KR100845409B1 - Synthesis process - Google Patents

Abstract

A method for preparing substituted or unsubstituted 9,10-diarylanthracene is disclosed. The method comprises the steps of reacting a substituted or unsubstituted aryl compound of an organic metal with a substituted or unsubstituted anthraquinone to produce a substituted or unsubstituted diol; And reacting the substituted or unsubstituted diol with a reducing agent to produce substituted or unsubstituted 9,10-diarylanthracene. Also disclosed is an electroluminescent device comprising a light emitting layer comprising substituted or unsubstituted 9,10-diarylanthracene.

Electroluminescent Devices, 9,10-Diarylanthracene

Description

Synthesis process

1 illustrates a conceptual diagram of an OLED according to an embodiment of the present invention having an electron injection and transport zone, a mixed charge transport layer and a hole injection and transport region.

2 illustrates the lifetime versus time of disclosed substituted or unsubstituted 9,10-diarylanthracene versus commercially available TBADN.

3 illustrates the drive voltage over time for the disclosed substituted or unsubstituted 9,10-diarylanthracene versus commercially available TBADN.

The present invention relates to a process for preparing substituted or unsubstituted 9,10 diarylanthracene.

Organic light emitting devices (OLEDs) are useful for indicator applications, especially for portable indicator applications. In order to achieve effective electroluminescence, OLEDs have typically been fabricated to include separate layers of hole transport material (HTM) and emission electron transport material (ETM). During operation, the applied electric field causes positive charges (holes) and negative charges (electrons) to be injected from the anode and cathode of the OLED, respectively, to recombine and emit light. In other known OLED indicators, hole transport and electron transport layers are doped with dyes to improve the efficiency and stability of the OLED. OLEDs in which the hole transport material and the emission electron transport material are mixed with each other in one layer have been developed.

One problem with OLEDs is the development of high performance materials with the desired properties. Many new materials with RGB (red, green, blue) emission colors have been developed to meet the demand for full-color indicators. Green luminescent materials have been developed relatively well for OLEDs, but satisfactory blue materials with good color purity, high efficiency, and good stability are still needed. One such known material is 2-tert-butyl-9,10-bis (β-naphthyl) -anthracene (TBADN).

In a typical OLED, the light emitting layer may be present between the hole transport layer and the electron transport layer. As shown in FIG. 1, the light emitting layer may include a host material doped with a guest material (dopant). The light emitting layer can provide an effective site for recombination of the injected hole-electron pair followed by energy transfer of the guest material, which can produce highly efficient electroluminescence. Ideally, the same host material should be able to be doped with the appropriate guest material to produce red, green and blue emission depending on the emission color from the guest material. It can be difficult to find a host material with a larger energy gap than a blue light emitting guest material. Compounds of 2-tert-butyl-9,10-bis (β-naphthyl) -anthracene (TBADN) may have a host with an excellent wide energy gap for color OLEDs.

It is an object of the present invention to provide a method for preparing a host material having good color purity, high efficiency and good stability and having a wide energy gap.

In various aspects of the invention, methods for preparing substituted or unsubstituted 9,10-diarylanthracene are provided. The method comprises the steps of reacting a substituted or unsubstituted aryl compound of an organic metal with a substituted or unsubstituted anthraquinone to produce a substituted or unsubstituted diol; And reacting the substituted or unsubstituted diol with a reducing agent to produce substituted or unsubstituted 9,10-diarylanthracene.

In still other aspects of the present invention, a method for preparing substituted or unsubstituted 9,10-diarylanthracene is provided. The method includes reacting a substituted or unsubstituted diol with a reducing agent to produce a substituted or unsubstituted 9,10-diarylanthracene.

In still other aspects of the present invention, there is provided an electroluminescent device comprising a light emitting layer comprising substituted or unsubstituted 9,10-diarylanthracene. The substituted or unsubstituted 9,10-diarylanthracene may be prepared by reacting a substituted or unsubstituted aryl compound of an organic metal with a substituted or unsubstituted anthraquinone to generate a substituted or unsubstituted diol; And reacting the substituted or unsubstituted diol with a reducing agent to produce substituted or unsubstituted 9,10-diarylanthracene.

Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.

It is to be understood that the foregoing general description and the following detailed description are exemplary and merely explanatory and do not limit the invention when claimed.

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one (several) embodiment (s) of the invention and, together with this description, serve to explain the principles of the invention.

Embodiments of the present invention are described in detail with reference to the accompanying drawings. Wherever possible, the same reference numbers in the drawings will be used to refer to the same or similar parts.

