may be selected from any one of the deuterium sources mentioned above, or may supplement an additional deuterium source mentioned above that is also provided in the composition in step a).
  • the deuterated wetting liquid and the additional deuterium source preferably are of the same compound, and more preferably are both D2O.
  • a catalyst wetted with more than 5% by weight, more preferably more than 10% by weight, for example 50% by weight, of the deuterated liquid, in particular D2O is employed.
  • the composition in step a) further comprises at least one additive to improve deuteration/H-D exchange rates and/or prevent formation of side-products.
  • the at least one additive may be mixed with the other components to provide the composition in step a).
  • the at least one additive is selected from hydrogen (that is, H2, D2 and/or HD), alcohols, in particular isopropanol (iPrOH), metal salts and metal hydride salts.
  • the metal of the metal salt is preferably selected from metals of the alkali and earth-alkali series, boron, aluminium, copper, nickel and cobalt.
  • the salts of the metal salts may be, for example, the chlorides, bromides, iodides, nitrates, sulfates, carboxylic acid salts such as acetates, propionates or pivalates, without being limited thereto.
  • the at least one additive is selected from hydrogen (H2, D2 and/or HD), alcohols and metal hydride salts.
  • the additive is selected from hydrogen (H2, D2, and/or HD), borohydride salts, and iPrOH, of which iPrOH is most preferred.
  • the amount of the at least one additive may depend on the deuterium source and the organic compound.
  • 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.
  • the composition in step a) further comprises a solvent to improve solubility of the organic compound.
  • a suitable solvent is a solvent in which the organic compound to be deuterated is at least partly soluble.
  • the solvent may be mixed with the other components to provide the composition in step a).
  • the solvent is selected from aromatic solvents, ethers, alcohols, alkanes, cycloalkanes, amides, esters, and mixtures thereof. More preferably, the solvent is selected from alkanes and cycloalkanes, and mixtures thereof, and particularly preferably from cycloalkanes comprising at least one ring having 5 or more aliphatic carbon atoms.
  • suitable cycloalkanes are cyclohexane, methyl cyclohexane and fused cycloalkanes like decalin (cis- or trans-decalin and mixture thereof).
  • the solvent is employed in such an amount that the organic compound dissolves at least partially; measured in volume preferably in a ratio of deuterium source:solvent of 2:1 to 1 :50, preferably 1 :1 to 1 :30, especially 1 : 1 .5 to 1 :30, most particularly at 1 : 1 .5 to 1 : 10.
  • the optimum amount here depends on the solubility of the organic compound.
  • the composition in step a) further comprises a grinding aid in order to improve conversation rates/H-D exchange rates.
  • the grinding aid preferably is a solid and more preferably is selected from carbons such as activated carbon or carbon black, aluminium oxides, titanium oxides, silicon oxides, silicates, and combinations thereof.
  • the grinding aid according to this embodiment may be added to the composition before or during the mechanochemical treatment, and preferably is added in a weight not exceeding a sum of the weight of the organic compound, the deuterium source and the catalyst, preferably in a weight less than 50% of said sum, more preferably in a weight less than 30% of said sum, in order to further improve process efficiency.
  • the organic compound to be deuterated can be any organic compound wherein the term organic compound is well known to the skilled person. Preferred organic compounds to be deuterated are defined elsewhere within the present application.
  • the organic compound to be deuterated is preferably a compound that is suitable for being used in an electronic device, in particular an organic electroluminescent (EL) device such as an OLED, or is a precursor of such a compound. Depending on the substitution, the compounds can be used in different functions and layers.
  • the organic compound to be deuterated should be understood to also include organometallic compounds, in particular organometallic compounds containing a metal atom selected from copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, indium, palladium, platinum, silver, gold or europium, which have at least one heteroaromatic ring system.
  • organometallic compounds are metal chelate complexes, in particular with at least one heteroaromatic ring system as chelating ligand for the metal.
  • the electronic device is preferably an organic electroluminescent (EL) devices comprising cathode, anode and at least one emitting layer as the functional layer.
  • organic electroluminescent devices may comprise further functional layers selected from, for example, in each case one or more hole injection layers (HIL), hole transport layers (HTL), hole blocker layers (HBL), electron transport layers (ETL), electron injection layers (EIL), electron blocker layers, exciton blocker layers (EBL), interlayers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and/or organic or inorganic p/n junctions.
  • OLEDs organic light emitting diodes
  • OlCs organic integrated circuits
  • OFETs organic fieldeffect transistors
  • OLETs organic thin-film transistors
  • OLETs organic lightemitting transistors
  • OSCs organic solar cells
  • DSSCs dye-sensitized organic solar cells
  • OFQDs organic field quench devices
  • OLEDs organic light-emitting electrochemical cells
  • O-lasers organic laser diodes
  • O plasmon emitting devices of which organic light emitting diodes (OLEDs) are especially preferred.
  • the organic compound to be deuterated is an organic functional material which can be employed for the production of functional layers of electronic devices.
  • Organic functional materials are generally the organic materials which are introduced in one or more functional layer between the anode and the cathode of an electronic device.
  • the organic functional material as the organic compound to be deuterated is preferably selected from fluorescent emitters, phosphorescent emitters, host or matrix materials, electron injection materials, electron transport materials, electron blocking materials, wide band gap materials, hole injection materials, hole transport materials, hole blocking materials, exciton blocking materials, n- dopants and p-dopants.
  • the organic compound to be deuterated is an organic functional material which is selected from the group of matrix materials, phosphorescent emitters and hole transport materials, still more preferably a matrix materials and hole transport materials, and most preferably a matrix material.
  • the matrix material to be deuterated can preferably be a hole transporting matrix material, and electron transporting matrix material or a bipolar matrix material, more preferably the matrix material is a hole transporting or bipolar matrix material, wherein bipolar matrix materials contain both electron transporting (e.g. triazinyl- pyrimidyl- dibenzothiophenyl- or dibenzofuranyl groups) and hole transporting groups (e.g. carbazolyl- biscarbazolyl-, indenocarbazolyl- or indolocarazolyl-groups).
  • electron transporting e.g. triazinyl- pyrimidyl- dibenzothiophenyl- or dibenzofuranyl groups
  • hole transporting groups e.g. carbazolyl- biscarbazolyl-, indenocarbazolyl- or indolocarazolyl-groups.
  • the matrix material to be deuterated is a hole transporting matrix material.
  • Very preferred hole transporting matrix materials to be deuterated are carbazoles and biscarbazoles.
  • the term “phosphorescent emitter” 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.
  • fluorescent emitters which can be employed as the organic compound to be deuterated are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines.
  • An aromatic anthracenamine is taken to mean a compound in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.
  • An aromatic anthracenediamine is taken to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position.
  • Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously thereto, where the diarylamino groups are preferably bonded to the pyrene in the 1 -position or in the 1 ,6-position.
  • emitters are indenofluorenamines or indenofluorenediamines, for example in accordance with WO 2006/108497 or WO 2006/122630, benzoindenofluorenamines or benzoindenofluorene- diamines, for example in accordance with WO 2008/006449, and dibenzo- indenofluorenamines or dibenzoindenofluorenediamines, for example in accordance with WO 2007/140847, and the indenofluorene derivatives containing condensed aryl groups which are disclosed in WO 2010/012328.
  • Still further preferred emitters are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, fluorene dimers connected via heteroaryl groups like in WO 2016/150544 or phenoxazine derivatives as disclosed in WO 2017/028940 and WO 2017/028941.
  • Preference is likewise given to the pyrenarylamines disclosed in WO 2012/048780 and WO 2013/185871.
  • the electron-conducting compounds in particular ketones, phosphine oxides, sulfoxides, etc. (for example according to WO 2005/084081 and WO 2005/084082), the atropisomers (for example according to WO 2006/048268), the 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 with naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, the oligoarylenevinylenes, the ketones, the phosphine oxides and the sulfoxides.
  • Very particularly preferred matrix materials are selected from the classes of oligoarylene comprising anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds.
  • an oligoarylene is to be understood as a compound in which at least three aryl or arylene groups are linked together.
  • Suitable phosphorescent emitting compounds which can be employed as the organic compound to be deuterated are especially compounds which, when suitably excited, emit light, preferably in the visible region, and also contain at least one atom of atomic number greater than 20, preferably greater than 38, and less than 84, more preferably greater than 56 and less than 80.
  • phosphorescent emitting compounds compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium, platinum or copper.
  • all luminescent indium, platinum or copper complexes are considered to be phosphorescent emitting compounds.
  • Examples of the above-described emitting compounds, which may be premixed with matrix materials, can be found in applications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US 2005/0258742.
  • all phosphorescent complexes as used for phosphorescent OLEDs according to the prior art and as known to those skilled in the art in the field of organic electroluminescent devices are suitable for being employed as the organic compound to be deuterated.
  • matrix materials for phosphorescent emitters which can be employed as the organic compound to be deuterated 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
  • CBP 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, biscarbazoles, indolo _, carbazole derivatives, e.g. e.g. 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.
  • EP 1617710, EP 1617711 , EP 1731584, J P 2005/347160 bipolar matrix materials, e.g. according to WO 2007/137725, silanes, e.g. according to WO 2005/111172, azaborols or boronic esters, e.g. according to WO 2006/117052, triazine derivatives, e.g. 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.
  • diazasilol or tetraazasilol 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
  • dibenzofuran derivatives e.g.
  • WO 2015/169412 WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565.
