JP2022501400A - Method for producing steric hindrance nitrogen-containing heteroaromatic compound - Google Patents

Abstract

The present invention relates to a method for preparing a sterically hindered nitrogen-containing heteroaromatic compound, particularly for the use of electronic devices. The present invention further relates to compounds that can be obtained by that method and electronic devices comprising those compounds.

Description

Detailed description of the invention

The present invention relates to a method for preparing a sterically hindered heteroaromatic nitrogen compound. The present invention further relates to compounds that can be obtained by that method and electronic devices comprising those compounds.

Structures of organic electroluminescence devices (OLEDs) using organic semiconductors as functional materials are described, for example, in US453957, US5151629, EP0676461, and WO98 / 27136. The luminescent material used is often a phosphorescent organometallic complex. For quantum mechanical reasons, the use of organometallic compounds for phosphorescent illuminants can achieve up to four times the energy and output efficiencies. In general, there is still a need for improvements in OLEDs, especially in phosphorescent OLEDs, for example, with respect to efficiency, working voltage and lifetime. Also known are organic electroluminescence devices comprising a fluorescent emitter or a light emitter exhibiting TADF (thermally activated delayed fluorescence).

The properties of organic electroluminescence devices are not determined solely by the illuminant used. Of particular importance here are also other materials of particular use, such as host / matrix materials, hole blocking materials, electron transporting materials, hole transporting materials, and electron or exciton blocking materials. Improvements in these materials can result in a clear improvement in electroluminescence devices.

According to prior art, compounds having a bicyclic or tricyclic ring system are particularly used in the preparation of compounds exhibiting phosphorescence. These compounds serve as ligands, among others, in the corresponding complexes. The prior art includes, in particular, WO2014 / 0994960A1, WO2014 / 094941A1, WO2015 / 104045A1, WO2015 / 117718A1 and WO2016 / 124304. These documents do not show matrix materials, electron transport materials, hole transport materials, fluorescent emitters, or light emitters exhibiting TADF (Thermal Activated Delayed Fluorescence).

Further, Document WO2015 / 036078 discloses, among other things, heterocyclic compounds that can be used as matrix materials, electron transport materials or hole transport materials. Many of these compounds include bicyclic ring systems condensed into a pyridine or pyrazine structure, to which aromatic or heteroaromatic ring systems are in turn condensed.

The above compounds are relatively complex in preparation and produce a relatively high proportion of by-products. Further, in the preparation of the above compounds, it is required to be a relatively inexpensive and reactive starting material.

Moreover, when these materials are used, for example, as matrix materials, hole conduction materials or electron transport materials, there are still generally demands for improvements in device life, in particular with respect to efficiency and working voltage. be. Further, this compound is required to have high color purity.

A further object of the present invention is a compound suitable as a fluorescent emitter or a light emitter exhibiting TADF (thermally activated delayed fluorescence) in an organic electronic device, particularly an organic electroluminescence device, when used in this device. To provide (showing good element characteristics), and to provide the corresponding electronic element.

Therefore, it is an object of the present invention to provide a method for preparing these compounds, which is particularly simple and inexpensive. More specifically, this method led to high yields and minimal by-products. Moreover, the reaction conditions were very mild. Furthermore, in the preparation of the above compounds, it has been possible to use relatively inexpensive, readily available and low reactive starting materials.

A further object of the present invention is to provide a compound suitable for use in an organic electronic device, particularly an organic electroluminescence device (which leads to good device properties when used in this device). And to provide the corresponding electronic device.

A particular object of the present invention is to provide compounds that lead to long life, good efficiency and low working voltage. In particular, the properties of the matrix material, hole conductive material or electron transport material also have a significant effect on the life and efficiency of the organic electroluminescence device.

It can be said that a further problem to be solved by the present invention is to provide a compound suitable for use in phosphorescent or fluorescent OLEDs, particularly as a matrix material. More specifically, a problem to be solved by the present invention is to provide a matrix material suitable for red, yellow, and green phosphorescent OLEDs.

In addition, the compounds will lead to devices with excellent color purity, especially when used as matrix materials, hole conductive materials, or electron transport materials in organic electroluminescence devices.

In addition, the compound must be very easy to process and, in particular, have good solubility and film forming properties. For example, the compound must exhibit high oxidative stability and improved glass transition temperature.

It can be said that another purpose is to provide an electronic device having excellent performance at a very low price and with stable quality.

In addition, electronic devices must be able to be used or adapted for many purposes. In particular, the performance of electronic devices must be maintained over a wide temperature range.

Surprisingly, certain methods and compounds described in detail below have been found to achieve these objectives and eliminate the shortcomings of prior art. The use of the compound results in very good properties of organic electronic devices, especially organic electroluminescence devices, especially with respect to lifetime, efficiency and working voltage. Electronic devices, particularly organic electroluminescence devices, and corresponding preferred embodiments, including such compounds, are therefore provided by the present invention.

Therefore, the present invention provides a method for preparing a sterically hindered heteroaromatic nitrogen compound comprising the following steps.
A) Providing 1,2,4-triazine;
B) To provide an active alkene having a non-aromatic or non-heteroaromatic polycyclic ring system; and C) react the compounds provided in steps A) and B) with a sterically hindered heteroaromatic nitrogen compound. Including getting
The at least one compound provided in steps A) and / or B) is characterized by comprising an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and optionally substituted. And.

Preferably, the active double bond of the alkene provided in step B) may be part of a few or oligocyclic rings.

In a preferred embodiment, the alkene provided in step B) is preferably cyclic enolate and / or enamine.

Preferably, the alkene provided in step B) may be a few or oligocyclic ketones.

ここで、使用される記号は、以下のとおりである：
Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃは、同一であるかまたは異なり、Ｈ、Ｄ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｎ（Ｒ^１）_２、ＣＮ、ＮＯ_２、ＯＨ、ＣＯＯＨ、Ｃ（＝Ｏ）Ｎ（Ｒ^１）_２、Ｓｉ（Ｒ^１）_３、Ｂ（ＯＲ^１）_２、Ｃ（＝Ｏ）Ｒ^１、Ｐ（＝Ｏ）（Ｒ^１）_２、Ｓ（＝Ｏ）Ｒ^１、Ｓ（＝Ｏ）_２Ｒ^１、ＯＳＯ_２Ｒ^１、１〜２０の炭素原子を有する、直鎖の、アルキル、アルコキシもしくはチオアルコキシ基または２〜２０の炭素原子を有する、アルケニルもしくはアルキニル基または３〜２０の炭素原子を有する、分岐もしくは環状の、アルキル、アルコキシもしくはチオアルコキシ基（ここで、前記アルキル、アルコキシ、チオアルコキシ、アルケニルまたはアルキニル基は、それぞれ、１以上のＲ^１ラジカルによって置換されていてもよく、ここで、１以上の非隣接ＣＨ_２基は、Ｒ^１Ｃ＝ＣＲ^１、Ｃ≡Ｃ、Ｓｉ（Ｒ^１）_２、Ｃ＝Ｏ、ＮＲ^１、Ｏ、ＳまたはＣＯＮＲ^１によって置き換えられていてもよい）、または５〜４０の芳香族環原子を有し、それぞれのケースにおいて１以上のＲ^１ラジカルによって置換されていてもよい、芳香族もしくはヘテロ芳香族環系、または５〜４０の芳香族環原子を有し、１以上のＲ^１ラジカルによって置換されていてもよい、アリールオキシもしくはヘテロアリールオキシ基であり；同時に、２つのＲ^ａ、Ｒ^ｂおよび／またはＲ^ｃラジカルが共に単環もしくは多環の、脂肪族または芳香族環系を形成していてもよく；
Ｒ^１は、出現毎に同一であるかまたは異なり、Ｈ、Ｄ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｎ（Ｒ^２）_２、ＣＮ、ＮＯ_２、Ｓｉ（Ｒ^２）_３、Ｂ（ＯＲ^２）_２、Ｃ（＝Ｏ）Ｒ^２、Ｐ（＝Ｏ）（Ｒ^２）_２、Ｓ（＝Ｏ）Ｒ^２、Ｓ（＝Ｏ）_２Ｒ^２、ＯＳＯ_２Ｒ^２、１〜２０の炭素原子を有する、直鎖の、アルキル、アルコキシもしくはチオアルコキシ基または２〜２０の炭素原子を有する、アルケニルもしくはアルキニル基または３〜２０の炭素原子を有する、分岐もしくは環状の、アルキル、アルコキシもしくはチオアルコキシ基（ここで、それぞれのアルキル、アルコキシ、チオアルコキシ、アルケニルまたはアルキニル基は、それぞれ、１以上のＲ^２ラジカルによって置換されていてもよく、ここで、１以上の非隣接ＣＨ_２基は、Ｒ^２Ｃ＝ＣＲ^２、Ｃ≡Ｃ、Ｓｉ（Ｒ^２）_２、Ｃ＝Ｏ、ＮＲ^２、Ｏ、ＳまたはＣＯＮＲ^２によって置き換えられていてもよい）、または５〜４０の芳香族環原子を有し、それぞれのケースにおいて１以上のＲ^２ラジカルによって置換されていてもよい、芳香族もしくはヘテロ芳香族環系、または５〜４０の芳香族環原子を有し、１以上のＲ^２ラジカルによって置換されていてもよい、アリールオキシもしくはヘテロアリールオキシ基、または５〜４０の芳香族環原子を有し、１以上のＲ^２ラジカルによって置換されていてもよい、アラルキルもしくはヘテロアラルキル基、または１０〜４０の芳香族環原子を有し、１以上のＲ^２ラジカルによって置換されていてもよい、ジアリールアミノ基、ジヘテロアリールアミノ基もしくはアリールヘテロアリールアミノ基であり；同時に、２以上の、好ましくは隣接するＲ^１ラジカルが共に、単環もしくは多環の、脂肪族または芳香族環系を形成していてもよく；
Ｒ^２は、出現毎に同一であるかまたは異なり、Ｈ、Ｄ、Ｆ、または１〜２０の炭素原子を有する、脂肪族、芳香族および／またはヘテロ芳香族有機ラジカル、特にヒドロカルビルラジカル、（ここで、１以上の水素原子がＦによって置き換えられていてもよい）であり、同時に、２以上の、好ましくは隣接する置換基Ｒ^２が共に、単環もしくは多環の、脂肪族または芳香族環系を形成していてもよい。 In a preferred embodiment, 1,2,4-triazine can be represented by formula (I).