The present invention relates to a method for preparing a substituted or unsubstituted 9,10-diarylanthracene, wherein the method is substituted by reacting a substituted or unsubstituted aryl compound of an organic metal with a substituted or unsubstituted anthraquinone. Producing an unsubstituted diol; And reacting the substituted or unsubstituted diol with a reducing agent to produce substituted or unsubstituted 9,10-diaryl anthracene.

Substituted or unsubstituted 9,10-diaryl anthracene may be represented by [Formula 1]:

Wherein R ₁ and R ₂ may be individual substituents or groups of substituents, and each substituent may be individually selected from the following groups: group 1-hydrogen, or from about 1 to about 24 carbon atoms Alkyl; Group 2-aryl or substituted aryl, consisting of about 5 to about 20 carbon atoms; Group 3-about 4 to about 24 carbon atoms, wherein the carbon atoms can complete a conjugated aromatic ring consisting of anthracenyl, pyrenyl, or perrylenyl; Group 4-heteroaryl or substituted heteroaryl of about 5 to about 24 carbon atoms, wherein the carbon atoms form a conjugated heteroaromatic ring consisting of furyl, thienyl, pyridyl, quinolinyl and other heterocyclic systems To complete; Group 5-alkoxy, amino, alkyl amino, or aryl amino consisting of about 1 to about 24 carbon atoms; And halogen elements such as group 6-fluorine, chlorine, bromine or cyano; And wherein R ₃ and R _4, which may be the same or different, may be individually selected from the group consisting of aryl amino of group 5 as defined above in groups 2, 3, 4 and above. In an embodiment, the substituted or unsubstituted 9,10-diarylanthracene can be 2-tert-butyl-9,10-bis (β-naphthyl) -anthracene (TBADN).

In another embodiment, the method can be described by the following reaction scheme:

Anthraquinones are typical substituents including alkyl groups, alkylene groups, aryl groups, arylene groups, alkoxy groups, aryl groups, aryloxy groups, and halogens such as fluorides, chlorides and bromide It may be substituted by. Various alkyl and alkylene moieties include about 1 to about 8 carbon atoms, for example about 2 to about 7 carbon atoms, and in another example, those consisting of about 4 carbon atoms can do. Cycloalkyl moieties may include about 3 to about 10 carbon atoms, for example about 5 to about 7 carbon atoms, and as another example, those consisting of about 5 to about 6 carbon atoms. Aryl and arylene moieties can be phenyl and phenylene moieties. In an embodiment, the anthraquinone may be substituted with a t-butyl group. For example, the substituted or unsubstituted anthraquinone can be 2- (t-butyl) anthraquinone.

Substituted or unsubstituted anthraquinone may be subjected to a coupling reaction between an organometallic substituted or unsubstituted aryl compound. Substituted or unsubstituted aryl compounds of organometals can be prepared from halogenated substituted or unsubstituted aryl groups. Substituted aryl compounds and halogenated and substituted aryl compounds of the organometallic are each independently alkyl groups, alkylene groups, aryl groups, arylene groups, alkoxy groups, aryl groups, aryloxy groups, And typical substituents including halogens such as fluoride, chloride and bromide. Various alkyl and alkylene moieties may include those consisting of about 1 to about 8 carbon atoms, for example about 2 to 7 carbon atoms, and yet another example about 4 carbon atoms. Cycloalkyl moieties may include from about 3 to about 10 carbon atoms, for example from about 5 to about 7 carbon atoms, and in another example from about 5 to about 6 carbon atoms. Aryl and arylene moieties can be phenyl and phenylene moieties.

In an embodiment, the halogenated, substituted or unsubstituted aryl compound may be a compound represented by [Formula 2]:

Wherein R ₇ may be halogen, such as chloride, bromide or iodide, and R ₆ may be any of the substituents described for formula (1). In an embodiment, the halogenated, substituted or unsubstituted aryl compound can be 2-bromonaphthalene.

Substituted or unsubstituted aryl compounds of organometals can be prepared by reacting halogenated, substituted or unsubstituted aryl compounds with metals or organometallates, as shown in formula (2). The metal may be selected from magnesium, lithium, sodium, beryllium, calcium, zinc, copper, titanium, zirconium, manganese, palladium and the like, or organic metalates such as (n-butyl) lithium and (t-butyl) lithium Can be selected. The metal source can be, for example, metallocenes with ferrocene. The term "metal" may be understood to include all elements, such as silicon, arsenic, or boron, which are not metals but are considered metalloids.