  • another phosphorescent emitter which emits shorter wavelengths than the actual emitter, can be present in the mixture as a cohost 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.
  • Suitable charge transport materials such as those that 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 device, in addition to the deuterated compounds, are 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.
  • Hole transporting materials that are preferably used in a hole transport layer, an electron blocker layer or a hole injection layer of an organic electroluminescent (EL) device, and which can be employed as the organic compound to be deuterated, include, 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.
  • WO 01/049806 amine derivatives with fused aromatics
  • 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 2016/13
  • Particularly preferred hole transport materials are 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.
  • Electron transporting materials that are preferably used in an electron transport layer, a hole blocker layer or an electron injection layer of organic electroluminescent (EL), which can be employed as the organic compound to be deuterated, are all materials which are used as electron transport materials according to the state of the art.
  • EL organic electroluminescent
  • Liq 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 include derivatives of the above compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975, and WO 2010/072300.
  • wide band gap materials will be understood to mean materials as disclosed in US 7,294,849, which are characterized in having a band gap of at least 3.5 eV.
  • band gap denotes the distance between the energy level of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of a compound.
  • HOMO highest occupied molecular orbital
  • LUMO lowest unoccupied molecular orbital
  • n-Dopants used according to the invention are preferably those organic electron donor compounds capable of reducing one or more of the other compounds in the mixture.
  • p-Dopants used according to the invention are preferably those organic electron acceptor compounds capable of oxidizing one or more of the other compounds in the mixture.
  • Preferred examples of p-dopants which can be employed as the organic compound to be deuterated are F4-TCNQ, Fe-TNAP, NDP-2 (company Novaled), NDP-9 (company Novaled), quinones (e.g.
  • WO 2007/134873 A1 WO 2008/061517 A2, WO 2008/061518 A2, DE 102008051737 A1 , WO 2009/089821 A1 , US 2010/096600 A1 ), bisimidazoles (e.g. WO 2008/138580 A1 ), phthalocyanines (e.g.
  • WO 2008/058525 A2 bora-tetraazapentalenes (e.g. WO 2007/115540 A1 ) fullerenes (e.g. DE 102010046040 A1 ) and main group halogenides (e.g. WO 2008/128519 A2).
  • the organic compound to be deuterated is not an organometallic compound.
  • the organic compound to be deuterated is an aliphatic compound, a heteroaliphatic compound, an aromatic compound or a heteroaromatic compound. It is to be understood that the aliphatic compound, the heteroaliphatic compound, the aromatic compound and the heteroaromatic compound may be substituted by one or more substituents, like for example, halogens, alkyl groups, aryl groups, aromatic or heteroaromatic ring systems.
  • the aromatic compound is preferably a compound comprising an aromatic ring system, and more preferably is an aromatic ring system.
  • the heteroaromatic compound is preferably a compound comprising a heteroaromatic ring system, and more preferably is a heteroaromatic ring system.
  • An aromatic ring system in the sense of this invention contains 6 to 60 aromatic C atoms in the ring system, preferably 6 to 40 C atoms, more preferably 6 to 20 C atoms.
  • a heteroaromatic ring system in the sense of this invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom.
  • the heteroatoms are preferably selected from N, O and/or S.
  • An aromatic or heteroaromatic ring system in the sense of this invention is intended to be taken to mean a system which does not necessarily contain only aryl or heteroaryl groups, but instead in which, in addition, a plurality of aryl or heteroaryl groups may be connected by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, an sp 3 -hybridised C, Si, N or O atom, an sp 2 -hybridised C or N atom or an sp- hybridised C atom.
  • a non-aromatic unit preferably less than 10% of the atoms other than H
  • systems such as 9,9’-spirobifluorene, 9, 9’ -diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also intended to be taken to be aromatic ring systems in the sense of this invention, as are systems in which two or more aryl groups are connected, for example, by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group.
  • systems in which two or more aryl or heteroaryl groups are linked to one another via single bonds are also taken to be aromatic or heteroaromatic ring systems in the sense of this invention, such as, for example, systems such as biphenyl, terphenyl or diphenyltriazine.
  • aromatic or heteroaromatic ring system having 6 to 60, respectively 5 to 60, aromatic ring atoms, which may in each case also be substituted by radicals and which may be linked to the aromatic or heteroaromatic group via any desired positions, is taken to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spiro- truxen
  • An aryl group in the sense of this invention contains 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms; a heteroaryl group in the sense of this invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom.
  • the heteroatoms are preferably selected from N, O and S.
  • An aryl group or heteroaryl group here is taken to mean either a simple aromatic ring, i.e.
  • benzene or a simple heteroaromatic ring, for example pyridine, pyrimidine or thiophene, or a condensed (annellated) aromatic or heteroaromatic polycycle, for example naphthalene, phenanthrene, quinoline or carbazole.
  • a condensed (annellated) aromatic or heteroaromatic polycycle in the sense of the present application consists of two or more simple aromatic or heteroaromatic rings condensed with one another.
  • An aryl or heteroaryl group which may in each case be substituted by the above-mentioned substituents and which may be linked to the aromatic or heteroaromatic ring system at any desired positions, is taken to mean, in particular, groups derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6- quino
  • An aryloxy group in accordance with the definition of the present invention is taken to mean an aryl group, as defined above, which is bonded via an oxygen atom.
  • An analogous definition applies to heteroaryloxy groups.
  • An aliphatic compound in the sense of this invention is a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms
  • a heteroaliphatic compound in the sense of this invention is a straight-chain alkyl group having 2 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 3 to 40 C atoms, at least one of which is a heteroatom.
  • the heteroatoms are preferably selected from N, O and S.
  • the (hetero)aliphatic compounds are taken to mean the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexen
  • An alkoxy or thioalkyl group having 1 to 40 C atoms is preferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-penty
  • the above-mentioned formulation is also intended to be taken to mean that, in the case where one of the two radicals represents hydrogen, the second radical is bonded at the position to which the hydrogen atom was bonded, with formation of a ring. This is illustrated by the following scheme:
  • Adjacent radicals in the sense of the present invention are radicals which are bonded to atoms which are linked directly to one another or which are bonded to the same atom.
  • the organic compound to be deuterated is an aromatic ring system having 6 to 60 aromatic ring atoms, which may be substituted by one or more radicals R R .
  • Preferred aromatic ring systems are selected from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, pery- lene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans- indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene,
  • Ar is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R ;
  • R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH 2 groups may be replaced by SO, SO 2 , O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.
  • the organic compound to be deuterated is a heteroaromatic ring system having 5— 60 aromatic ring atoms, which may be substituted by one or more radicals R R , where R R is as defined above.
  • Preferred heteroaromatic ring systems are selected from furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quino- line, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthi
  • heteroaromatic ring systems are selected from dibenzofuran, dibenzothiophene, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzoquinoline, phenothiazine, phenoxazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, phenoxazine, phenothiazine and combinations of these groups, which may be substituted by one or more radicals R R , where R R is as defined above.
  • R R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(R') 2 , N(Ar) 2 , B(OR') 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, wherein each of the aforementioned straight-chain or branched groups may be substituted by one or more radicals R , and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be substituted by one or more radicals R , or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more
  • R R stands on each occurrence, identically or differently, for H, D, F, CN, N(R') 2 , N(Ar) 2 , a straight-chain alkyl group having 1 to 40 C atoms or branched or a cyclic alkyl group having 3 to 40 C atoms, wherein each of the aforementioned straight-chain or branched groups may be substituted by one or more radicals R , and wherein one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be substituted by one or more radicals R , where two radicals R R may form an aliphatic or aromatic ring system together, which may be substituted by one or more radicals R .
  • R R stands on each occurrence, identically or differently, for H, D, a straight-chain alkyl group having 1 to 40 C atoms or branched or a cyclic alkyl group having 3 to 40 C atoms, wherein each of the aforementioned straight-chain or branched groups may be substituted by one or more radicals R , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be substituted by one or more radicals R , where two radicals R R may form an aliphatic or aromatic ring system together, which may be substituted by one or more radicals R .
  • R R stands on each occurrence, identically or differently, for H, D, a straight-chain alkyl group having 1 to 40 C atoms or branched or a cyclic alkyl group having 3 to 40 C atoms, wherein each of the aforementioned straight-chain or branched groups may be substituted by one or more radicals R , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be substituted by one or more radicals R ;
  • R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, wherein in each of the aforementioned straight-chain or branched groups one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S and wherein one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.
  • R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, wherein in each of the aforementioned straight-chain or branched groups one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S and wherein one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.
  • R stands on each occurrence, identically or differently, for H, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or branched or cyclic alkyl group having 3 to 20 C atoms, wherein in each of the aforementioned straight-chain or branched groups one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.
  • the invention is also directed to deuterated compounds which are obtained by a deuteration method as described above.
  • organic functional materials mentioned above which are all suitable as materials for organic electroluminescent (EL) devices such as OLEDs, can be deuterated by a method according to the present invention.
  • the deuterated compounds according to the invention are suitable for use in an electronic device, in particular in an organic electroluminescent (EL) device such as an OLED. Depending on the substitution, the compounds can be used in different functions and layers.
  • EL organic electroluminescent
  • the invention is further directed to an electronic device comprising a deuterated compound obtained by a deuteration method as described above.
  • the electronic device is preferably an organic electroluminescent device comprising cathode, 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.
  • 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.