Here, the symbols used are:
R ^a , R ^b , R ^c are the same or different, H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , OH, COOH, C (= O). N (R ¹ ) ₂ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S ( = O) ₂ R ¹ , OSO ₂ R ¹ , linear, alkyl, alkoxy or thioalkoxy groups with 1 to 20 carbon atoms or alkenyl or alkynyl groups or 3 to 20 with 2 to 20 carbon atoms. carbon atoms having a branched or cyclic alkyl, wherein the alkoxy or thioalkoxy group (said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group, respectively, substituted by one or more R ¹ radicals well, wherein one or more non-adjacent CH ₂ groups ^{may, R 1 C = CR 1,} C≡C, Si (R 1) 2, C = O, NR 1, O, has been replaced by S or CONR ¹ may be), or a 5 to 40 aromatic ring atoms, which may be substituted by one or more R ¹ radicals in each case, an aromatic or heteroaromatic ring system, or 5 to 40 of It is an aryloxy or heteroaryloxy group that has an aromatic ring atom and may ^{be substituted with one or more R 1} radicals; at the same time, the two ^Ra , R ^b and / or R ^c radicals are both single. It may form a ring or polycyclic, aliphatic or aromatic ring system;
R ¹ is the same or different for each appearance, H, D, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , Si (R ² ) ₃ , B (OR ² ). ₂ , C (= O) R ² , P (= O) (R ² ) ₂ , S (= O) R ² , S (= O) ₂ R ² , OSO ₂ R ² , 1 to 20 carbon atoms A linear, alkyl, alkoxy or thioalkoxy group or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms ( wherein each alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group, respectively, may be optionally substituted by one or more R ² radicals, wherein one or more non-adjacent CH ₂ groups, R ² C = CR ² , C≡C, Si (R ² ) ₂ , C = O, NR ² , may be replaced by O, S or CONR ² ), or having 5-40 aromatic ring atoms. in each case may be substituted by one or more R ² radicals, have aromatic or aromatic ring atom of a heteroaromatic ring system or 5 to 40, optionally substituted by one or more R ² radicals may have aryloxy or heteroaryloxy group or 5 to 40 aromatic ring atoms, it may be substituted by one or more R ² radicals, aralkyl or heteroaralkyl group, or 10 to 40, It has an aromatic ring atoms, optionally substituted by one or more R ² radicals, diarylamino group, a di-heteroarylamino group or aryl heteroarylamino group; simultaneously, two or more, preferably adjacent R ¹ radicals are both monocyclic or polycyclic, may form an aliphatic or aromatic ring system;
R ² is, to or different on each occurrence, identically with H, D, F, or 1 to 20 carbon atoms, aliphatic, aromatic and / or heteroaromatic organic radical, especially hydrocarbyl radicals, (wherein in a one or more hydrogen atoms may be replaced by F), at the same time, 2 or more, preferably both substituents R ² adjacent, monocyclic or polycyclic, aliphatic or aromatic ring It may form a system.

Preferably, at least one of the R ^a , R ^b , R ^c radicals has 5 to 40 aromatic ring atoms and may be substituted with ^{one or more R 1 radicals in each case.} Alternatively, it may be a heteroaromatic ring system, wherein preferably ^{at least one of the Ra} and / or ^Rb radicals is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms. , R ^b radicals are more preferably aromatic or heteroaromatic ring systems with 5-40 aromatic ring atoms.

In the context of the present invention, adjacent carbon atoms are carbon atoms that are directly bonded to each other. Further, in the definition of radical, "adjacent radical" means that these radicals are bonded to the same carbon atom or to an adjacent carbon atom. These definitions also apply, in particular, to the terms "adjacent groups" and "adjacent substituents".

The expression that two or more radicals may form a ring with each other is in the context of the invention, in particular, the two radicals are linked together by chemical bonds under the formal removal of two hydrogen atoms. It is understood to mean that. This is illustrated by the scheme below:

Furthermore, however, the above expression also means that if one of the two radicals is hydrogen, the second radical binds to the bonded position of the hydrogen atom to form a ring. It is understood that. This is illustrated by the scheme below:

A fused aryl group, a fused aromatic ring system, or a fused heteroaromatic ring system, in the context of the present invention, has two or more aromatic groups fused to each other via one common side, that is, fused rings. Yes, for example, two carbon atoms are groups that belong to at least two aromatic or heteroaromatic rings, such as in naphthalene. In contrast, for example, fluorene is not a condensed aryl group in the context of the present invention, as the two aromatic groups in fluorene do not have a common edge. Corresponding definitions apply to heteroaryl groups and to fused ring systems that may or may not contain heteroatoms.

When two or more, preferably adjacent R, R ¹ and / or R ² radicals together form a ring system, the result is a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system. It may be there.

In the context of the present invention, the aryl group comprises 6-60 carbon atoms, preferably 6-40 carbon atoms, more preferably 6-30 carbon atoms; in the context of the present invention, the heteroaryl group is 2 It contains from 60 to 60 carbon atoms, preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and the heteroatoms is at least 5. This heteroatom is preferably selected from N, O and / or S. Here, the aryl group or heteroaryl group is a single aromatic ring, that is, benzene, or a single heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as naphthalene. It is understood to mean anthracene, benzene, quinoline, isoquinolin, etc.

In the context of the present invention, the aromatic ring system has 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms in the ring system. In the context of the present invention, a heteroaromatic ring system comprises 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms and at least one heteroatom in the ring system. However, the total of carbon atoms and heteroatoms is at least 5. This heteroatom is preferably selected from N, O and / or S. In the context of the present invention, aromatic or heteroaromatic ring systems do not necessarily contain only aryl or heteroaryl groups, in which two or more aryl or heteroaryl groups are non-aromatic units (other than H). It should be understood to mean a system in which the atoms are preferably less than 10%), eg, can also be blocked by carbon, nitrogen or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilben and the like are also therefore also considered aromatic ring systems in the context of the present invention and are also thereof. The same applies to a system in which two or more aryl groups are blocked by, for example, a linear or cyclic, an alkyl group, or a silyl group. Further, a system in which a plurality of aryl or heteroaryl groups are directly bonded to each other, for example, biphenyl, terphenyl, quarterphenyl or bipyridine, is also regarded as an aromatic or heteroaromatic ring system.

In the context of the present invention, cyclic, alkyl, alkoxy or thioalkoxy groups are understood to mean monocyclic, bicyclic or polycyclic groups.