In an embodiment, the substituted or unsubstituted aryl compound of the organometal is halogenated of the metal or organometallate such as n-butyllithium and the compound substituted or unsubstituted from about 1 minute to about 1 hour, for example about It may be formulated by addition over a period of 10 minutes to about 45 minutes, another example about 15 minutes. The reaction may proceed from about 1 hour to about 5 hours, for example from about 2 hours to about 4 hours, and in another example about 3 hours while the temperature reaches about room temperature (23 ° C.). The reaction temperature may be reduced below room temperature, for example, below about 0 ° C., and in another example below about −76 ° C. Substituted or unsubstituted anthraquinones can be added to the reaction. The reaction temperature may be increased to temperatures higher than about −76 ° C., for example higher than 0 ° C., as another example to room temperature, to produce substituted or unsubstituted diols.

In an embodiment, the diol may be substituted with any of the typical substituents of Formula 1, such as alkyl groups, for example t-butyl groups. For example, the diol can be represented by Formula 3:

.

.

Substituted or unsubstituted diols can be reacted with a reducing agent to produce substituted or unsubstituted 9,10-diarylanthracene. The reducing agent can be selected from stenos chloride, vanadate chloride, and titanos chloride in an acid such as acetic acid or hydrochloric acid with or without water and can be carried out in a solvent such as dioxane.

In an embodiment, the reducing agent may be potassium iodide in an acid such as acetic acid or hydrochloric acid and with or without potassium hypophosphite, optionally a solvent will be present. One of ordinary skill in the art will appreciate that other reducing agents, including combinations of reducing agents, may be used to affect this conversion.

The reducing agent may be added and the reaction temperature is at least about 1 hour, for example at least about 2 hours, and in another example, at least about room temperature, for example at least about 40 ° C., and again, for a period of at least about 3 hours. As another example, it may be increased to at least about 50 ° C. The reaction can be cooled to about room temperature, filtered and washed.

Substituted or unsubstituted 9,10-diarylanthracene can be dried and purified, for example, by sublimation at 320 ° C. with a Kaufman column.

As shown in FIG. 2, substituted or unsubstituted 9,10-diarylanthracene can have an increased lifetime in OLEDs compared to commercially available TBADN. In addition, as shown in FIG. 3, substituted or unsubstituted 9,10-diarylanthracene may have approximately the same drive voltage over time as compared to commercially available TBADN.

An exemplary embodiment of an organic light emitting device (OLED) according to the invention is shown in FIG. The organic light emitting device 10 may include a light emitting region 20, which includes the mixed charge transport layer 30, the electron injection and transport zone 40, and the selective hole injection and transport zone 50. It may include. The cathode 60 may be provided adjacent to and in contact with the electron injection and transport zone 40. The anode 70 may be in direct contact with the mixed charge transport layer 30 or may be in direct contact in alternating proximity with the selective hole injection and transport zone 50. Although not shown in FIG. 1, an organic light emitting device may be provided on a substrate with an anode 70, and the anode 70 may be in direct contact with and above the substrate. An optional protective layer may be provided in contact with the cathode 60 on top. Anthracene compounds of the present invention may be provided within the electron injection and transport zone 40 and / or in the mixed charge transport layer.

In an embodiment, the electroluminescent (EL) device of the present invention is made of, for example, a support substrate made of glass, such as indium tin oxide (ITO) and from about 1 to about 500 nanometers, and for example An anode disposed on the support substrate at a thickness of about 30 to about 100 nanometers (thickness ranges for each layer may be selected as examples), and in contact with the anode and from about 5 to about 500 nanometers For example, an optional buffer layer consisting of a conductive component to a thickness of about 10 to about 100 nanometers, consisting of an aromatic tertiary amine and of about 1 to about 200 nanometers, for example about 5 to about 100 nanometers. An organic hole injection and transport zone disposed over the buffer layer in thickness and in contact with the hole injection and transport zone and composed of anthracene compounds of the formula or illustrated herein Organic electron injection and transport consisting of anthracene compounds included by and having a thickness of about 5 to about 300 nanometers, eg, about 10 to about 100 nanometers, and in contact with a low work function metal as cathode It may include a zone. In an embodiment, the hole injecting and transporting zone or the electron injecting and transporting zone may, for example, selectively contain from about 0.01% to about 10% by weight of a fluorescent dye or from about 0.01% to about 25% by weight of a phosphorescent dye. It may further include as.