  • organic electroluminescent devices may comprise further functional layers selected from, for example, in each case one or more hole injection layers (HIL), hole transport layers (HTL), hole blocker layers (HBL), electron transport layers (ETL), electron injection layers (EIL), electron blocker layers, exciton blocker layers (EBL), interlayers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and/or organic or inorganic p/n junctions.
  • HIL hole injection layers
  • HBL hole blocker layers
  • ETL electron transport layers
  • EIL electron injection layers
  • EBL exciton blocker layers
  • interlayers charge generation layers
  • the organic electroluminescent device may contain one emitting layer, or it may contain several emitting layers. If several emitting layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, so that white emission results overall, i.e. different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. In particular, systems with three emitting layers are preferred, with the three layers showing blue, green and orange or red emission (the principle 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.
  • a hole transport layer according to the present application is a layer having a hole-transporting function between the anode and emitting layer.
  • Hole injection layers and electron blocker layers are understood in the context of the present application to be specific embodiments of hole transport layers.
  • a hole injection layer in the case of a plurality of hole transport layers between the anode and emitting layer, is a hole transport layer which directly adjoins the anode or is separated therefrom only by a single coating of the anode.
  • An electron blocker layer in the case of a plurality of hole transport layers between the anode and emitting layer, is that hole transport layer which directly adjoins the emitting layer on the anode side.
  • An electron transport layer according to the present application is a layer having an electron-transporting function between the cathode and the emitting layer.
  • the organic electroluminescent device contains one hole transport layer comprising at least one deuterated hole-transport material obtained by a method according to the present invention.
  • the organic electroluminescent device contains an organic layer, preferably one emitting layer, comprising at least one host or matrix material selected from deuterated aromatic or heteroaromatic compounds obtained by a method according to the present invention.
  • the organic electroluminescent device contains one emitting layer comprising at least one deuterated phosphorescent emitter obtained by a method according to the present invention.
  • the organic electroluminescent device contains one emitting layer comprising at least one deuterated fluorescent emitter obtained by a method according to the present invention.
  • 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 transport layer and/or in an exciton blocking layer.
  • Preferred cathodes of the organic electroluminescent device are metals with low work function, metal alloys or multilayer structures 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.). Additionally suitable are alloys of an alkali or alkaline earth metal and silver, e.g. an alloy of magnesium and silver. In multilayer structures, other metals with a relatively high work function can be used in addition to the metals mentioned, e.g. Ag or Al, with combinations of the metals such as Ca/Ag, Mg/Ag or Ba/Ag usually being used.
  • metal alloys or multilayer structures 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.).
  • a thin interlayer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor examples include alkali or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose.
  • the thickness of this layer is preferably between 0.5 and 5 nm.
  • Preferred anodes of the organic electroluminescent device 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
  • metal/metal oxide electrodes e.g. AI/Ni/NiOx, Al/PtOx
  • at least one of the electrodes must be transparent or partially transparent to allow irradiation of the organic material (organic solar cell) or emission of light (OLED, O-laser).
  • Preferred anode materials are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Further preferred are conductively doped organic materials, in particular conductively doped polymers.
  • 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.
  • the electronic device is an organic electroluminescent (EL) device selected from organic light emitting diodes (OLEDs), organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic plasmon emitting devices, but more preferably from organic light emitting diodes (OLEDs).
  • OLEDs organic light emitting diodes
  • OlCs organic integrated circuits
  • OFETs organic field-effect transistors
  • OFTs organic thin-film transistors
  • OLETs organic light-emitting transistors
  • OSCs organic solar cells
  • DSSCs dye-sensitized organic solar
  • the device is structured, contacted and finally sealed to exclude harmful influences from water and air.
  • the organic electroluminescent device comprises one or more layers, which are deposited by a sublimation process.
  • the materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10’ 5 mbar, preferably less than 10’ 6 mbar.
  • the initial pressure it is also possible for the initial pressure to be even lower, for example less than 10’ 7 mbar.
  • An organic electroluminescent device is also preferred, characterized in that one or more layers are coated using the OVPD (organic vapor phase deposition) process or with the aid of carrier gas sublimation.
  • the materials are applied at a pressure between 10’ 5 mbar and 1 bar.
  • OVJP Organic Vapour Jet Printing
  • an organic electroluminescent device comprising one or more layers, which 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 (inkjet printing) or nozzle printing. Soluble compounds are required for this, which can be obtained by suitable substitution, for example.
  • Hybrid processes are also possible, in which, for example, one or more layers of solution are applied and one or more further layers are vapor-deposited.
  • Example 1 Deuteration of biphenyl utilizing a ball-mill
  • Mechanochemical treatment is conducted for 60 min at room temperature applying a frequency of 35 Hz. Each sample mixture is then extracted from the cup with 10 mL THF, filtered, and evaporated to dryness, leaving 229 mg of biphenyl with a deuteration degree (“%D”) as listed in Table 1 .
  • the deuteration degree in Example 1 and Examples 2 and 3 below is determined by GC-MS. The %D-value is elucidated by simulation of the isotope pattern of the M + -signal with an approximate error of ⁇ 5%.
  • Example 2 Deuteration of biphenyl utilizing a resonance acoustic mixer
  • 9-Phenylcarbazole 1000 mg, 4.11 mmol
  • catalyst 10% Pt/C 1000 mg dry basis
  • 1000 pL D2O 1000 pL
  • 300 pL iPrOH 300 pL
  • Mechanochemical treatment is conducted for 60 min at room temperature applying a frequency of 35 Hz.
  • the mixture is then extracted from the cup with 10 mL THF, filtered, and evaporated to dryness, leaving 915 mg of 9-Ph-carbazole with a deuteration degree of 30% adjudicated by GC-MS.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de deutération de composés organiques au moyen d'un traitement mécanochimique.
PCT/EP2024/087052 2023-12-21 2024-12-18 Procédé mécanochimique de deutération de composés organiques Pending WO2025132547A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23219429 2023-12-21
EP23219429.0 2023-12-21

Publications (1)

Publication Number Publication Date
WO2025132547A1 true WO2025132547A1 (fr) 2025-06-26

Family

ID=89321495

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/087052 Pending WO2025132547A1 (fr) 2023-12-21 2024-12-18 Procédé mécanochimique de deutération de composés organiques

Country Status (1)

Country Link
WO (1) WO2025132547A1 (fr)

Citations (157)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4539507A (en) 1983-03-25 1985-09-03 Eastman Kodak Company Organic electroluminescent devices having improved power conversion efficiencies
US5061569A (en) 1990-07-26 1991-10-29 Eastman Kodak Company Electroluminescent device with organic electroluminescent medium
US5151629A (en) 1991-08-01 1992-09-29 Eastman Kodak Company Blue emitting internal junction organic electroluminescent device (I)
WO1995009147A1 (fr) 1993-09-29 1995-04-06 Idemitsu Kosan Co., Ltd. Element electroluminescent organique et derive d'arylenediamine
EP0652273A1 (fr) 1993-11-09 1995-05-10 Shinko Electric Industries Co. Ltd. Matériau organique pour dispositif électroluminescent et dispositif électroluminescent
EP0676461A2 (fr) 1994-04-07 1995-10-11 Hoechst Aktiengesellschaft Composés spiro et leur application comme matières électroluminescentes
WO1998027136A1 (fr) 1996-12-16 1998-06-25 Aventis Research & Technologies Gmbh & Co Kg POLY(p-ARYLENEVINYLENES) A SUBSTITUTION ARYLE, LEUR PROCEDE DE PREPARATION ET LEUR UTILISATION DANS DES COMPOSANTS ELECTROLUMINESCENTS
JP2000053957A (ja) 1998-06-23 2000-02-22 Koto Gijutsu Kenkyuin Kenkyu Kumiai 新規な有機金属発光物質およびそれを含む有機電気発光素子