In the context of the present invention, each hydrogen atom or CH ₂ group may be substituted with the groups described above, wherein _{the alkyl groups C 1 to} C ₂₀ are, for example, methyl, ethyl, n-propyl. , I-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, Cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo [2.2.2] octyl, 2-bicyclo [2.2.2] octyl, 2- (2,6-- Dimethyl) octyl, 3- (3,7-dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1 , 1-dimethyl-n-hepta-1-yl, 1,1-dimethyl-n-octa-1-yl, 1,1-dimethyl-n-dece-1-yl, 1,1-dimethyl-n- Dodece-1-yl, 1,1-dimethyl-n-tetradece-1-yl, 1,1-dimethyl-n-hexadece-1-yl, 1,1-dimethyl-n-octadese-1-yl, 1, 1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hepta-1-yl, 1,1-diethyl-n-octa-1-yl, 1,1-diethyl-n-dece -1-yl, 1,1-diethyl-n-dodece-1-yl, 1,1-diethyl-n-tetradeceth-1-yl, 1,1-diethyl-n-hexadeceth-1-yl, 1,1 -Diethyl-n-octadece-1-yl, 1- (n-propyl) cyclohexa-1-yl, 1- (n-butyl) cyclohexa-1-yl, 1- (n-hexyl) cyclohexa-1-yl, It is understood to mean 1- (n-octyl) cyclohexa-1-yl and 1- (n-decyl) cyclohexa-1-yl radicals. The alkenyl group is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, or cyclooctadienyl. The alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, or octynyl. Alkoxy groups C _{1 to} C ₄₀ can be, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, or 2-methylbutoxy. It is understood to mean.

It has 5 to 60, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 30 aromatic ring atoms, which may be substituted with the above-mentioned radicals in each case, and may be optionally substituted. An aromatic or heteroaromatic ring system, which may be attached to an aromatic or heteroaromatic system at a position, is understood to mean, for example, a group derived from: benzene, naphthalene. , Anthracene, Benzanthracen, Phenantren, Benzophenanthrene, Pyrene, Chrysen, Perylene, Fluolanthen, Benzofluoranthen, Naphthase, Pentacen, Bentopylene, Biphenyl, Biphenylene, Tarphenyl, Turphenylene, Fluorene, Spirobifluorene, Dihydrophenantren, Dihydro Pyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-monobenzoindenofluorene, cis-or trans-dibenzoindenofluorene, turxin, isotorxene, spirothulficene, spirisoturxene, furan, benzofurans, Isobenzofurans, dibenzofurans, thiophenes, benzothiophenes, isobenzothiophenes, dibenzothiophenes, pyrroles, indols, isoindoles, carbazoles, indolocarbazoles, indenocarbazoles, pyridines, quinolines, isoquinolins, acridins, phenanthridines, benzo-5, 5, 6-Kinolin, Benzo-6,7-Kinolin, Benzo-7,8-Kinolin, Phenothiazine, Phenoxazine, Pyrazole, Indazole, Imidazole, Benzimidazole, Naftimidazole, Phenantry imidazole, Pyridyl imidazole, Pyrazine imidazole, Kinoxalin imidazole , Oxazole, benzoxazole, naphthoxazole, antroxazole, phenanthrooxazole, isooxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxalin, 1, 5-diazaanthracene, 2,7-diazapylene, 2,3-diazapylene, 1,6-diazapylene, 1,8-diazapylene, 4,5-diazapylene, 4,5,9,10-tetraazaperylene, pyrazine, Phenazine, phenoxazine, phenothiazine, fluorbin, naphthylidine, azacarbazole, benzocarbo Phosphorus, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxa Diazol, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5 -Triazine, 1,2,4-triazine, 1,2,3-triazole, tetrazole, 1,2,4,5-tetrazole, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine , Purine, pteridine, indolidin, and benzothiadiazole.

ここで、使用される記号は以下のとおりである：
Ｘは、ＯＨ、ＯＲ^ｄまたはＮＲ^ｄ _２であり；
Ｒ^ｄは、Ｈ、Ｄ、１〜２０の炭素原子を有する、直鎖の、アルキル、アルコキシもしくはチオアルコキシ基または２〜２０の炭素原子を有する、アルケニルもしくはアルキニル基または３〜２０の炭素原子を有する、分岐もしくは環状の、アルキル、アルコキシもしくはチオアルコキシ基（ここで、前記アルキル、アルコキシ、チオアルコキシ、アルケニルまたはアルキニル基は、それぞれのケースにおいて、１以上のＲ^１ラジカルによって置換されていてもよい）であり；同時に、２つのＲ^ｄラジカルが共に、環系を形成していてもよく、ここで、Ｒ^１は上記、特に式（Ｉ）、に記載のとおりであり；
ここで、前記二環／多環は、１以上の置換基Ｒを有していてもよく、かつ
Ｒは、出現毎に同一であるかまたは異なり、Ｈ、Ｄ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｎ（Ｒ^１）_２、ＣＮ、ＮＯ_２、ＯＨ、ＣＯＯＨ、Ｃ（＝Ｏ）Ｎ（Ｒ^１）_２、Ｓｉ（Ｒ^１）_３、Ｂ（ＯＲ^１）_２、Ｃ（＝Ｏ）Ｒ^１、Ｐ（＝Ｏ）（Ｒ^１）_２、Ｓ（＝Ｏ）Ｒ^１、Ｓ（＝Ｏ）_２Ｒ^１、ＯＳＯ_２Ｒ^１、１〜２０の炭素原子を有する、直鎖の、アルキル、アルコキシもしくはチオアルコキシ基または２〜２０の炭素原子を有する、アルケニルもしくはアルキニル基または３〜２０の炭素原子を有する、分岐もしくは環状の、アルキル、アルコキシもしくはチオアルコキシ基（ここで、前記アルキル、アルコキシ、チオアルコキシ、アルケニルまたはアルキニル基は、それぞれ、１以上のＲ^１ラジカルによって置換されていてもよく、ここで、１以上の非隣接ＣＨ_２基は、Ｒ^１Ｃ＝ＣＲ^１、Ｃ≡Ｃ、Ｓｉ（Ｒ^１）_２、Ｃ＝Ｏ、ＮＲ^１、Ｏ、ＳまたはＣＯＮＲ^１によって置き換えられていてもよい）、または５〜４０の芳香族環原子を有し、それぞれのケースにおいて、１以上のＲ^１ラジカルによって置換されていてもよい、芳香族もしくはヘテロ芳香族環系、または５〜４０の芳香族環原子を有し、それぞれのケースにおいて、１以上のＲ^１ラジカルによって置換されていてもよい、アリールオキシもしくはヘテロアリールオキシ基であり；同時に、２つのＲラジカルが共に、単環もしくは多環の、脂肪族または芳香族環系を形成していてもよく、ここで、Ｒ^１は上記、特に式（Ｉ）、に記載のとおりである。 The active alkene can preferably be represented by formula (II).

Here, the symbols used are:
X is OH, OR ^d or NR ^d ₂ ;
R ^d is a linear, alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or 3 to 20 carbon atoms. having, branched or cyclic, alkyl, alkoxy or thioalkoxy group (wherein said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group, in each case, may be substituted by one or more R ¹ radicals ); At the same time, the two R ^d radicals may together form a ring system, where R ¹ is as described above, in particular in formula (I);
Here, the bicyclic / polycyclic ring may have one or more substituents R, and R may be the same or different for each appearance, H, D, F, Cl, Br, I. , N (R ¹ ) ₂ , CN, NO ₂ , OH, COOH, C (= O) N (R ¹ ) ₂ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ , OSO ₂ R ¹ , linear, alkyl, alkoxy having 1 to 20 carbon atoms. Alternatively, a branched or cyclic, alkyl, alkoxy or thioalkoxy group having an alkoxy or alkynyl group or 3 to 20 carbon atoms having a thioalkoxy group or 2 to 20 carbon atoms (here, said alkyl, alkoxy, thio). alkoxy, alkenyl or alkynyl group, respectively, may be optionally substituted by one or more ^{R 1} radicals, wherein one or more non-adjacent CH ₂ groups ^{may, R 1 C = CR 1,} C≡C, Si ( _{^{R 1) 2, C = O}} , NR 1, O, may be replaced by S or CONR ^1), or a 5 to 40 aromatic ring atoms, in each case, one or more of ^{R 1} may be substituted by a radical, have aromatic or aromatic ring atom of a heteroaromatic ring system or 5 to 40, in each case, it may be substituted by one or more R ¹ radicals, It is an aryloxy or heteroaryloxy group; at the same time, the two R radicals may both form a monocyclic or polycyclic, aliphatic or aromatic ring system, where R ¹ is described above, in particular. It is as described in the formula (I).