In another embodiment, the EL device disclosed herein is made of, for example, a support substrate made of glass, such as indium tin oxide (ITO) and from about 1 to about 500 nanometers, and for example about 30 An anode disposed on the support substrate at a thickness of about 100 nanometers, a conductive component or hole transport material in contact with the anode and having a thickness of about 5 to about 500 nanometers, for example, about 10 to about 100 nanometers Buffer layer, consisting of an aromatic tertiary amine and having an organic hole injection and transport zone disposed above said buffer layer at a thickness of about 1 to about 200 nanometers, for example, about 5 to about 100 nanometers, For example, a mixed charge number consisting of an organic light emitting material consisting of a fluorescent or phosphorescent material and having a thickness of about 1 to about 200 nanometers, and for example about 5 to about 100 nanometers. Layer, consisting of anthracene compounds in contact with the mixed charge transport layer and composed of anthracene compounds of the formula or included by the formulas illustrated herein, and from about 5 to about 300 nanometers, for example from about 10 to about It has a thickness of 100 nanometers and may include an organic electron injection and transport zone in contact with the low work function metal as the cathode. In the EL device, light emission can be started from the mixed charge transport layer, and the mixed charge transport layer can be, for example, about 0.01 wt% to about 10 wt% fluorescent dye or about 0.01 wt% to about 25 wt% phosphorescent dye Optionally may further include.

In yet another embodiment, the disclosed EL device is, for example, a support substrate made of glass, such as indium tin oxide (ITO) and from about 1 to about 500 nanometers, and for example from about 30 to about An anode disposed on the support substrate at a thickness of 100 nanometers, in contact with the anode and having conductive components or hole transport materials at a thickness of about 5 to about 500 nanometers, for example, about 10 to about 100 nanometers. Optional buffer layer consisting of: an organic hole injection and transport zone, a hole transport material, consisting of an aromatic tertiary amine and disposed above said buffer layer to a thickness of about 1 to about 200 nanometers, eg, about 5 to about 100 nanometers; Mixed charge transport layer composed of an electron transport material and having a thickness of about 1 to about 200 nanometers, and for example about 5 to about 100 nanometers, in contact with the mixed charge transport layer And an anthracene compounds comprised by the formulas exemplified herein and having a thickness of about 5 to about 300 nanometers, eg, about 10 to about 100 nanometers, and contacting the low work function metal as a cathode. Organic electron injection and transport zones. Typically, the mixed charge transport layer described herein comprises from about 20 wt% to about 80 wt% of the hole transport material, and from about 80 wt% to about 20 wt% of the electron transport material, for example from about 35 wt% to About 65 wt% hole transport material, and about 65 wt% to about 35 wt% electron transport material. Suitable hole transport materials for forming the mixed layer include tertiary aromatic amines, indolocarbazoles, aromatic hydrocarbon compounds and mixtures thereof. The electron transporting material of the mixed layer may comprise an anthracene compound included by the formulas exemplified herein, or optionally the electron transporting material may be a metal chelate, stilbene, triazine, aromatic hydrocarbons, analogs, and mixtures thereof Known conventional electron transport materials such as these. In addition, the mixed charge transport layer may include a light emitting material, for example, about 0.01% to about 10% by weight of a fluorescent light emitting material or about 0.01% to about 25% by weight of a phosphorescent light emitting material, or other light emitting materials. Wherein all weight percentages are based on the total weight of the materials comprising the mixed layer. For this embodiment, the organic electron injection and transport zone can optionally include known conventional electron transport materials such as metal chelates, stilbenes, triazines, aromatic hydrocarbons, analogs, and mixtures thereof. The electron transporting material of the mixed charge transporting layer may include anthracene compounds included by the formulas illustrated herein. At least one (or both) of the electron transport material present in the electron injection and transport zone or the mixed charge transport layer adjacent to the cathode comprises the anthracene compound of the present invention. In this embodiment, it is also possible to provide the anthracene compound of the invention in the mixed charge transport layer as well as in the electron injection and transport zone. In addition, where the mixed charge transport layer comprises a hole transport material, additional hole injection and transport zones may be optional within the light emitting region of the device.

In each disclosed embodiment, it is understood by those skilled in the art that the electron injection and transport zone may comprise one or more layers, and the one or more layers may contain an anthracene compound. It is also understood that such layers may combine one or more conventionally used electron transport materials such as Alq ₃ . In addition, the anthracene compounds may be bonded to any layer or just a portion of the layers of the electron injection and transport zone.

All organic layers, buffer layers, hole transport layers, light emitting layers, and electron transport layers described herein may be formed by any suitable method, for example vacuum deposition as understood by one of ordinary skill in the art. . The method may also be applied to form any of the layers comprising one or more components. For example, the mixed layer can be formed by co-depositing a hole transport material, an electron transport material, and a selective light emitting material.

The organic EL elements of the present invention may include a support substrate. Examples of support substrates include polymer components, glass, and the like, and polyesters such as MYLAR ^® , polycarbonate, polyacrylate, polymethacrylate, polysulfone, quartz, and the like. Other substrates may also be selected, for example, if they can effectively support other layers and do not interfere with the functional performance of the device. The thickness of the substrate is, for example. Depending on the structural requirements of the device, for example, it may have a range of about 25 to 1,000 μm or more, for example, about 50 to about 500 μm.