WO2000070655A2 (fr) 1999-05-13 2000-11-23 The Trustees Of Princeton University Dispositifs electroluminescents organiques a tres haute performance utilisant l'electrophosphorescence
WO2001041512A1 (fr) 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes de forme l2mx en tant que dopants phosphorescents pour del organiques
WO2001049806A1 (fr) 1999-12-31 2001-07-12 Lg Chemical Co., Ltd Dispositif electronique comprenant un compose organique presentant les caracteristiques de semi-conduction du dopage p
WO2002002714A2 (fr) 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Composes d'iridium electroluminescents contenant des phenylpyridines fluores, des phenylpyrimidines et des phenylquinolines, et dispositifs fabriques avec ces composes
WO2002015645A1 (fr) 2000-08-11 2002-02-21 The Trustees Of Princeton University Composes organometalliques et electrophosphorescence organique presentant un deplacement d'emission
EP1191614A2 (fr) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Dispositif luminescent et composé complexe d'un métal utilisé pour ce dispositif
EP1191612A2 (fr) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Dispositif luminescent, dispositif d'affichage et composé complexe d'un métal
EP1191613A2 (fr) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Dispositif luminescent, dispositif d'affichage et composé complexe d'un métal
EP1205527A1 (fr) 2000-03-27 2002-05-15 Idemitsu Kosan Co., Ltd. Dispositif a electroluminescence organique
WO2003060956A2 (fr) 2002-01-18 2003-07-24 Lg Chem, Ltd. Nouveau materiau permettant de transporter des electrons et affichage organique electroluminescent utilisant ledit materiau
WO2004013080A1 (fr) 2002-08-01 2004-02-12 Covion Organic Semiconductors Gmbh Derives de spirobifluorene, leur preparation et leurs utilisations
WO2004028217A1 (fr) 2002-09-20 2004-04-01 Idemitsu Kosan Co., Ltd. Element organique electroluminescent
WO2004058911A2 (fr) 2002-12-23 2004-07-15 Covion Organic Semiconductors Gmbh Element electroluminescent organique
WO2004080975A1 (fr) 2003-03-13 2004-09-23 Idemitsu Kosan Co., Ltd. Derive heterocyclique contenant de l'azote et element electroluminescent organique utilisant ce derive
WO2004081017A1 (fr) 2003-03-11 2004-09-23 Covion Organic Semiconductors Gmbh Complexes metalliques
JP2004288381A (ja) 2003-03-19 2004-10-14 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子
WO2004093207A2 (fr) 2003-04-15 2004-10-28 Covion Organic Semiconductors Gmbh Melanges de semi-conducteurs organiques aptes a l'emission et de matieres matricielles, leur utilisation et composants electroniques contenant ces melanges
WO2005011013A1 (fr) 2003-07-21 2005-02-03 Covion Organic Semiconductors Gmbh Element electroluminescent organique
WO2005019373A2 (fr) 2003-08-19 2005-03-03 Basf Aktiengesellschaft Complexes de metal de transition comportant des ligands de carbene faisant office d'emetteurs pour diodes electroluminescentes organiques (delo)
US20050069729A1 (en) 2003-09-30 2005-03-31 Konica Minolta Holdings, Inc. Organic electroluminescent element, illuminator, display and compound
WO2005033244A1 (fr) 2003-09-29 2005-04-14 Covion Organic Semiconductors Gmbh Complexes metalliques
EP1553154A1 (fr) 2002-08-23 2005-07-13 Idemitsu Kosan Co., Ltd. Dispositif organique electroluminescent et derive d'anthracene
WO2005084081A1 (fr) 2004-02-20 2005-09-09 Merck Patent Gmbh Dispositifs electroniques organiques
WO2005086251A2 (fr) 2004-03-03 2005-09-15 Novaled Gmbh Utilisation d'un complexe metallique comme dopant n d'un materiau matrice semi-conducteur organique et composant electronique, ainsi que dopant et ligand, et son procede de production
WO2005111172A2 (fr) 2004-05-11 2005-11-24 Merck Patent Gmbh Nouveaux melanges de materiaux pour applications electroluminescentes
US20050258742A1 (en) 2004-05-18 2005-11-24 Yui-Yi Tsai Carbene containing metal complexes as OLEDs
JP2005347160A (ja) 2004-06-04 2005-12-15 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、照明装置及び表示装置
EP1617711A1 (fr) 2003-04-23 2006-01-18 Konica Minolta Holdings, Inc. Dispositif organique electroluminescent et affichage
WO2006005627A1 (fr) 2004-07-15 2006-01-19 Merck Patent Gmbh Derives oligomeres de spirobifluorene, leur elaboration et leur utilisation
WO2006048268A1 (fr) 2004-11-06 2006-05-11 Merck Patent Gmbh Dispositif electroluminescent organique
EP1661888A1 (fr) 2004-11-29 2006-05-31 Samsung SDI Co., Ltd. Composé contenant un phenylcarbazole et dispositif organiques électroluminiscent l'utilisant
WO2006097208A1 (fr) 2005-03-16 2006-09-21 Merck Patent Gmbh Nouveaux materiaux pour des dispositifs electroluminescents organiques
WO2006100896A1 (fr) 2005-03-18 2006-09-28 Idemitsu Kosan Co., Ltd. Derive d’amine aromatique et dispositif electroluminescent organique l’utilisant
WO2006108497A1 (fr) 2005-04-14 2006-10-19 Merck Patent Gmbh Composes pour dispositifs electroniques organiques
WO2006117052A1 (fr) 2005-05-03 2006-11-09 Merck Patent Gmbh Dispositif electroluminescent organique, et derives d'acide boronique et d'acide borinique utilises pour produire ce dispositif electroluminescent organique
WO2006122630A1 (fr) 2005-05-20 2006-11-23 Merck Patent Gmbh Composes pour dispositifs electroniques organiques
EP1731584A1 (fr) 2004-03-31 2006-12-13 Konica Minolta Holdings, Inc. Matériau de dispositif électroluminescent organique, dispositif électroluminescent organique, écran et dispositif d'éclairage
WO2006131192A1 (fr) 2005-06-09 2006-12-14 Merck Patent Gmbh Nouveaux materiaux destines a des dispositifs electroluminescents organiques
EP1749809A1 (fr) 2004-05-27 2007-02-07 Idemitsu Kosan Co., Ltd. Derive de pyrene asymetrique et dispositif electroluminescent organique utilisant celui-ci
WO2007063754A1 (fr) 2005-12-01 2007-06-07 Nippon Steel Chemical Co., Ltd. Compose pour element electroluminescent organique et element electroluminescent organique
WO2007065678A1 (fr) 2005-12-08 2007-06-14 Merck Patent Gmbh Nouvelles matieres pour dispositifs electroluminescents organiques
WO2007065550A1 (fr) 2005-12-08 2007-06-14 Merck Patent Gmbh Nouvelles matières pour dispositifs électroluminescents organiques
EP1837926A1 (fr) 2006-03-21 2007-09-26 Novaled AG Radicaux ou diradicaux hétérocycliques, leur dimères, oligomères, polymères, composés spiro et polycycliques. Leur usage dans des semi-conducteurs organiques et dispositifs électroniques.
WO2007107306A1 (fr) 2006-03-22 2007-09-27 Novaled Ag Utilisation de radicaux heterocycliques pour le dopage de semi-conducteurs organiques
WO2007110129A1 (fr) 2006-03-24 2007-10-04 Merck Patent Gmbh Nouveaux materiaux pour disposifs electroluminescents organiques
WO2007115540A1 (fr) 2006-03-30 2007-10-18 Novaled Ag Utilisation de bora-tétraazapentalènes
US7294849B2 (en) 2001-03-14 2007-11-13 The Trustees Of Princeton University Materials and devices for blue phosphorescence based organic light emitting diodes
WO2007137725A1 (fr) 2006-05-31 2007-12-06 Merck Patent Gmbh Nouveaux matériaux pour dispositifs électroluminescents organiques
WO2007140847A1 (fr) 2006-06-02 2007-12-13 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2008006449A1 (fr) 2006-07-11 2008-01-17 Merck Patent Gmbh Nouveaux matériaux destinés à des dispositifs électroluminescents organiques
EP1905754A1 (fr) 2005-07-06 2008-04-02 Idemitsu Kosan Co., Ltd. Dérivé du pyrène et dispositif électroluminescent organique l utilisant
WO2008056746A1 (fr) 2006-11-09 2008-05-15 Nippon Steel Chemical Co., Ltd. Composé pour un dispositif électroluminescent organique et dispositif électroluminescent organique
WO2008058525A2 (fr) 2006-11-13 2008-05-22 Novaled Ag Utilisation d'une liaison de coordination pour doper des semiconducteurs organiques
WO2008086851A1 (fr) 2007-01-18 2008-07-24 Merck Patent Gmbh Dérivés de carbazole pour des dispositifs électroluminescents organiques
EP1988587A1 (fr) 2007-04-30 2008-11-05 Novaled AG Composés de matière d'oxyde de carbone, de pseudo oxyde de carbone et de radialène ainsi que leur utilisation
WO2008138580A1 (fr) 2007-05-10 2008-11-20 Novaled Ag Dérivés imidazole et leur utilisation comme dopant pour un matériau matrice semi-conducteur organique
WO2008145239A2 (fr) 2007-05-29 2008-12-04 Merck Patent Gmbh Nouveaux matériaux destinés à des dispositifs électroluminescents organiques
WO2009000237A1 (fr) 2007-06-22 2008-12-31 Novaled Ag Utilisation du précurseur d'un dopant n pour le dopage d'un matériau semi-conducteur, précurseur et composant électronique ou optoélectronique
DE102008051737A1 (de) 2007-10-24 2009-05-07 Novaled Ag Quadratisch planare Übergangsmetallkomplexe und diese verwendende organische halbleitende Materialien sowie elektronische oder optoelektronische Bauelemente
WO2009062578A1 (fr) 2007-11-12 2009-05-22 Merck Patent Gmbh Dispositifs organiques électroluminescents contenant des complexes azométhine/métal
WO2009089821A1 (fr) 2008-01-15 2009-07-23 Novaled Ag Complexes de dithiolène-métaux de transition, et composants électroniques ou optoélectroniques
WO2009100925A1 (fr) 2008-02-13 2009-08-20 Merck Patent Gmbh Nouveaux matériaux pour des dispositifs organiques électroluminescents