ここで、示された式（ＩＩａ）〜（ＩＩｏ）の構造は、１以上のＲ^１ラジカルによって置換されていてもよく、ここで、Ｒ^１は、上記、特に式（Ｉ）、に記載のとおりである In a preferred embodiment, the alkene provided in step B) may be derived from a ketone of formulas (IIa)-(IIo).

Here, the structure of the indicated formula (IIa) ~ (IIo), may be optionally substituted by one or more ^{R 1} radicals, wherein, ^{R 1} is above, in particular formula (I), according to Is right

In one embodiment, the active alkene provided in step B) may be a chiral compound and may be used in excess of enantiomer.

In a further form, the active alkene provided in step B) may be a chiral compound and may be used in a racemate.

As already presented, the active alkene provided in step B) can be obtained from a ketone via an appropriate reaction. The corresponding ketones, in particular the ketones of formulas (IIa)-(IIo), are commercially available in many cases, and both racemic and enantiomeric excess compositions can be used. An overview of the corresponding CAS numbers is as follows:

Preferred two or three or oligocyclic ketones may be used, for example, in the form of enolate or in the form of enamine derivatives.

For example, preferred enamines are secondary amines, particularly preferably cyclic secondary amines such as pyrrolidine [123-75-1], piperidine [110-89-4] and morpholine [110-91-8]. ] Can be prepared using. The reaction can be carried out in a suitable solvent, preferably a hydrocarbon solvent such as heptane, cyclohexane. In addition, the reaction can be accelerated by a catalyst such as titanium tetrachloride.

The preparation of enolates or enamines from a few or oligocyclic ketones is, in principle, known from the literature of similar compounds and is readily applicable to the preparation of compounds of the invention by those of skill in the art. Further information is confirmed from the examples.

Step C) is performed at a temperature of less than 200 ° C, preferably less than 160 ° C.

Further, step C) may be a case performed in a solvent. Preferably, a high boiling point inert solvent can also be used. Typical solvents include dichlorobenzene, benzonitrile, nitrobenzene, DMSO, DMAC, NMP, di-, tri-, oligo- / polyether such as tetraethylene glycol dimethyl ether and the like. A more suitable solvent has a boiling point of less than 150 ° C., in which case the reaction is preferably carried out in a stirred autoclave. Typical solvents having a boiling point of less than 150 ° C. are, for example, heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, dioxane, acetone, ethyl acetate, butyl acetate, acetonitrile and the like. The above solvent may be used alone or in combination.

Further, the molar ratio of 1,2,4-triazine to the active alkene, preferably enamine or enolate, is preferably in the range of 2.0: 1.0 to 0.5: 2.0, more preferably 1. The case may be in the range of 0.0: 1.0 to 1.0: 1.2.

The above preparation method is known from the literature of similar compounds in principle, and is easily applied to the preparation of the compound of the present invention by those skilled in the art. For example, the reaction of 1,2,4-triazine with an active alkene is described in the following literature: Boger, Dale L. Boger, Dale L. Zhang, Minsheng, e-EROS Encyclopedia of Reagents for Organic Synthesis (2001); Boger, Dale L. Boger, Dale L. and Panek, James S. , Journal of Organic Chemistry, 46 (10), 2179-82; 1981. However, these documents do not include suggestions for compounds as active ingredients in electronic devices. More specifically, the 1,2,4-triazines used in the prior art do not react with polycyclic compounds. Further information is given in the examples.

1,2,4-triazine is preferably obtained by the reaction of 1,2-dicarbonyl with formamide razone. In one form, formamide razone is preferably obtained in situ by reacting the amidine compound with hydrazine.

The combination of steps A), B) and C) of the present invention, which prepares 1,2,4-triazine by the reaction of 1,2-dicarbonyl with formamide razone, makes predictions in terms of cost, purity and yield. It can give you more benefits. Therefore, this combination can achieve a synergistic effect.

ここで、記号Ｒ^ｂおよびＲ^ｃは上記、特に式（Ｉ）、に記載の意味を有する。 In a preferred embodiment, may be the case represented by formula (III).

Here, the symbols R ^b and R ^c have the meanings described above, particularly in formula (I).

ここで、記号Ｒ^ｂは上記、特に式（Ｉ）、に記載の意味を有する。 Formamide razone can preferably be represented by formula (IV).

Here, the symbol R ^b has the meaning described above, particularly in the formula (I).

The principle of the above preparation method of 1,2,4-triazine by the reaction of 1,2-dicarbonyl and formamide razone is known in principle from the literature of similar compounds, and those skilled in the art will appreciate the compounds of the present invention. It can be easily applied to the preparation. Further information can be obtained from the examples.

Furthermore, the reaction with formamide razone and / or 1,2-dicarbonyl compounds may be carried out in a solvent. Typical solvents include, for example, alcohol, methanol, ethanol and the corresponding polar solvents. The above solvent may be used alone or in combination. The resulting 1,2,4-triazine can be obtained by a known method, eg, a suitable solvent or solvent mixture (typical solvents are, for example: heptane, cyclohexane, toluene, methyltert-butyl ether, THF, dioxane, etc. It can be purified by crystallization from acetone, ethyl acetate, butyl acetate, acetonitrile, isopropanol, ethanol, methanol, etc., or by chromatography / flash chromatography on silica gel or aluminum oxide.

The principle of the above preparation method is known from the literature of similar compounds in principle, and those skilled in the art can easily apply it to the preparation of the compound of the present invention. For example, the preparation of formamide razone was made by Patrick J. et al. G. Saris and Mark E. Thomasson, Org. Let. 2016, 18, 3960-3963, their reaction with 1,2-dicarbonyl compounds is described in Science of Synthesis. Further information can be obtained from the examples.

In a further embodiment of the invention, 1,2,4-triazine may be the case obtained by reaction of a nitroaromatic or nitroheteroaromatic with an amidine compound.

The principle of the above preparation method for 1,2,4-triazine by the reaction of a nitroaromatic or nitroheteroaromatic with an amidine compound is known in principle from the literature of similar compounds, and those skilled in the art are skilled in the art. Can be easily applied to the preparation of compounds of. For example, such reactions are described in Suzuki, Hitomi and Kawakami, Takehiko in Journal of Organic Chemistry (JOC), 1999, 64, 3361 (DOI: 10.102 / jo982139m). Further information can be obtained from the examples.

The compounds obtained by steps A) to C) can be reacted with a further compound comprising at least one aromatic or heteroaromatic atmosphere in a known coupling reaction, which is a necessary condition for this purpose. Is known to those of skill in the art, and the detailed description in the examples assists one of ordinary skill in the art in carrying out these reactions.

Particularly preferred and preferred coupling reactions that result in CC and / or CN bond formation are by Buchwald, Suzuki, Yamamoto, Stille, Heck, Negishi, Sonogashira and Hiyama. These reactions are well known and the examples provide further guidance to those of skill in the art.

The principle of the above preparation method is known from the literature of similar compounds in principle, and those skilled in the art can easily apply it to the preparation of the compound of the present invention. Further information can be obtained from the examples.

By these methods, the compounds according to the invention can be obtained in high purity (preferably greater than 99%) by subsequent purification (eg, recrystallization or sublimation) as needed ( ^{1 1} H NMR and / or). Specified by HPLC).

In a further embodiment, the compound obtained by the method of the invention may comprise at least two, preferably three fused rings, which may be substituted if desired.

In a further form, at least one of the compounds provided in step A) and / or step B) comprises a hole transport group, or the product obtained in step C) comprises a hole transport group. It may be a compound case, in which case the R, ^Ra , R ^b or R ^c group comprises a hole transport group in the structures of formulas (I)-(IV), preferably positive. It constitutes a hole transport group. Hole transport groups are known in the art and they preferably contain a triarylamine or carbazole group.