Examples of anodes in contact with a substrate include positive charge injection electrodes, which may be, for example, indium tin oxide, tin oxide, gold, platinum, or other suitable materials such as electrically conductive carbon, such as polyaniline, polypyrrole, and the like. Π-conjugated polymers, which have a work function of at least about 4 eV (electron volts), more specifically, from about 4 eV to about 6 eV. The thickness of the anode can range from about 1 to about 500 nanometers, for example, the appropriate range is selected by the optical constants of the anode material. One suitable non-limiting exemplary range of anode thickness is about 30 nm to about 100 nm.

An optional buffer layer may be provided adjacent to the anode of the electroluminescent device of the present invention. The buffer layer primarily functions to facilitate efficient injection of holes from the anode and to improve device operation stability by improving adhesion between the anode and organic hole injection and transport zones. The buffer layer may comprise a conductive material such as polyaniline and its acid-doped forms, polypyrrole, poly (phenylene vinylene), and known semiconducting organic materials; Porphyrin derivatives disclosed in US Pat. No. 4,356,429, the disclosure of which is incorporated herein by reference, such as 1,10,15,20-tetraphenyl-21H, 23H-porphyrin copper (II); Copper phthalocyanine, copper tetramethyl phthalocyanine; Zinc phthalocyanine; Titanium oxide phthalocyanine; Magnesium phthalocyanine; And the like.

Another class of hole transport materials that can be selected for the buffer layer are the aromatic tertiary amines disclosed in US Pat. No. 4,539,507, the disclosure of which is incorporated herein by reference in its entirety.

Representative examples of aromatic tertiary amines include, but are not limited to, bis (4-dimethylamino-2-methylphenyl) phenylmethane; N, N, N-tri (p-tolyl) amine; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; 1,1-bis (4-di-p-tolylaminophenyl) -4-phenyl cyclohexane; N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine; N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine; N, N'-diphenyl-N, N'-bis (4-methoxyphenyl) -1,1'-biphenyl-4,4'-diamine; N, N, N ', N'-tetra-p-tolyl-1,1'-biphenyl-4,4'-diamine; N, N'-di-1-naphthyl-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine; Include analogs.

Another class of aromatic tertiary amines selected for hole transport materials include N, N-bis- [4 '-(N-phenyl-N-m-tolylamino) -4-biphenylyl] aniline; N, N-bis- [4 '-(N-phenyl-N-m-tolylamino) -4-biphenylyl] -m-toluidine; N, N-bis- [4 '-(N-phenyl-N-m-tolylamino) -4-biphenylyl] -p-toluidine; N, N-bis- [4 '-(N-phenyl-Np-tolylamino) 4-biphenylyl] aniline: N, N-bis- [4'-(N-phenyl-Np-tolylamino) -4 -Biphenylyl] -m-toluidine; N, N-bis- [4 '-(N-phenyl-N-p-tolylamino) -4-biphenylyl] -p-toluidine; N, N-bis- [4 '-(N-phenyl-N-p-chlorophenylamino) -4-biphenylyl] -m-toluidine; N, N-bis- [4 '-(N-phenyl-N-m-chlorophenylamino) -4-biphenylyl] -m-toluidine; N, N-bis- [4 '-(N-phenyl-N-m-chlorophenylamino) -4-biphenylyl] -p-toluidine; N, N-bis- [4 '-(N-phenyl-N-m-tolylamino) -4-biphenylyl] -p-chloroaniline; N, N-bis- [4 '-(N-phenyl-N-p-tolylamino) -4-biphenylyl] -m-chloroaniline; And multinuclear aromatic amines such as N, N-bis- [4 '-(N-phenyl-N-m-tolylamino) -4-biphenylyl] -1-aminonaphthalene and the like.

The buffer layer may also include aromatic tertiary amines and may further comprise a stabilizer, as disclosed in US Pat. No. 5,846,666, the disclosure of which is incorporated herein by reference in its entirety, wherein the stabilizer is selected from rublin, 4 Certain hydrocarbon compounds such as 8-diphenylanthracene and the like. The buffer layer can be prepared by forming one of the compounds into a thin film by known methods such as vapor deposition or spin coating. The thickness of the buffer layer thus formed is not particularly limited and may range from about 5 to about 300 nanometers, such as from about 10 to about 100 nanometers.

The hole injection and transport zone may comprise a hole transport material having a thickness in the range of about 1 nanometer to about 200 nanometers, eg, in the range of about 5 nanometers to about 100 nanometers. Any conventional suitable aromatic amine hole transport material described for the buffer layer can be selected to form this layer.