WO2010006680A1 (fr) 2008-07-18 2010-01-21 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2010012328A1 (fr) 2008-07-29 2010-02-04 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2010015306A1 (fr) 2008-08-08 2010-02-11 Merck Patent Gmbh, Dispositif électroluminescent organique
US20100096600A1 (en) 2008-10-16 2010-04-22 Novaled Ag Square Planar Transition Metal Complexes and Organic Semiconductive Materials Using Them as Well as Electronic or Optoelectric Components
EP2180029A1 (fr) 2008-10-23 2010-04-28 Novaled AG Composés de Radialène et leur utilisation
US20100102709A1 (en) 2008-04-29 2010-04-29 Olaf Zeika Radialene compounds and their use
WO2010054729A2 (fr) 2008-11-11 2010-05-20 Merck Patent Gmbh Matières pour des dispositifs électroluminescents organiques
WO2010054730A1 (fr) 2008-11-11 2010-05-20 Merck Patent Gmbh Dispositifs électroluminescents organiques
WO2010072300A1 (fr) 2008-12-22 2010-07-01 Merck Patent Gmbh Dispositif électroluminescent organique contenant des dérivés triazine
WO2010099534A2 (fr) 2009-02-27 2010-09-02 E. I. Du Pont De Nemours And Company Composés deutérés pour applications électroniques
WO2010097433A1 (fr) 2009-02-26 2010-09-02 Basf Se Composés quinoniques convenant comme impureté de dopage en électronique organique
WO2010108579A1 (fr) 2009-03-23 2010-09-30 Merck Patent Gmbh Dispositif électroluminescent organique
WO2010136109A1 (fr) 2009-05-29 2010-12-02 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2011000455A1 (fr) 2009-06-30 2011-01-06 Merck Patent Gmbh Matériaux destinés à des dispositifs d'électroluminescence organique
WO2011042107A2 (fr) 2009-10-08 2011-04-14 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2011050888A1 (fr) 2009-10-29 2011-05-05 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2011053334A1 (fr) 2009-10-26 2011-05-05 E. I. Du Pont De Nemours And Company Procédé pour la préparation de composés aromatiques deutérés
WO2011054442A2 (fr) 2009-11-06 2011-05-12 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2011057706A2 (fr) 2009-11-14 2011-05-19 Merck Patent Gmbh Matières pour dispositif électroniques
WO2011060859A1 (fr) 2009-11-17 2011-05-26 Merck Patent Gmbh Matériaux pour des dispositifs électroluminescents organiques
WO2011060867A1 (fr) 2009-11-18 2011-05-26 Merck Patent Gmbh Hétérocycles condensés contenant de l'azote pour des oled
WO2011060877A2 (fr) 2009-11-17 2011-05-26 Merck Patent Gmbh Matériaux pour des dispositifs électroluminescents organiques
WO2011088877A1 (fr) 2010-01-25 2011-07-28 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2011116865A1 (fr) 2010-03-25 2011-09-29 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
WO2011131185A1 (fr) 2010-04-21 2011-10-27 Novaled Ag Mélange pour la fabrication d'une couche semi-conductrice dopée
WO2011134458A1 (fr) 2010-04-27 2011-11-03 Novaled Ag Matériau semi-conducteur organique et composant électronique
WO2011137951A1 (fr) 2010-05-04 2011-11-10 Merck Patent Gmbh Dispositifs électroluminescents organiques
WO2012031735A1 (fr) 2010-09-10 2012-03-15 Novaled Ag Composés pour dispositifs photovoltaïques organiques
WO2012034627A1 (fr) 2010-09-15 2012-03-22 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
DE102010046040A1 (de) 2010-09-22 2012-03-22 Novaled Ag Verfahren zur Herstellung von Fulleren-Derivaten
WO2012048780A1 (fr) 2010-10-15 2012-04-19 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2012048781A1 (fr) 2010-10-15 2012-04-19 Merck Patent Gmbh Matériaux à base de triphényles pour dispositifs électroluminescents organiques
EP2452946A1 (fr) 2010-11-16 2012-05-16 Novaled AG Oxides de pyridylphosphine pour dispositif électronique organique et dispositif électronique organique
EP2463927A1 (fr) 2010-12-08 2012-06-13 Novaled AG Matériau pour dispositif électronique organique et dispositif électronique organique
US20120187826A1 (en) 2009-12-21 2012-07-26 Idemitsu Kosan Co., Ltd. Organic electroluminescent element using pyrene derivative
US20120223296A1 (en) 2011-03-01 2012-09-06 Sensient Imaging Technologies Gmbh Organic Semiconducting Materials and Organic Component
WO2012143080A2 (fr) 2011-04-18 2012-10-26 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2012150001A1 (fr) 2011-05-05 2012-11-08 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2012168358A1 (fr) 2011-06-09 2012-12-13 Novaled Ag Composé destiné à un dispositif électronique organique
WO2012175219A1 (fr) 2011-06-22 2012-12-27 Novaled Ag Dispositif électronique et composé
WO2012175535A1 (fr) 2011-06-22 2012-12-27 Novaled Ag Composant electronique organique
WO2013041176A1 (fr) 2011-09-21 2013-03-28 Merck Patent Gmbh Dérivés de carbazole pour des dispositifs électroluminescents organiques
WO2013056776A1 (fr) 2011-10-20 2013-04-25 Merck Patent Gmbh Matériaux destinés à des dispositifs électroluminescents organiques
WO2013083216A1 (fr) 2011-11-17 2013-06-13 Merck Patent Gmbh Dérivés de spiro-dihydroacridine et leur application comme matériaux pour dispositifs électroluminescents organiques
WO2013120577A1 (fr) 2012-02-14 2013-08-22 Merck Patent Gmbh Composés de spirobifluorène pour dispositifs organiques électroluminescents
WO2013185871A1 (fr) 2012-06-12 2013-12-19 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2014015935A2 (fr) 2012-07-23 2014-01-30 Merck Patent Gmbh Composés et dispositifs electroniques organiques
WO2014015937A1 (fr) 2012-07-23 2014-01-30 Merck Patent Gmbh Composés et dispositifs electroluminescents organiques
WO2014015938A1 (fr) 2012-07-23 2014-01-30 Merck Patent Gmbh Dérivés de 2-diarylaminofluorène et composés électroniques organiques les contenant
WO2014037077A1 (fr) 2012-09-04 2014-03-13 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2014072017A1 (fr) 2012-11-12 2014-05-15 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2014106522A1 (fr) 2013-01-03 2014-07-10 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2014111269A2 (fr) 2013-10-14 2014-07-24 Merck Patent Gmbh Matériaux pour dispositifs électroniques
EP2816008A1 (fr) * 2012-02-17 2014-12-24 Shiono Chemical Co., Ltd. Procédé de fabrication d'hydrogène ou de deutérium, procédé de fabrication d'un composé organique hydrogéné ou deutéré, procédé pour hydrogéner ou deutérer un composé organique, procédé pour déshalogéner un composé organique ayant un halogène et bille destinée à être utilisée dans une réaction mécano-chimique
WO2015022051A1 (fr) 2013-08-15 2015-02-19 Merck Patent Gmbh Matériaux destinés à des dispositifs électroniques
WO2015082056A1 (fr) 2013-12-06 2015-06-11 Merck Patent Gmbh Composés et dispositifs électroniques organiques
WO2015086108A1 (fr) 2013-12-12 2015-06-18 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2015102118A1 (fr) 2014-02-18 2015-07-09 学校法人関西学院 Composé aromatique polycyclique
WO2015131976A1 (fr) 2014-03-07 2015-09-11 Merck Patent Gmbh Matières pour dispositifs électroniques
WO2015158409A1 (fr) 2014-04-16 2015-10-22 Merck Patent Gmbh Matières pour dispositifs électroniques
WO2015158411A1 (fr) 2014-04-14 2015-10-22 Merck Patent Gmbh Matières pour dispositifs électroniques
WO2015169412A1 (fr) 2014-05-05 2015-11-12 Merck Patent Gmbh Matières pour des dispositifs organiques électroluminescents
WO2016015810A1 (fr) 2014-07-29 2016-02-04 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2016023608A1 (fr) 2014-08-13 2016-02-18 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2016073425A2 (fr) 2014-11-06 2016-05-12 E. I. Du Pont De Nemours And Company Procédé de préparation de composés aromatiques deutérés
WO2016078738A1 (fr) 2014-11-18 2016-05-26 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
WO2016087017A1 (fr) 2014-12-01 2016-06-09 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
WO2016102048A1 (fr) 2014-12-22 2016-06-30 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2016131521A1 (fr) 2015-02-16 2016-08-25 Merck Patent Gmbh Matériaux à base de dérivés de spirobifluorène pour dispositifs électroniques
WO2016150544A1 (fr) 2015-03-25 2016-09-29 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2017025165A1 (fr) 2015-08-12 2017-02-16 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2017028940A1 (fr) 2015-08-14 2017-02-23 Merck Patent Gmbh Dérivés de phénoxazine pour dispositifs électroluminescents organiques
WO2017028941A1 (fr) 2015-08-14 2017-02-23 Merck Patent Gmbh Dérivés de phénoxazine pour dispositifs électroluminescents organiques
WO2017036574A1 (fr) 2015-08-28 2017-03-09 Merck Patent Gmbh Dérivés de 6,9,15,18-tétrahydro-s-indacéno[1,2-b:5,6-b']difluorène et leur utilisation dans des dispositifs électroniques
WO2017036573A1 (fr) 2015-08-28 2017-03-09 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2017148565A1 (fr) 2016-03-03 2017-09-08 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
CN107266484A (zh) 2017-07-14 2017-10-20 瑞声科技（南京）有限公司 有机电致发光材料及其发光器件
WO2017195669A1 (fr) 2016-05-13 2017-11-16 コニカミノルタ株式会社 Matériau d'élément électroluminescent organique, élément électroluminescent organique, appareil d'affichage et appareil d'éclairage
WO2018007421A1 (fr) 2016-07-08 2018-01-11 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
US20180069182A1 (en) 2016-09-07 2018-03-08 Kwansei Gakuin Educational Foundation Polycyclic aromatic compound
WO2018095940A1 (fr) 2016-11-25 2018-05-31 Merck Patent Gmbh Dérivés d'indéno [1,2-b] fluorène à fusion bisbenzofurane et composés apparentés en tant que matériaux pour des dispositifs électroluminescents organiques (oled)