ここで、点線は接続位置を示し、そして
Ａｒ^２、Ａｒ^３、Ａｒ^４は、それぞれ独立に、６〜４０の炭素原子を有するアリール基または３〜４０の炭素原子を有するヘテロアリール基（これらのそれぞれは１以上のＲ^１ラジカルによって置換されていてもよい）であり；
ｐは、０または１であり、かつ
Ｚは、結合、またはＣ（Ｒ^１）_２、Ｓｉ（Ｒ^１）_２、Ｃ＝Ｏ、Ｎ−Ｒ^１、Ｎ−Ａｒ^１、ＢＲ^１、ＰＲ^１、ＰＯ（Ｒ^１）、ＳＯ、ＳＯ_２、Ｓｅ、ＯまたはＳであり、好ましくは、結合、またはＣ（Ｒ^１）_２、Ｎ−Ｒ^１、ＯまたはＳ、（ここで記号Ｒ^１は、上記、特に式（Ｉ）、に記載の意味を有する）であり、Ａｒ^１は、６〜４０の炭素原子を有するアリール基または３〜４０の炭素原子を有するヘテロアリール基（これらのそれぞれは１以上のＲ^１ラジカルによって置換されていてもよい）である。さらに、Ｎ−Ｎ結合の存在は、好ましくは除外される。 The hole transport group preferably comprises the formulas (H-1) to (H-3), and is preferably a group selected from the formulas (H-1) to (H-3). You can do it.

Here, the dotted line indicates the connection position, and Ar ² , Ar ³ , and Ar ⁴ are independently aryl groups having 6 to 40 carbon atoms or heteroaryl groups having 3 to 40 carbon atoms (of these). each be optionally substituted by one or more R ¹ radicals);
p is 0 or 1 and Z is a bond or C (R ¹ ) ₂ , Si (R ¹ ) ₂ , C = O, N-R ¹ , N-Ar ¹ , BR ¹ , PR ¹ , PO (R ¹ ), SO, SO ₂ , Se, O or S, preferably coupled or C (R ¹ ) ₂ , N-R ¹ , O or S, (where the symbol R ¹ is above. , In particular having the meaning set forth in formula (I), where Ar ¹ is an aryl group having 6-40 carbon atoms or a heteroaryl group having 3-40 carbon atoms (each of which is one or more). substituted by R ¹ radicals may also be). Furthermore, the presence of NN bonds is preferably excluded.

ここで、Ｙ^１は、Ｏ、Ｓ、Ｃ（Ｒ^１）_２、ＮＲ^１またはＮＡｒ^１であり、点線は接続位置を示し、ｅは、０、１または２であり、ｊは、０、１、２または３であり、ｈは、出現毎に同一であるかまたは異なり、０、１、２、３または４であり、ｐは、０または１であり、Ｒ^１は、上記、特に式（Ｉ）、に記載の意味を有し、Ａｒ^１およびＡｒ^２は、上記、特に式（Ｈ−１）または（Ｈ−２）、に記載の意味を有する。同時に、Ｎ−Ｎ結合の存在は、好ましくは除外される。 Further, the hole transport group comprises a group selected from the formulas (H-4) to (H-26), preferably a group selected from the formulas (H-4) to (H-26). It may be a case.

Here, Y ¹ is O, S, C (R ¹ ) ₂ , NR ¹ or NA ¹ , the dotted line indicates the connection position, e is 0, 1 or 2, and j is 0, 1. , 2 or 3, h is the same or different for each appearance, 0, 1, 2, 3 or 4, p is 0 or 1, and R ¹ is the above, in particular the formula ( ^{I), and Ar 1} and Ar ² have the meanings described in the above, in particular, the formula (H-1) or (H-2). At the same time, the presence of NN bonds is preferably excluded.

It is clear from the above description that when the subscript p = 0, the corresponding Ar ² groups do not exist and a bond is formed.

Preferably, the Ar ² groups are directly conjugated with an ^{aromatic or heteroaromatic radical, or a nitrogen atom to which the Ar 2} groups of formulas (H-1)-(H-26) may be attached. ) May be formed.

In a further preferred embodiment of the invention, Ar ² is an aromatic heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms. , which is one or more of R ¹ may be substituted by a radical, preferably unsubstituted, wherein, R ¹ is above, in particular have the meanings described in formula (I) May be good. More preferably, Ar ² is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which is one or more. R may be substituted by ¹ radical, but is preferably unsubstituted, wherein, R ¹ is, the may be particularly have the meaning according to formula (I).

^{More preferably, the symbols Ar 2} represented by the formulas (H-1) to (H-26) are, in particular, 5 to 24 ring atoms, preferably 6 to 13 ring atoms, and more preferably 6 to 10 rings. Aryl or heteroaryl radicals having atoms, the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system, directly attaches to each atom of the additional group, i.e. aromatic or heteroaromatic group. Joined through.

^{It may be the case where the symbol Ar 2} represented by the formulas (H-1) to (H-26) comprises an aromatic ring system having 2 or less aromatic and / or heteroaromatic 6-membered rings; Preferably, it does not contain any fused aromatic or heteroaromatic ring system that condenses with the fused 6-membered ring. Therefore, the naphthyl structure is preferred over the anthracene structure. Further, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures. Particularly preferred are structures without condensation, such as phenyl, biphenyl, terphenyl and / or quarterphenyl structures.

^{The two} Ar groups represented by the formulas (H-1) to (H-26) have, in particular, 1 or less nitrogen atoms, preferably 2 or less heteroatoms, particularly preferably 1 or less heteroatoms, and are special. It may be a case that does not have a hetero atom.

In a further preferred embodiment of the invention, Ar ³ and / or Ar ⁴ are the same or different at each appearance and have 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms. Group or heteroaromatic ring systems, more preferably aromatic ring systems with 6-12 aromatic ring atoms, or heteroaromatic ring systems with 6-13 aromatic ring atoms, these. it may be substituted by one or more R ¹ radicals are each, but is preferably unsubstituted, wherein, R ¹ is, the may be particularly have the meanings formula (I), the.

In a more preferred embodiment, at least one of the compounds provided in step A) and / or step B) comprises an electron-transporting group-containing radical, or the product obtained in step C) contains an electron-transporting property. It may be a case of reacting with a radical-containing compound, and in this case, in the formulas (I) to (IV), the R, R ^a , R ^b or R ^c group is preferably an electron transporting group-containing radical. Containing, preferably composed of an electron transporting group-containing radical. Electron transport groups are widely known in the art and facilitate the ability of a compound to transport and / or conduct electrons.

Further, it comprises at least one structure selected from the group of pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole, particularly preferably pyrimidine, triazine and quinazoline. The compounds obtained by the method of the present invention show surprising advantages. These structures generally promote the ability of the compound to transport and / or conduct electrons.

ここで、Ｌ^１は、結合、または５〜４０、好ましくは５〜３０の芳香族環原子を有し、１以上のＲ^１ラジカルによって置換されていてもよい、芳香族もしくはヘテロ芳香族環系であり、Ｑは電子輸送基であり、ここで、Ｒ^１は、上記、特に式（Ｉ）、に記載の意味を有し、点線は接続位置を示す。 In a preferred embodiment of the present invention, the electron transporting group-containing radical comprises a group represented by the formula (QL), and may be preferably a group represented by the formula (QL).

Here, L ¹ is a bond, or 5 to 40, preferably having 5 to 30 aromatic ring atoms, which may be substituted by one or more R ¹ radical, an aromatic or heteroaromatic ring system Where Q is an electron transport radical, where R ¹ has the meaning described above, in particular, in formula (I), where the dotted line indicates the connection position.

Preferably, L ¹ groups, Q groups, and with equation (QL) atom L ¹ group is attached to (preferably a carbon or nitrogen atom) may form a conjugated directly. Direct conjugation of aromatic or heteroaromatic systems is formed as soon as a direct bond is formed between adjacent aromatic or heteroaromatic rings. Further bonds between the above-mentioned conjugated groups, for example via sulfur, nitrogen or oxygen atoms or carbonyl groups, do not impair the conjugate. In the case of fluorene systems, the two aromatic rings are directly bonded, where the SP ³ -hybrid carbon atom at position 9 interferes with the condensation of these rings, but conjugation is possible. This is because the SP ³ -mixed carbon atom at the 9-position is not necessarily located between the electron-transporting Q group and the atom (through which the group of formula (QL) is attached to a further structural element of the compound of the invention). This is not always the case. In contrast, in the case of the second spirobifluorene structure, and Q groups, the bond between aromatic or heteroaromatic radical L ¹ group of formula (QL) is bonded, in spirobifluorene structure Direct conjugation can be formed when bonded via the same phenyl radicals or directly bonded to each other and via phenyl groups in a spirobifluorene structure present in one plane. And Q group, the bond between the aromatic or heteroaromatic radical L ¹ group of formula (QL) are attached, the 9-position of SP 3 ^- second spirobi attached through a hybridized carbon atoms Conjugation is hindered when mediated by different phenyl radicals of the fluorene structure.