An exemplary class of hole transport materials selected for forming a hole injection and transport zone or for use as a hole transport material in a mixed charge transport layer is N, N'-diphenyl-N, N'-bis (4-methoxyphenyl) -1,1'-biphenyl-4,4'-diamine, N, N, N ', N'-tetra-p-tolyl-1,1'-biphenyl-4,4'-diamine, N, N N, N, N ', N'-tetraaryl benzidines, such as' -di-1-naphthyl-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine and the like, 4, 4,4'-bis (9-carbazoryl) -1,1'-biphenyl compounds such as 4'-bis (9-carbazoryl) -1,1'-biphenyl compounds are 4,4'-bis (9-carbazolyl) -1,1'-biphenyl and 4,4'-bis (3-methyl-9-carbazoryl) -1,1'-biphenyl, and the like.

Non-limiting examples of suitable luminescent materials for use in the mixed charge transport layer include US Pat. No. 4,539,507; 5,151,629; And metal chelates of 8-hydroxyquinoline as described in 5,150,006 (the disclosures of which are hereby incorporated by reference in their entirety). Specific illustrative examples of luminescent materials or compounds include tris (8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium, bis (8-hydroxyquinolinate) magnesium, bis ( 8-hydroxyquinolinate) zinc, tris (5-methyl-8-hydroxyquinolinate) aluminum, tris (7-propyl-8-quinolinolato) aluminum, bis [benzo {f} -8- Quinolinate] zinc, bis (10-hydroxybenzo [h] quinolinate) beryllium, and the like. Another exemplary class of luminescent materials include butadienes such as 1,4-diphenylbutadiene and tetraphenylbutadiene, and stilbenes, and US Pat. Nos. 4,356,429 and 5,516,577, the disclosures of which are hereby incorporated by reference in their entirety. It includes those exemplified in.

The luminescent materials are present, for example, in about 0.01 to about 10 weight percent of the layer, and for example, in about 1 to about 5 weight percent. Examples of luminescent materials include dyes selected from the group consisting of coumarin, dicyanomethylene pyranes, polymethine, oxabenzantran, xanthene, pyryllium, carbostil, perylene, etc., the dye being quinacridone derivatives. Is selected from. Examples of quinacridone dyes include quinacridone, 2-methylquinacridone, 2,9-dimethylquinacridone, 2-chloroquinacridone, 2-fluoroquinacridone, 1,2-benzoquinacrid Money, N, N'-dimethylquinacridone, N, N'-dimethyl-2-chloroquinacridone, N, N'-dimethyl-2-fluoroquinacridone, N, N'-dimethyl-1, 2-benzoquinacridone and the like. Exemplary classes of fluorescent materials are conjugated ring fluorescent dyes, examples of which are illustrated in US Pat. No. 3,172,862, the disclosure of which is incorporated herein by reference in its entirety, as perylene, rublin, anthracene, coronine, Phenanthressen and pyrene. In addition, fluorescent materials that can be used as dopants include butadienes such as 1,4-diphenylbutadiene and tetraphenylbutadiene, and stilbenes, and US Pat. Nos. 4,356,429 and 5,516,577 (the disclosures of which are incorporated herein by reference in their entirety). It includes those illustrated in).

Phosphorescent dyes are attracted to strong spin-orbit bonds, such as those disclosed in, for example, "Highly efficient organic phosphorescent emission from organic electroluminescent devices", Baldo et al., Letters to Nature, 395, pp 151-154 (1998). Organometallic compounds containing heavy metal elements. Non-limiting examples of such phosphors include 2,3,7,8,12,13,17,18-octaethyl, such as those disclosed in US Pat. No. 6,048,630, the disclosure of which is incorporated herein by reference in its entirety. -21H23H-phorpine platinum (II) (PtOEP) and others, and fac tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ).

The cathode comprises low work function components, such as metals having high work function components, such as metals having a work function in the range of about 4 eV to about 6 eV or metals having work function in the range of about 2.5 eV to about 4 eV. And suitable metals such as metals. The cathode may be derived from a combination of a low work function (about 4 eV, for example about 2 to about 4 eV) metal and at least one other metal. Effective fractions of the low work function metal relative to the second or other metal are from about 0.1% to about 99.9% by weight. Examples of low work function metals include, but are not limited to, alkali metals such as lithium or sodium; Group 2A or alkaline earth metals such as beryllium, magnesium, calcium or barium; And Group III metals including rare earth metals and actinide metals such as scandium, yttrium, lanthanum, cerium, europium, terbium or actinium. Lithium, magnesium, and calcium are preferred low work function metals.