WO2018095888A1 (fr) 2016-11-25 2018-05-31 Merck Patent Gmbh Dérivés de 2,8-diaminoindéno [1,2-b] fluorène à fusion bisbenzofurane et composés apparentés en tant que matériaux pour des dispositifs électroluminescents organiques (oled)
CN108409769A (zh) 2016-07-29 2018-08-17 江苏三月光电科技有限公司 一种发光效率高的含硼有机电致发光化合物及其应用
KR20180130970A (ko) 2017-05-31 2018-12-10 삼성에스디에스 주식회사 도어락 모티스
WO2019076789A1 (fr) 2017-10-17 2019-04-25 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2019170572A1 (fr) 2018-03-06 2019-09-12 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
EP3689817A1 (fr) * 2010-08-18 2020-08-05 Shiono Chemical Co., Ltd. Procédé de production d'hydrogène ou d'hydrogènes lourds et hydrogénation (protiation, deuteration ou tritiation) de composés organiques l'utilisant

Patent Citations (161)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4539507A (en) 1983-03-25 1985-09-03 Eastman Kodak Company Organic electroluminescent devices having improved power conversion efficiencies
US5061569A (en) 1990-07-26 1991-10-29 Eastman Kodak Company Electroluminescent device with organic electroluminescent medium
US5151629A (en) 1991-08-01 1992-09-29 Eastman Kodak Company Blue emitting internal junction organic electroluminescent device (I)
WO1995009147A1 (fr) 1993-09-29 1995-04-06 Idemitsu Kosan Co., Ltd. Element electroluminescent organique et derive d'arylenediamine
EP0652273A1 (fr) 1993-11-09 1995-05-10 Shinko Electric Industries Co. Ltd. Matériau organique pour dispositif électroluminescent et dispositif électroluminescent
EP0676461A2 (fr) 1994-04-07 1995-10-11 Hoechst Aktiengesellschaft Composés spiro et leur application comme matières électroluminescentes
WO1998027136A1 (fr) 1996-12-16 1998-06-25 Aventis Research & Technologies Gmbh & Co Kg POLY(p-ARYLENEVINYLENES) A SUBSTITUTION ARYLE, LEUR PROCEDE DE PREPARATION ET LEUR UTILISATION DANS DES COMPOSANTS ELECTROLUMINESCENTS
JP2000053957A (ja) 1998-06-23 2000-02-22 Koto Gijutsu Kenkyuin Kenkyu Kumiai 新規な有機金属発光物質およびそれを含む有機電気発光素子
WO2000070655A2 (fr) 1999-05-13 2000-11-23 The Trustees Of Princeton University Dispositifs electroluminescents organiques a tres haute performance utilisant l'electrophosphorescence
WO2001041512A1 (fr) 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes de forme l2mx en tant que dopants phosphorescents pour del organiques
WO2001049806A1 (fr) 1999-12-31 2001-07-12 Lg Chemical Co., Ltd Dispositif electronique comprenant un compose organique presentant les caracteristiques de semi-conduction du dopage p
EP1205527A1 (fr) 2000-03-27 2002-05-15 Idemitsu Kosan Co., Ltd. Dispositif a electroluminescence organique
WO2002002714A2 (fr) 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Composes d'iridium electroluminescents contenant des phenylpyridines fluores, des phenylpyrimidines et des phenylquinolines, et dispositifs fabriques avec ces composes
WO2002015645A1 (fr) 2000-08-11 2002-02-21 The Trustees Of Princeton University Composes organometalliques et electrophosphorescence organique presentant un deplacement d'emission
EP1191614A2 (fr) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Dispositif luminescent et composé complexe d'un métal utilisé pour ce dispositif
EP1191612A2 (fr) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Dispositif luminescent, dispositif d'affichage et composé complexe d'un métal
EP1191613A2 (fr) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Dispositif luminescent, dispositif d'affichage et composé complexe d'un métal
US7294849B2 (en) 2001-03-14 2007-11-13 The Trustees Of Princeton University Materials and devices for blue phosphorescence based organic light emitting diodes
WO2003060956A2 (fr) 2002-01-18 2003-07-24 Lg Chem, Ltd. Nouveau materiau permettant de transporter des electrons et affichage organique electroluminescent utilisant ledit materiau
WO2004013080A1 (fr) 2002-08-01 2004-02-12 Covion Organic Semiconductors Gmbh Derives de spirobifluorene, leur preparation et leurs utilisations
EP1553154A1 (fr) 2002-08-23 2005-07-13 Idemitsu Kosan Co., Ltd. Dispositif organique electroluminescent et derive d'anthracene
WO2004028217A1 (fr) 2002-09-20 2004-04-01 Idemitsu Kosan Co., Ltd. Element organique electroluminescent
WO2004058911A2 (fr) 2002-12-23 2004-07-15 Covion Organic Semiconductors Gmbh Element electroluminescent organique
WO2004081017A1 (fr) 2003-03-11 2004-09-23 Covion Organic Semiconductors Gmbh Complexes metalliques
WO2004080975A1 (fr) 2003-03-13 2004-09-23 Idemitsu Kosan Co., Ltd. Derive heterocyclique contenant de l'azote et element electroluminescent organique utilisant ce derive
JP2004288381A (ja) 2003-03-19 2004-10-14 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子
WO2004093207A2 (fr) 2003-04-15 2004-10-28 Covion Organic Semiconductors Gmbh Melanges de semi-conducteurs organiques aptes a l'emission et de matieres matricielles, leur utilisation et composants electroniques contenant ces melanges
EP1617710A1 (fr) 2003-04-23 2006-01-18 Konica Minolta Holdings, Inc. Materiau pour dispositif electroluminescent organique, dispositif electroluminescent organique, dispositif d'eclairage et affichage
EP1617711A1 (fr) 2003-04-23 2006-01-18 Konica Minolta Holdings, Inc. Dispositif organique electroluminescent et affichage
WO2005011013A1 (fr) 2003-07-21 2005-02-03 Covion Organic Semiconductors Gmbh Element electroluminescent organique
WO2005019373A2 (fr) 2003-08-19 2005-03-03 Basf Aktiengesellschaft Complexes de metal de transition comportant des ligands de carbene faisant office d'emetteurs pour diodes electroluminescentes organiques (delo)
WO2005033244A1 (fr) 2003-09-29 2005-04-14 Covion Organic Semiconductors Gmbh Complexes metalliques
US20050069729A1 (en) 2003-09-30 2005-03-31 Konica Minolta Holdings, Inc. Organic electroluminescent element, illuminator, display and compound
WO2005039246A1 (fr) 2003-09-30 2005-04-28 Konica Minolta Holdings, Inc. Dispositif electroluminescent organique, dispositif d'eclairage et afficheur
WO2005084082A1 (fr) 2004-02-20 2005-09-09 Merck Patent Gmbh Dispositifs electroniques organiques
WO2005084081A1 (fr) 2004-02-20 2005-09-09 Merck Patent Gmbh Dispositifs electroniques organiques
WO2005086251A2 (fr) 2004-03-03 2005-09-15 Novaled Gmbh Utilisation d'un complexe metallique comme dopant n d'un materiau matrice semi-conducteur organique et composant electronique, ainsi que dopant et ligand, et son procede de production
EP1731584A1 (fr) 2004-03-31 2006-12-13 Konica Minolta Holdings, Inc. Matériau de dispositif électroluminescent organique, dispositif électroluminescent organique, écran et dispositif d'éclairage
WO2005111172A2 (fr) 2004-05-11 2005-11-24 Merck Patent Gmbh Nouveaux melanges de materiaux pour applications electroluminescentes
US20050258742A1 (en) 2004-05-18 2005-11-24 Yui-Yi Tsai Carbene containing metal complexes as OLEDs
EP1749809A1 (fr) 2004-05-27 2007-02-07 Idemitsu Kosan Co., Ltd. Derive de pyrene asymetrique et dispositif electroluminescent organique utilisant celui-ci
JP2005347160A (ja) 2004-06-04 2005-12-15 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、照明装置及び表示装置
WO2006005627A1 (fr) 2004-07-15 2006-01-19 Merck Patent Gmbh Derives oligomeres de spirobifluorene, leur elaboration et leur utilisation
WO2006048268A1 (fr) 2004-11-06 2006-05-11 Merck Patent Gmbh Dispositif electroluminescent organique
EP1661888A1 (fr) 2004-11-29 2006-05-31 Samsung SDI Co., Ltd. Composé contenant un phenylcarbazole et dispositif organiques électroluminiscent l'utilisant
WO2006097208A1 (fr) 2005-03-16 2006-09-21 Merck Patent Gmbh Nouveaux materiaux pour des dispositifs electroluminescents organiques
WO2006100896A1 (fr) 2005-03-18 2006-09-28 Idemitsu Kosan Co., Ltd. Derive d’amine aromatique et dispositif electroluminescent organique l’utilisant
WO2006108497A1 (fr) 2005-04-14 2006-10-19 Merck Patent Gmbh Composes pour dispositifs electroniques organiques
WO2006117052A1 (fr) 2005-05-03 2006-11-09 Merck Patent Gmbh Dispositif electroluminescent organique, et derives d'acide boronique et d'acide borinique utilises pour produire ce dispositif electroluminescent organique
WO2006122630A1 (fr) 2005-05-20 2006-11-23 Merck Patent Gmbh Composes pour dispositifs electroniques organiques
WO2006131192A1 (fr) 2005-06-09 2006-12-14 Merck Patent Gmbh Nouveaux materiaux destines a des dispositifs electroluminescents organiques
EP1905754A1 (fr) 2005-07-06 2008-04-02 Idemitsu Kosan Co., Ltd. Dérivé du pyrène et dispositif électroluminescent organique l utilisant
WO2007063754A1 (fr) 2005-12-01 2007-06-07 Nippon Steel Chemical Co., Ltd. Compose pour element electroluminescent organique et element electroluminescent organique
WO2007065550A1 (fr) 2005-12-08 2007-06-14 Merck Patent Gmbh Nouvelles matières pour dispositifs électroluminescents organiques
WO2007065678A1 (fr) 2005-12-08 2007-06-14 Merck Patent Gmbh Nouvelles matieres pour dispositifs electroluminescents organiques
EP1837926A1 (fr) 2006-03-21 2007-09-26 Novaled AG Radicaux ou diradicaux hétérocycliques, leur dimères, oligomères, polymères, composés spiro et polycycliques. Leur usage dans des semi-conducteurs organiques et dispositifs électroniques.