In a further preferred embodiment of the present invention, L ¹ is a bond, or an aromatic or heteroaromatic ring atoms 5-14 is preferably an aromatic ring system having 6 to 12 carbon atoms, one or more of R ¹ It may be substituted with radicals, but is preferably unsubstituted, where R ¹ may have the meaning described above, particularly in formula (I). More preferably, L ¹ is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which has one or more Rs. ^It may be substituted with one radical, but is preferably unsubstituted, where R ¹ may have the meaning described above, particularly in formula (I).

More preferably, the symbol L ¹ represented in formula (QL) is, among other things, identical or different for each appearance, with bonds or 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably. An aryl or heteroaryl radical having 6 to 10 ring atoms, the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system directly to each atom of the additional group, i.e. aromatic or heteroaromatic. It is bonded via a radical.

^{Further, the L 1} group represented by the formula (QL) comprises an aromatic ring system having 2 or less aromatic and / or heteroaromatic 6-membered rings, preferably any condensed aromatic or heteroaromatic ring. Does not include the system. Therefore, the naphthyl structure is preferred over the anthracene structure. Further, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures.

Particularly preferred are structures without condensation, such as phenyl, biphenyl, terphenyl and / or quarterphenyl structures.

Examples of suitable aromatic or heteroaromatic ring system L ¹ is ortho -, meta - or para - phenylene, ortho -, meta - or para - biphenylene, terphenylene, particularly branched terphenylene, Quarter phenylene, especially branched Quarter phenylene, fluorenylene, spirobifluorene fluorenylene Ren, dibenzo furanyl lens is selected from the group consisting of dibenzo thienylene, and carbazolylene, each of which may be optionally substituted by one or more R ¹ radicals, preferably unsubstituted Is.

^{Further, the L 1} group represented by the formula (QL) has, in particular, 1 or less nitrogen atoms, preferably 2 or less heteroatoms, particularly preferably 1 or less heteroatoms, and more preferably does not contain heteroatoms. It may be a case.

ここで、点線は接続位置を示し、
Ｑ’は、出現毎に同一であるかまたは異なり、ＣＲ^１またはＮであり
Ｑ’’は、ＮＲ^１、ＯまたはＳであり；
ここで、少なくとも１つのＱ’はＮであり、
Ｒ^１は、上記、特に式（Ｉ）、に記載の意味を有する。 Preferably, in particular, the Q group or electron transporting group represented by the formula (QL) is the formula (Q-1), (Q-2), (Q-4), (Q-4), (Q-5). , (Q-6), (Q-7), (Q-8), (Q-9) and / or (Q-10) may be selected.

Here, the dotted line indicates the connection position,
Q'is the same or different for each appearance, CR ¹ or N and Q'' is NR ¹ , O or S;
Here, at least one Q'is N,
R ¹ has the meaning described above, in particular, in the formula (I).

ここで、記号Ｒ^１は、上記、特に式（Ｉ）、に記載の意味を有し、Ｘ’は、ＮまたはＣＲ^１であり、点線は接続位置を示し、ここでＸ’は、好ましくは窒素原子である。 Further, in particular, the Q group or electron transporting group represented by the formula (QL) is preferably the formulas (Q-11), (Q-12), (Q-13), (Q-14) and / or (Q-14). It is selected from the structure of -15).

Here, the symbol R ¹ has the meaning described in the above, in particular, the formula (I), where X'is N or CR ¹ , where the dotted line indicates the connection position, where X'is preferably. It is a nitrogen atom.

ここで、記号Ｒ^１は、上記、特に式（Ｉ）、に記載の意味を有し、点線は接続位置を示し、ｍは０、１、２、３または４であり、好ましくは０、１または２であり、ｎは０、１、２または３であり、好ましくは０、１または２であり、ｏは０、１または２であり、好ましくは１または２である。好ましくは、式（Ｑ−１６）、（Ｑ−１７）、（Ｑ−１８）および（Ｑ−１９）の構造である。 In a further form, the Q group represented by the formula (QL), or the electron transporting group, is the formulas (Q-16), (Q-17), (Q-18), (Q-19), (Q-20). , (Q-21) and / or may be selected from the structures of (Q-22).

Here, the symbol R ¹ has the meaning described in the above, particularly the formula (I), the dotted line indicates the connection position, and m is 0, 1, 2, 3 or 4, preferably 0, 1. Or 2, n is 0, 1, 2 or 3, preferably 0, 1 or 2, o is 0, 1 or 2, preferably 1 or 2. The structures of the formulas (Q-16), (Q-17), (Q-18) and (Q-19) are preferable.

ここで、記号Ｒ^１は上記、特に式（Ｉ）、に記載の意味を有し、点線は接続位置を示す。 In further embodiments, the Q group, or electron transporting group, represented in formula (QL), may be selected from the structures of formula (Q-23), (Q-24) and / or (Q-25).

Here, the symbol R ¹ has the meaning described in the above, particularly the formula (I), and the dotted line indicates the connection position.

ここで、記号Ａｒ^１およびＲ^１は、上記、特に式（Ｉ）、に記載の意味を有し、Ｘ’はＮまたはＣＲ^１であり、点線は接続位置を示す。好ましくは、式（Ｑ−２６）、（Ｑ−２７）および（Ｑ−２８）の構造において、ちょうど１つのＸ’が窒素原子である。 In a further form, the Q group, or electron transporting group, particularly represented by formula (QL), is the formula (Q-26), (Q-27), (Q-28), (Q-29) and / or (Q). It may be selected from the structure of -30).

Here, the symbols Ar ¹ and R ¹ have the meanings described in the above, in particular, the formula (I), where X'is N or CR ¹ and the dotted line indicates the connection position. Preferably, in the structures of formulas (Q-26), (Q-27) and (Q-28), exactly one X'is a nitrogen atom.

ここで、記号Ａｒ^１およびＲ^１は、上記、特に式（Ｉ）または（Ｈ−１）、に記載の意味を有し、点線は接続位置を示し、ｍは、０、１、２、３または４、好ましくは０、１または２であり、ｎは０、１、２または３、好ましくは０または１であり、ｎは０、１、２または３、好ましくは０、１または２であり、ｌは１、２、３、４または５、好ましくは０、１または２である。 Preferably, in particular, the Q group represented by the formula (QL) or the electron transporting group is the formula (Q-31), (Q-32), (Q-33), (Q-34), (Q-35), and so on. (Q-36), (Q-37), (Q-38), (Q-39), (Q-40), (Q-41), (Q-42), (Q-43) and / or It may be selected from the structure of (Q-44).

Here, the symbols Ar ¹ and R ¹ have the meanings described above, particularly in the formula (I) or (H-1), the dotted line indicates the connection position, and m is 0, 1, 2, 3 Or 4, preferably 0, 1 or 2, n is 0, 1, 2 or 3, preferably 0 or 1, and n is 0, 1, 2 or 3, preferably 0, 1 or 2. , L is 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

In a further preferred embodiment of the invention, Ar ¹ is the same or different on each appearance and has 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, aromatic or hetero. Aromatic ring systems, preferably aryl or heteroaryl radicals, more preferably aromatic ring systems, preferably aryl radicals, or 5 to 13 aromatic ring atoms having 6-12 aromatic ring atoms. heteroaromatic ring system having preferably a heteroaryl group, each of which may be substituted by one or more R ¹ radical, but is preferably unsubstituted, wherein, R ¹ is above, in particular It may have the meaning described in the formula (I).

Preferably, the symbol Ar ¹ is an aryl or heteroaryl radical, and the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is directly, i.e., via the atom of the aromatic or heteroaromatic group. It is attached to each atom of the additional group, eg, the carbon or nitrogen atom of the (H-1)-(H-26) or (Q-26)-(Q-44) groups shown above.

Advantageously, Ar ¹ of formula (H-1) ~ (H -26) or (Q-26) ~ (Q -44) has from 6 to 12 aromatic ring atoms, one or more of ^{R 1} It may be radically substituted, but preferably unsubstituted, an aromatic ring system, wherein R ¹ may have the meaning described above, in particular the formula (I). ..

^{Preferably, R 1} or R ² of formulas (H-1) to (H-26) or (Q-26) to (Q-44) is an aryl group or hetero to which the ^{R 1} or R ^{2 radical is attached.} Aryl groups Ar ¹ , Ar ² , Ar ³ and / or Ar ⁴ ring atoms do not form a fused ring system. This also encompasses the formation of fused ring systems and R ¹ radical any which may be bonded to a substituent R ^2.