The thickness of the cathode may, for example, range from about 10 nanometers to about 500 nanometers. The Mg: Ag cathodes of US Pat. No. 4,885,211, the disclosure of which is hereby incorporated by reference in its entirety, constitute one exemplary cathode structure. Another exemplary cathode is described in US Pat. No. 5,429,884, the disclosure of which is hereby incorporated by reference in its entirety, wherein the cathodes are formed from lithium alloys together with other high work function metals such as aluminum and indium. .

Both the anode and the cathode of the EL elements of the present invention may include a protective coating thereon, as will be understood by those skilled in the art. In addition, the positive electrode and the negative electrode may be formed in any convenient forms. The thin conductive layer can be coated onto a light transmissive substrate, for example a transparent or substantially transparent glass plate or plastic film. The EL element may comprise a light transmissive anode formed from tin oxide or indium tin oxide coated on a glass plate. Also, very thin, translucent metal anodes, such as gold, platinum, palladium, and the like, for example, in the range of less than about 200 angstroms, more specifically, from about 75 to about 150 angstroms, may be used. In addition, transparent or translucent thin film layers, such as conductive carbon or conjugated polymers such as polyaniline, polypyrrole, etc. in the range of about 50 to about 175 angstroms, may be selected as the anode. Any translucent polymer film can be employed as the substrate. Additional suitable forms of positive and negative electrodes are illustrated in US Pat. No. 4,885,211, the disclosure of which is incorporated herein by reference in its entirety.

The optional protective layer provided in contact with the cathode over the cathode may comprise any suitable metal such as silver, gold, or nonmetallic materials such as silicon oxide or the like.

Example I

2-bromonaphthalene (11.75 g 56.76 mmol) dissolved in anhydrous THF (150 mL) was placed in a 500 mL round bottom flask in argon atmosphere. The reaction was cooled to −78 ° C. (dry ice / acetone) and ⁿ BuLi (28.4 mL, 56.76 mmol) was added slowly over 15 minutes. The reaction was stirred for 3 hours, during which time the reaction temperature rose to room temperature. The reaction was again cooled to −78 ° C. and 2-t-butylanthraquinone (5.0 g, 18.92 mmol) (dissolved in 20 mL THF) was added dropwise to the reaction. Once addition was complete, the reaction was allowed to stir overnight at room temperature. The reaction was quenched with saturated aqueous ammonium chloride solution and ethyl acetate (100 mL) was added. The aqueous layer was removed and the organic layer was washed twice more with ammonium chloride sodium. The organic layer was collected, dried (MgSO ₄ ) and concentrated in vacuo to give a yellow oil which was used immediately in the next step. The product was dissolved in 1,4-dioxane (50 mL) and a mixture of 1: 1 H ₂ O: AcOH (25 mL) was added. Tin (II) chloride dihydrate (21.34 g, 94.60 mmol) was added and the reaction heated at 50 ° C. for 3 hours. The reaction was cooled to room temperature and methanol (50 mL) was added. The reaction mixture was filtered and the precipitate was washed with methanol. The solid was collected, dried and purified by Kaufmann column (alumina, cyclohexane). Further purification was achieved by sublimation (twice) at 320 ° C. to provide TBADN of greater than 99% purity.

Yes II

2-bromonaphthalene (10 g 63.69 mmol) dissolved in anhydrous THF (150 mL) was placed in a 500 mL round bottom flask in argon atmosphere. The reaction was cooled to −78 ° C. (dry ice / acetone) and ⁿ BuLi (32 mL, 63.69 mmol) was added slowly over 15 minutes. The reaction was stirred for 3 hours, during which time the reaction temperature rose to room temperature. The reaction was again cooled to -78 ° C and 2-t-butylanthraquinone (5.6 g, 21.23 mmol) (dissolved in 20 mL THF) was added dropwise to the reaction. Once addition was complete, the reaction was allowed to stir overnight at room temperature. The reaction was quenched with saturated aqueous ammonium chloride solution and ethyl acetate (100 mL) was added. The aqueous layer was removed and the organic layer was washed twice more with ammonium chloride sodium. The organic layer was collected, dried (MgSO ₄ ) and concentrated in vacuo to give a yellow oil which was used immediately in the next step. The product was dissolved in 1,4-dioxane (50 mL) and a mixture of 1: 1 H ₂ O: AcOH (75 mL) was added. Tin (II) chloride dihydrate (33.48 g, 148.73 mmol) was added and the reaction heated at 50 ° C. for 3 hours. The reaction was cooled to room temperature and methanol (50 mL) was added. The reaction mixture was filtered and the precipitate was washed with methanol. The solid was collected, dried and purified by Kaufmann column (alumina, cyclohexane). Further purification was achieved by sublimation (twice) at 260 ° C. to provide 2-tert-butyl-9,10-diphenylanthracene of greater than 99% purity.