WO2007107306A1 (fr) 2006-03-22 2007-09-27 Novaled Ag Utilisation de radicaux heterocycliques pour le dopage de semi-conducteurs organiques
WO2007110129A1 (fr) 2006-03-24 2007-10-04 Merck Patent Gmbh Nouveaux materiaux pour disposifs electroluminescents organiques
WO2007115540A1 (fr) 2006-03-30 2007-10-18 Novaled Ag Utilisation de bora-tétraazapentalènes
WO2007137725A1 (fr) 2006-05-31 2007-12-06 Merck Patent Gmbh Nouveaux matériaux pour dispositifs électroluminescents organiques
WO2007140847A1 (fr) 2006-06-02 2007-12-13 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2008006449A1 (fr) 2006-07-11 2008-01-17 Merck Patent Gmbh Nouveaux matériaux destinés à des dispositifs électroluminescents organiques
WO2008056746A1 (fr) 2006-11-09 2008-05-15 Nippon Steel Chemical Co., Ltd. Composé pour un dispositif électroluminescent organique et dispositif électroluminescent organique
WO2008058525A2 (fr) 2006-11-13 2008-05-22 Novaled Ag Utilisation d'une liaison de coordination pour doper des semiconducteurs organiques
WO2008086851A1 (fr) 2007-01-18 2008-07-24 Merck Patent Gmbh Dérivés de carbazole pour des dispositifs électroluminescents organiques
EP1988587A1 (fr) 2007-04-30 2008-11-05 Novaled AG Composés de matière d'oxyde de carbone, de pseudo oxyde de carbone et de radialène ainsi que leur utilisation
WO2008138580A1 (fr) 2007-05-10 2008-11-20 Novaled Ag Dérivés imidazole et leur utilisation comme dopant pour un matériau matrice semi-conducteur organique
WO2008145239A2 (fr) 2007-05-29 2008-12-04 Merck Patent Gmbh Nouveaux matériaux destinés à des dispositifs électroluminescents organiques
WO2009000237A1 (fr) 2007-06-22 2008-12-31 Novaled Ag Utilisation du précurseur d'un dopant n pour le dopage d'un matériau semi-conducteur, précurseur et composant électronique ou optoélectronique
DE102008051737A1 (de) 2007-10-24 2009-05-07 Novaled Ag Quadratisch planare Übergangsmetallkomplexe und diese verwendende organische halbleitende Materialien sowie elektronische oder optoelektronische Bauelemente
WO2009062578A1 (fr) 2007-11-12 2009-05-22 Merck Patent Gmbh Dispositifs organiques électroluminescents contenant des complexes azométhine/métal
WO2009089821A1 (fr) 2008-01-15 2009-07-23 Novaled Ag Complexes de dithiolène-métaux de transition, et composants électroniques ou optoélectroniques
WO2009100925A1 (fr) 2008-02-13 2009-08-20 Merck Patent Gmbh Nouveaux matériaux pour des dispositifs organiques électroluminescents
US20100102709A1 (en) 2008-04-29 2010-04-29 Olaf Zeika Radialene compounds and their use
WO2010006680A1 (fr) 2008-07-18 2010-01-21 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2010012328A1 (fr) 2008-07-29 2010-02-04 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2010015306A1 (fr) 2008-08-08 2010-02-11 Merck Patent Gmbh, Dispositif électroluminescent organique
US20100096600A1 (en) 2008-10-16 2010-04-22 Novaled Ag Square Planar Transition Metal Complexes and Organic Semiconductive Materials Using Them as Well as Electronic or Optoelectric Components
EP2180029A1 (fr) 2008-10-23 2010-04-28 Novaled AG Composés de Radialène et leur utilisation
WO2010054730A1 (fr) 2008-11-11 2010-05-20 Merck Patent Gmbh Dispositifs électroluminescents organiques
WO2010054729A2 (fr) 2008-11-11 2010-05-20 Merck Patent Gmbh Matières pour des dispositifs électroluminescents organiques
WO2010072300A1 (fr) 2008-12-22 2010-07-01 Merck Patent Gmbh Dispositif électroluminescent organique contenant des dérivés triazine
WO2010097433A1 (fr) 2009-02-26 2010-09-02 Basf Se Composés quinoniques convenant comme impureté de dopage en électronique organique
WO2010099534A2 (fr) 2009-02-27 2010-09-02 E. I. Du Pont De Nemours And Company Composés deutérés pour applications électroniques
WO2010108579A1 (fr) 2009-03-23 2010-09-30 Merck Patent Gmbh Dispositif électroluminescent organique
WO2010136109A1 (fr) 2009-05-29 2010-12-02 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2011000455A1 (fr) 2009-06-30 2011-01-06 Merck Patent Gmbh Matériaux destinés à des dispositifs d'électroluminescence organique
WO2011042107A2 (fr) 2009-10-08 2011-04-14 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2011053334A1 (fr) 2009-10-26 2011-05-05 E. I. Du Pont De Nemours And Company Procédé pour la préparation de composés aromatiques deutérés
WO2011050888A1 (fr) 2009-10-29 2011-05-05 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2011054442A2 (fr) 2009-11-06 2011-05-12 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2011057706A2 (fr) 2009-11-14 2011-05-19 Merck Patent Gmbh Matières pour dispositif électroniques
WO2011060859A1 (fr) 2009-11-17 2011-05-26 Merck Patent Gmbh Matériaux pour des dispositifs électroluminescents organiques
WO2011060877A2 (fr) 2009-11-17 2011-05-26 Merck Patent Gmbh Matériaux pour des dispositifs électroluminescents organiques
WO2011060867A1 (fr) 2009-11-18 2011-05-26 Merck Patent Gmbh Hétérocycles condensés contenant de l'azote pour des oled
US20120187826A1 (en) 2009-12-21 2012-07-26 Idemitsu Kosan Co., Ltd. Organic electroluminescent element using pyrene derivative
WO2011088877A1 (fr) 2010-01-25 2011-07-28 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2011116865A1 (fr) 2010-03-25 2011-09-29 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
WO2011131185A1 (fr) 2010-04-21 2011-10-27 Novaled Ag Mélange pour la fabrication d'une couche semi-conductrice dopée
WO2011134458A1 (fr) 2010-04-27 2011-11-03 Novaled Ag Matériau semi-conducteur organique et composant électronique
WO2011137951A1 (fr) 2010-05-04 2011-11-10 Merck Patent Gmbh Dispositifs électroluminescents organiques
EP3689817A1 (fr) * 2010-08-18 2020-08-05 Shiono Chemical Co., Ltd. Procédé de production d'hydrogène ou d'hydrogènes lourds et hydrogénation (protiation, deuteration ou tritiation) de composés organiques l'utilisant
WO2012031735A1 (fr) 2010-09-10 2012-03-15 Novaled Ag Composés pour dispositifs photovoltaïques organiques
WO2012034627A1 (fr) 2010-09-15 2012-03-22 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
DE102010046040A1 (de) 2010-09-22 2012-03-22 Novaled Ag Verfahren zur Herstellung von Fulleren-Derivaten
WO2012048781A1 (fr) 2010-10-15 2012-04-19 Merck Patent Gmbh Matériaux à base de triphényles pour dispositifs électroluminescents organiques
WO2012048780A1 (fr) 2010-10-15 2012-04-19 Merck Patent Gmbh Composés pour dispositifs électroniques
EP2452946A1 (fr) 2010-11-16 2012-05-16 Novaled AG Oxides de pyridylphosphine pour dispositif électronique organique et dispositif électronique organique
EP2463927A1 (fr) 2010-12-08 2012-06-13 Novaled AG Matériau pour dispositif électronique organique et dispositif électronique organique
US20120223296A1 (en) 2011-03-01 2012-09-06 Sensient Imaging Technologies Gmbh Organic Semiconducting Materials and Organic Component
WO2012143080A2 (fr) 2011-04-18 2012-10-26 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2012150001A1 (fr) 2011-05-05 2012-11-08 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2012168358A1 (fr) 2011-06-09 2012-12-13 Novaled Ag Composé destiné à un dispositif électronique organique
WO2012175535A1 (fr) 2011-06-22 2012-12-27 Novaled Ag Composant electronique organique
WO2012175219A1 (fr) 2011-06-22 2012-12-27 Novaled Ag Dispositif électronique et composé
WO2013041176A1 (fr) 2011-09-21 2013-03-28 Merck Patent Gmbh Dérivés de carbazole pour des dispositifs électroluminescents organiques