If X is CR, CR ^a , CR ^b or CR ^c , or if the aromatic and / or heteroaromatic groups are substituted with substituents R, these substituents R are preferably H, D. , F, CN, N (Ar) ₂ , C (= O) Ar, P (= O) (Ar) ₂ , a linear, alkyl or alkoxy group or 3 to 10 having 1 to 10 carbon atoms. carbon atoms, branched or cyclic, may be substituted by one or more R ¹ radical alkenyl group (each of which having carbon atoms in the alkyl or alkoxy group or a 2-10, wherein one or more of _Two non-adjacent CH groups may be replaced by O, where one or more hydrogen atoms may be replaced by D or F), having 5 to 24 aromatic ring atoms. in each case, it may be substituted by one or more R ¹ radicals, but preferably is unsubstituted, having an aromatic ring atom of an aromatic or heteroaromatic ring system or 5 to 25, one or more ^{Selected from the group consisting of aromatic or heteroaromatic groups that may be substituted with one or more} of the R1 radicals; where, if desired, preferably two substituents R attached to adjacent carbon atoms are one or more. same R ¹ may be substituted by radicals, monocyclic or polycyclic, aliphatic, it is also possible to form an aromatic or heteroaromatic ring system, wherein, Ar group is on each occurrence or different is, having 5 to 40 aromatic ring atoms, which may be substituted by one or more R ¹ radicals, aromatic or heteroaromatic ring system; wherein the same silicon atom , Two Ar radicals attached to a nitrogen atom, a phosphorus atom or a boron atom are single-bonded or B (R ¹ ), C (R ¹ ) ₂ , Si (R ¹ ) ₂ , C = O, C = NR ¹ , Cross-bridged with each other by a bridge selected from C = C (R ¹ ) ₂ , O, S, S = O, SO ₂ , N (R ¹ ), P (R ¹ ) and P (= O) R ^1. It is also possible.

More preferably, these substituents or a linear alkyl having H, D, F, CN, N (Ar) ₂ , 1-8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms. A branched or cyclic alkyl group having a radical or 3-8 carbon atoms, preferably 3 or 4 carbon atoms, or an alkenyl group having 2-8 carbon atoms, preferably 2, 3 or 4 carbon atoms (these). of which may be substituted by one or more R ¹ radicals are each, but preferably is unsubstituted), the aromatic ring atoms of 5 to 24, preferably 6 to 18 aromatic ring atoms, more preferably 6 has an aromatic ring atom of -13, in each case, it may be substituted by one or more non-aromatic R ¹ radicals, but is preferably unsubstituted, aromatic or heteroaromatic ring system it is selected from the group consisting of; simultaneously, optionally, and preferably two substituents R ¹ bonded to adjacent carbon atoms is unsubstituted preferably may be substituted by one or more R ² radicals, It is also possible to form monocyclic or polycyclic, aliphatic ring systems, where Ar may have the meaning described above.

Most preferably, the substituents R, ^Ra , R ^b or R ^c have H and 6-18 aromatic ring atoms, preferably 6-13 aromatic ring atoms, in each case 1 above preferably may be substituted by non-aromatic R ¹ radicals, which are unsubstituted, it is selected from the group consisting of an aromatic or heteroaromatic ring system. Examples of suitable radicals R are phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quarterphenyl, especially branched quarterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrinidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl, and indeno-carbazolyl (each of which may be optionally substituted by one or more R ¹ radicals, preferably unsubstituted a) from the group consisting of Be selected.

^{Further, the substituents R, Ra} , R ^b or R ^c of the ring system of the formula (I) or (II) are present together with or with each other, that is, particularly the substituent R, of the ring system to which these radicals are bonded. ^b and R ^c together it may be a case which does not form a fused aromatic or heteroaromatic ring system. This also includes the formation of a fused ring system with any of the substituents R ¹ , R ² which may be attached to R, ^Ra , R ^b or R ^c.

Ar, Ar ¹ , Ar ² , Ar ³ and / or Ar ⁴ groups are phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quarterphenyl, especially branched quarterphenyl, 1, 2 -, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrinidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2- , 3- or 4-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, indenocarbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl, and / or may be a case that is selected from the group consisting of triphenylenyl, each of which may be substituted by one or more R ¹ and / or R ² radical Is preferably unsubstituted, and particularly preferably a phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, or triphenylene group.

In a further preferred embodiment, the compound obtained by the present invention comprises at least two, preferably at least three, non-aromatic or non-heteroaromatic ring systems having at least two, preferably at least three rings.

If X'is CR ¹ , or if the aromatic and / or heteroaromatic groups are substituted with substituent R ¹ , these substituents R ¹ are preferably H, D, F, CN, N (Ar ¹ ) ₂ , C (= O) Ar ¹ , P (= O) (Ar ¹ ) ₂ , Linear, alkyl or alkoxy group with 1 to 10 carbon atoms or 3 to 10 carbon atoms having a branched or cyclic alkyl or alkoxy group or alkenyl group having 2 to 10 carbon atoms (each of which one or more R ² radicals may be substituted by but wherein one or more non _Two adjacent CHs may be replaced by O, where one or more hydrogen atoms may be replaced by D or F), having 5 to 24 aromatic ring atoms, respectively. in the case, it may be substituted by one or more R ² radicals are preferably unsubstituted, aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, 1 or more R may be substituted by ² radicals, selected from the group consisting of Aararukiru or heteroaralkyl groups; simultaneously, preferably are attached to adjacent carbon atoms, the two substituents R ¹ are optionally 1 or more R It is also possible to form monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring systems that may be substituted with ^{one radical; where the Ar 1} group is described above, in particular the formula ( It has the meaning described in H-1) to (H-3).

More preferably, these substituents R ¹ are straight lines having H, D, F, CN, N (Ar ¹ ) ₂ , 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms. Alkyl group or an alkenyl group having a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3 or 4 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms. (each of these one or more preferably may be substituted by R ² radical is unsubstituted), or an aromatic ring atom of 5-24, preferably 6 to 18 aromatic ring atoms, more preferably has an aromatic ring atom of a 6-13, in each case, it may be substituted by one or more non-aromatic R ¹ radicals are preferably unsubstituted, aromatic or heteroaromatic ring system it is selected from the group consisting of; simultaneously, attached to a carbon atom which is preferably adjacent, the two substituents R ¹ are optionally 1 or more R ² may be substituted by a radical, preferably unsubstituted It may form a monocyclic or polycyclic, aliphatic ring system, where Ar ¹ may have the meaning described above.

Most preferably, the substituent ^{R 1} is, H or 6-18 aromatic ring atoms, preferably having an aromatic ring atom of a 6-13, in each case, one or more non-aromatic ^{R 2} radical It may be substituted with, but is preferably unsubstituted, it is selected from the group consisting of aromatic or heteroaromatic ring systems. Examples of suitable radicals R ¹ are phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quarterphenyl, especially branched quarterphenyl, 1-, 2-, 3- or 4-fluorenyl. , 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrinidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl , 1-, 2-, 3- or 4-carbazolyl, and (is each of these preferably may be substituted by one or more R ² radicals unsubstituted is) indeno carbazolyl from the group consisting of Be selected.

Furthermore, the substituents R ¹ heteroaromatic ring system of the formula (I) ~ (IV), together with an aromatic or heteroaromatic ring system ring atoms do not form a fused aromatic or heteroaromatic ring system, preferably May be the case where no fused ring system is formed. This also encompasses the formation of fused ring systems and R ¹ radical any which may be bonded to a substituent R ^2.

ここで、使用される記号は以下のとおりである：
Ｙ^１は、Ｏ、ＳまたはＮＲ^２、好ましくは、ＯまたはＳであり；
ｋは、出現毎に独立に、０または１であり；
ｉは、出現毎に独立に、０、１または２であり；
ｊは、出現毎に独立に、０、１、２または３であり；
ｈは、出現毎に独立に、０、１、２、３または４であり；
ｇは、出現毎に独立に、０、１、２、３、４または５であり；
Ｒ^２は、上記、特に式（Ｉ）、に記載の意味を有し、かつ破線の結合は、結合部位を示す。 Furthermore the compounds of formula (I), a group selected from (II), (III) and / or at least one ^{R 1} radical has the formula ^(R 1 ^{-1) ~} in (IV) (R 1 -92) or the formula (H-1) ~ (H -26) and / or (Q-1) ~ (Q -44) of at least one of Ar ¹ or ^{R 1} radicals in the structure of the formula ^(R 1 -1 ) ^- (it may be a case a group selected from R 1 -92).