Yes III

2-bromonaphthalene (10 g 58.47 mmol) dissolved in anhydrous THF (150 mL) was placed in a 500 mL round bottom flask in argon atmosphere. The reaction was cooled to −78 ° C. (dry ice / acetone) and ⁿ BuLi (29.2 mL, 58.47 mmol) was added slowly over 15 minutes. The reaction was stirred for 3 hours, during which time the reaction temperature rose to room temperature. The reaction was again cooled to −78 ° C. and 2-t-butylanthraquinone (5.2 g, 19.5 mmol) (dissolved in 20 mL THF) was added dropwise to the reaction. Once addition was complete, the reaction was allowed to stir overnight at room temperature. The reaction was quenched with saturated aqueous ammonium chloride solution and ethyl acetate (100 mL) was added. The aqueous layer was removed and the organic layer was washed twice more with ammonium chloride sodium. The organic layer was collected, dried (MgSO ₄ ) and concentrated in vacuo to give a yellow oil which was used immediately in the next step. The product was dissolved in 1,4-dioxane (50 mL) and a mixture of 1: 1 H ₂ O: AcOH (50 mL) was added. Tin (II) chloride dihydrate (21.93 g, 97.45 mmol) was added and the reaction heated at 50 ° C. for 3 hours. The reaction was cooled to room temperature and methanol (50 mL) was added. The reaction mixture was filtered and the precipitate was washed with methanol. The solid was collected, dried and purified by Kaufmann column (alumina, cyclohexane). Further purification was achieved by sublimation (twice) at 260 ° C. to provide 2-tert-butyl-9,10- (2-methyl) -diphenylanthracene of greater than 99% purity.

For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or ratios used in this specification and claims, and other numbers are modified in all instances to the term "about". Will be understood. Accordingly, unless indicated to the contrary, the numerical variables claimed in the following specification and the appended claims are approximations that may vary depending on the desired properties that the present disclosure attempts to obtain. At the very least, and not as an attempt to limit the application of the principles of equivalents to the scope of the claims, each numerical variable should at least be construed in light of the significant numbers reported and by applying ordinary approximation techniques.

As used in this specification and the appended claims, note that the singular forms "a", "an", and "the" include plural objects unless the context clearly and obviously is limited to one object. . Thus, for example, "a polar liquid" includes two or more different polar liquids. As used herein, the term "include" and its grammatical variants are used for non-limiting purposes, with the result that an enumeration of items in the list may be replaced or added to items in the list. It does not exclude similar items.

Although particular embodiments have been described, alternatives, modifications, changes, improvements, and substantial equivalents that may or may not be currently foreseen may occur to applicants or others skilled in the art. Accordingly, the claims appended at the time of submission and if there were amendments are considered to include all such alternatives, modifications, changes, improvements, and substantial equivalents.

According to the present invention, there is an advantage of providing a method of preparing a host material having a good color purity, high efficiency and good stability and having a wide energy gap.

Claims (20)

Reacting the naphthyllithium compound with 2-butylanthraquinone to generate a diol [Formula 3] ; And The [formula 3] of the diol by reaction with a reducing agent 2-tert-9,10-diaryl anthracene, the comprising the step of generating (β- naphthyl) anthracene-butyl-9,10-bis Method for dispensing . [Formula 3]

delete delete delete delete delete According to claim 1, A method for preparing 9,10-diarylanthracene , further comprising the step of reacting 2-bromonaphthalene with lithium to produce a naphthylithium compound. delete delete According to claim 1, The naphthyllithium compound is a method for preparing 9,10-diarylanthracene, characterized in that the reaction with the 2-butyl anthraquinone at room temperature. According to claim 1, The diol of [Formula 3] is a method for preparing 9,10- diaryl anthracene, characterized in that reacted with the reducing agent at 50 ℃ for 3 hours. delete According to claim 1, The reducing agent is a method for the preparation of 9,10-diaryl anthracene, characterized in that tin (II) chloride dihydrate. Preparing a 9,10-diarylanthracene comprising reacting a diol of Formula 3 with a reducing agent to produce 2-tert-butyl-9,10-bis- (β-naphthyl) anthracene Way for . [Formula 3]

delete The method of claim 14, The diol of [Formula 3] is a method for preparing 9,10- diaryl anthracene, characterized in that reacted with the reducing agent at 50 ℃ for 3 hours. The method of claim 14, The reducing agent is a method for the preparation of 9,10-diaryl anthracene, characterized in that tin (II) chloride dihydrate. delete delete delete

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