WO2013056776A1 (fr) 2011-10-20 2013-04-25 Merck Patent Gmbh Matériaux destinés à des dispositifs électroluminescents organiques
WO2013083216A1 (fr) 2011-11-17 2013-06-13 Merck Patent Gmbh Dérivés de spiro-dihydroacridine et leur application comme matériaux pour dispositifs électroluminescents organiques
WO2013120577A1 (fr) 2012-02-14 2013-08-22 Merck Patent Gmbh Composés de spirobifluorène pour dispositifs organiques électroluminescents
EP2816008A1 (fr) * 2012-02-17 2014-12-24 Shiono Chemical Co., Ltd. Procédé de fabrication d'hydrogène ou de deutérium, procédé de fabrication d'un composé organique hydrogéné ou deutéré, procédé pour hydrogéner ou deutérer un composé organique, procédé pour déshalogéner un composé organique ayant un halogène et bille destinée à être utilisée dans une réaction mécano-chimique
WO2013185871A1 (fr) 2012-06-12 2013-12-19 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2014015937A1 (fr) 2012-07-23 2014-01-30 Merck Patent Gmbh Composés et dispositifs electroluminescents organiques
WO2014015938A1 (fr) 2012-07-23 2014-01-30 Merck Patent Gmbh Dérivés de 2-diarylaminofluorène et composés électroniques organiques les contenant
WO2014015935A2 (fr) 2012-07-23 2014-01-30 Merck Patent Gmbh Composés et dispositifs electroniques organiques
WO2014037077A1 (fr) 2012-09-04 2014-03-13 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2014072017A1 (fr) 2012-11-12 2014-05-15 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2014106522A1 (fr) 2013-01-03 2014-07-10 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2015022051A1 (fr) 2013-08-15 2015-02-19 Merck Patent Gmbh Matériaux destinés à des dispositifs électroniques
WO2014111269A2 (fr) 2013-10-14 2014-07-24 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2015082056A1 (fr) 2013-12-06 2015-06-11 Merck Patent Gmbh Composés et dispositifs électroniques organiques
WO2015086108A1 (fr) 2013-12-12 2015-06-18 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2015102118A1 (fr) 2014-02-18 2015-07-09 学校法人関西学院 Composé aromatique polycyclique
WO2015131976A1 (fr) 2014-03-07 2015-09-11 Merck Patent Gmbh Matières pour dispositifs électroniques
WO2015158411A1 (fr) 2014-04-14 2015-10-22 Merck Patent Gmbh Matières pour dispositifs électroniques
WO2015158409A1 (fr) 2014-04-16 2015-10-22 Merck Patent Gmbh Matières pour dispositifs électroniques
WO2015169412A1 (fr) 2014-05-05 2015-11-12 Merck Patent Gmbh Matières pour des dispositifs organiques électroluminescents
WO2016015810A1 (fr) 2014-07-29 2016-02-04 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2016023608A1 (fr) 2014-08-13 2016-02-18 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2016073425A2 (fr) 2014-11-06 2016-05-12 E. I. Du Pont De Nemours And Company Procédé de préparation de composés aromatiques deutérés
WO2016078738A1 (fr) 2014-11-18 2016-05-26 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
WO2016087017A1 (fr) 2014-12-01 2016-06-09 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
WO2016102048A1 (fr) 2014-12-22 2016-06-30 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2016131521A1 (fr) 2015-02-16 2016-08-25 Merck Patent Gmbh Matériaux à base de dérivés de spirobifluorène pour dispositifs électroniques
WO2016150544A1 (fr) 2015-03-25 2016-09-29 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2017025165A1 (fr) 2015-08-12 2017-02-16 Merck Patent Gmbh Matériaux pour dispositifs électroniques
WO2017028940A1 (fr) 2015-08-14 2017-02-23 Merck Patent Gmbh Dérivés de phénoxazine pour dispositifs électroluminescents organiques
WO2017028941A1 (fr) 2015-08-14 2017-02-23 Merck Patent Gmbh Dérivés de phénoxazine pour dispositifs électroluminescents organiques
WO2017036574A1 (fr) 2015-08-28 2017-03-09 Merck Patent Gmbh Dérivés de 6,9,15,18-tétrahydro-s-indacéno[1,2-b:5,6-b']difluorène et leur utilisation dans des dispositifs électroniques
WO2017036573A1 (fr) 2015-08-28 2017-03-09 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2017148565A1 (fr) 2016-03-03 2017-09-08 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2017148564A1 (fr) 2016-03-03 2017-09-08 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2017195669A1 (fr) 2016-05-13 2017-11-16 コニカミノルタ株式会社 Matériau d'élément électroluminescent organique, élément électroluminescent organique, appareil d'affichage et appareil d'éclairage
WO2018007421A1 (fr) 2016-07-08 2018-01-11 Merck Patent Gmbh Matières pour dispositifs électroluminescents organiques
CN108409769A (zh) 2016-07-29 2018-08-17 江苏三月光电科技有限公司 一种发光效率高的含硼有机电致发光化合物及其应用
US20180069182A1 (en) 2016-09-07 2018-03-08 Kwansei Gakuin Educational Foundation Polycyclic aromatic compound
WO2018095940A1 (fr) 2016-11-25 2018-05-31 Merck Patent Gmbh Dérivés d'indéno [1,2-b] fluorène à fusion bisbenzofurane et composés apparentés en tant que matériaux pour des dispositifs électroluminescents organiques (oled)
WO2018095888A1 (fr) 2016-11-25 2018-05-31 Merck Patent Gmbh Dérivés de 2,8-diaminoindéno [1,2-b] fluorène à fusion bisbenzofurane et composés apparentés en tant que matériaux pour des dispositifs électroluminescents organiques (oled)
KR20180130970A (ko) 2017-05-31 2018-12-10 삼성에스디에스 주식회사 도어락 모티스
CN107266484A (zh) 2017-07-14 2017-10-20 瑞声科技（南京）有限公司 有机电致发光材料及其发光器件
WO2019076789A1 (fr) 2017-10-17 2019-04-25 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
WO2019170572A1 (fr) 2018-03-06 2019-09-12 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
BJELOPETROVIC ALEN ET AL: "Deuteration of Pd-activated C(sp 2 )-H bonds in the solid state", INORGANIC CHEMISTRY FRONTIERS, vol. 10, no. 20, 1 January 2023 (2023-01-01), pages 6005 - 6014, XP093257675, ISSN: 2052-1553, DOI: 10.1039/D3QI00932G *
DO ET AL., ACS CENTRAL SCIENCE, vol. 3, 2017, pages 13 - 19
J. PHYS. CHEM. C, vol. 111, 2007, pages 3490 - 3494
LIU ET AL., ADVANCED MATERIALS, vol. 34, 2022, pages 2108327
SAWAMA YOSHINARI ET AL: "Stainless-Steel Ball-Milling Method for Hydro-/Deutero-genation using H 2 O/D 2 O as a Hydrogen/Deuterium Source", CHEMSUSCHEM, vol. 8, no. 22, 23 October 2015 (2015-10-23), DE, pages 3773 - 3776, XP093257597, ISSN: 1864-5631, DOI: 10.1002/cssc.201501019 *
T. MATSUMOTOT. NAKADAJ. ENDOK. MORIN. KAWAMURAA. YOKOIJ. KIDO, MULTIPHOTON ORGANIC EL DEVICE HAVING CHARGE GENERATION LAYER
Y. SHIROTA ET AL., CHEM. REV., vol. 107, no. 4, 2007, pages 953 - 1010

Similar Documents

Publication Publication Date Title
KR102268695B1 (ko) 전자 소자
JP6591433B2 (ja) 電子素子のための材料
CN109346615B (zh) 电子器件
CN104640958B (zh) 用于电子器件的材料
KR102608491B1 (ko) 유기 전자 디바이스용 조성물
KR102769406B1 (ko) 유기 전계발광 디바이스용 재료
JP6498667B2 (ja) 電子素子のための材料としてのトリアリールアミン置換ベンゾ［ｈ］キノリン誘導体
JP6469673B2 (ja) 電子素子のための材料
KR102557516B1 (ko) 유기 전자 디바이스용 재료
JP2016507475A (ja) 電子素子のための材料
JP2023502908A (ja) 有機エレクトロルミネッセンス素子のための材料
KR102837851B1 (ko) 전자 디바이스
KR20210096630A (ko) 전자 디바이스
KR102777515B1 (ko) 전자 디바이스용 재료
CN117440703A (zh) 有机电致发光器件
KR20200090177A (ko) 유기 전계발광 디바이스용 재료
EP3762387A1 (fr) Composés pour dispositifs électroniques
JP2025170237A (ja) 電子デバイス
WO2025196145A1 (fr) Matériaux pour dispositifs électroluminescents organiques
KR20200020841A (ko) 유기 전계발광 디바이스용 재료
WO2024133048A1 (fr) Procédé de préparation de composés aromatiques deutérés
KR20210031711A (ko) 전자 디바이스용 재료
WO2025132547A1 (fr) Procédé mécanochimique de deutération de composés organiques
KR20240128020A (ko) 중수소화 유기 화합물의 제조 방법
KR102650253B1 (ko) 유기 전계발광 디바이스용 재료

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24833570

Country of ref document: EP

Kind code of ref document: A1