Here, the symbols used are:
Y ¹ is O, S or NR ² , preferably O or S;
k is 0 or 1 independently for each appearance;
i is 0, 1 or 2 independently for each appearance;
j is 0, 1, 2 or 3 independently for each appearance;
h is 0, 1, 2, 3 or 4 independently for each appearance;
g is 0, 1, 2, 3, 4 or 5 independently for each appearance;
R ² is described above, in particular have the meanings described in Formula (I), and the dashed bond represents a binding site.

Here, preferably, a group of the formula ^{R 1 -1~R} 1 -54, particularly preferably ^{R 1 -1, R 1 -3,} R 1 -5, R 1 -6, R 1 -15, R ^{1 -29, R 1 -30, R} 1 -31, R 1 -32, R 1 -33, R 1 -38, R 1 -39, R 1 -40, R 1 -41, R 1 -42, R ^{1 -43,} an R 1 -44 and / or ^R 1 -45 group.

In the structure of the formula ^{(R 1 -1) ~ (R} 1 -92), subscript k, i, j, the sum of h and g is in each case, 3 or less, preferably 2 or less, more preferably 1 or less It is preferable to make it.

Preferably, ^{R 2} radicals in the formula ^{(R 1 -1) ~ (R} 1 -92) is, ^{R 2} radicals are bonded, a ring atom of an aryl or heteroaryl group, fused, aromatic or heteroaromatic It does not bind aromatic ring systems and preferably does not form any fused ring system.

ここで、破線の結合は、それぞれのケースにおいて、結合部位を示し、添え字ｋは、０または１であり、添え字ｌは、０、１または２であり、添え字ｊは、出現毎に独立して、０、１、２または３であり；添え字ｈは、出現毎に独立して、０、１、２、３または４であり、添え字ｇは、０、１、２、３、４または５であり；記号Ｙ^１は、Ｏ、ＳまたはＮＲ^２、好ましくはＯまたはＳであり；かつ記号Ｒ^１は、上記、特に式（Ｉ）、に記載の意味を有する。 Preferably, at least one comprising a compound of structural formula (H-1) ~ (H -26) ( wherein, Ar ² groups, the formula ^{(L 1 -1) ~ (L} 1 -108) group in a) and / or formula is selected (structure comprising a compound of QL) (wherein, ^{L 1} group is a bond, the formula ^(L 1 ^-1) from ~ (L 1 -108) Is the base of choice).

Here, the chain of broken lines indicates the binding site in each case, the subscript k is 0 or 1, the subscript l is 0, 1 or 2, and the subscript j is each appearance. Independently, 0, 1, 2 or 3; the subscript h is 0, 1, 2, 3 or 4 independently for each appearance, and the subscript g is 0, 1, 2, 3 4 or 5; the symbol Y ¹ is O, S or NR ² , preferably O or S; and the symbol R ¹ has the meaning set forth above, in particular in formula (I).

Preferably, in the structure of formula ^{(L 1 -1) ~ (L} 1 -108), subscript k, l, g, the sum of h and j, in each case, up to three, preferably up to It is also preferable to set it to 2, and more preferably 1 at the maximum.

Preferred compounds of the present invention having a group of the formula (H-1) ~ (H -26) has the formula ^{(L 1 -1) ~ (L} 1 -78) and / or ^{(L 1 -92) ~ (L} 1 -108), preferably of formula ^{(L 1 -1) ~ (L} 1 -54) and / or ^{(L 1 -92) ~ (L} 1 -108), particularly preferably of the formula ^(L 1 -1) ~ ⁽ L becomes ¹ -29) and / or ^(L 1 ^-92) contain ~ (L 1 -103) Ar ² groups selected from one of the. Advantageously, the formula ^{(L 1 -1) ~ (L} 1 -78) and / or ^{(L 1 -92) ~ (L} 1 -108), preferably of formula ^{(L 1 -1) ~ (L} 1 -54 ) and / or ^{(L 1 -92) ~ (L} 1 -108), especially preferably the formula ^{(L 1 -1) ~ (L} 1 -29) and / or ^{(L 1 -92) ~ (L} 1 - 103), the sum of the subscripts k, l, g, h and j in the structure may be 3 or less, preferably 2 or less, more preferably 1 or less in each case.

Preferred compounds of the present invention having a group of the formula (QL) is comprises a group ^{L 1,} or the group ^{L 1} represents a bond or a formula ^{(L 1 -1) ~ (L} 1 -78), and / or ^{(L 1 -92) ~ (L} 1 -108), preferably, the formula ^{(L 1 -1) ~ (L} 1 -54) and / or ^{(L 1 -92) ~ (L} 1 -108), in particular preferably, those selected from one of formulas ^{(L 1 -1) ~ (L} 1 -29) and / or ^{(L 1 -92) ~ (L} 1 -103). Advantageously, the formula ^{(L 1 -1) ~ (L} 1 -78) and / or ^{(L 1 -92) ~ (L} 1 -108), preferably, the formula ^{(L 1 -1) ~ (L} 1 - 54) and / or ^{(L 1 -92) ~ (L} 1 -108), particularly preferably the formula ^{(L 1 -1) ~ (L} 1 -29) and / or ^{(L 1 -92) ~ (L} 1 The sum of the subscripts k, l, g, h and j in the structure of −103) may be up to 3, preferably up to 2, and more preferably up to 1 in each case. can.

Preferably, ^{R 1} radicals in the formula ^{(L 1 -1) ~ (L} 1 -108) is, ^{R 1} radicals are bonded, fused to ring atoms of the aryl or heteroaryl group, an aromatic or heteroaromatic It does not form a group ring system, and preferably does not form a fused ring system at all. This may be bonded to R ² radicals, including formation of any of the substituents R ² and fused ring systems.

Containing compound of the present invention, when it is substituted by an aromatic or heteroaromatic R ¹ or R ² groups, these may, aryl or heteroaryl group having more than two aromatic 6-membered ring fused directly to each other It is preferable not to do so. It is more preferred that the substituents have no aryl or heteroaryl groups with 6-membered rings directly fused to each other. The preferred reason for this is the low triplet energy of such structures. Phenanthrene and triphenylene are suitable fused aryl groups for the present invention, although they have more than two aromatic 6-membered rings that are directly fused to each other. Because they also have a high triplet level.

In the case of the compound form obtained by the present invention for use as a fluorescent emitter or as a blue OLED material, the preferred compound may ^{be substituted with R 1} or R ² or corresponds to (R ^{1). -1) ~} (R 1 ^-95) group, preferably ^{(R 1 -33) ~ (R} 1 -57) and ^{(R 1 -76) ~ (R} 1 -86), or ^(L 1 -1) ~ ^(L 1 -109), preferably formed by ^{(L 1 -30) ~ (L} 1 -60) and ^(L 1 ^-71) by the corresponding substituents of the ^~ (L 1 -91), the substituents ^{R 2} It may contain the corresponding group (eg, fluorene, anthracene, and / or pyrene group).

In a further preferred embodiment of the invention, for example, in the preferred embodiments of formulas (I)-(IV) and this structure or structures with reference to these formulas, R ² is the same or different for each appearance, H. D, an aliphatic hydrocarbyl radical having 1 to 10 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms. An aromatic or heteroaromatic ring system preferably substituted with one or more alkyl groups having 5 to 13 aromatic ring atoms and each having 1 to 4 carbon atoms, but preferably unsubstituted. It is selected from the group consisting of.

Preferably, the R ² radical does not form a fused aromatic or heteroaromatic ring system with the ring atom of the aryl group or heteroaryl group to which the ^{R 2 radical is bonded, and preferably does not form any fused ring system.}

Preferred forms of the compounds of the invention are specifically described in the Examples, which can be used alone or in combination with another compound for all purposes of the invention.

As long as the conditions specified in claim 1 are satisfied, the above preferred embodiments can be combined with each other, if desired. In a particularly preferred embodiment of the invention, the preferred embodiments described above are applied simultaneously.

The compounds obtained by the method of the present invention are novel. Therefore, the present invention further provides compounds obtained by the method.

ここで、記号Ｒ^ａ、Ｒ^ｂおよびＲ^ｃは、上記、特に式（Ｉ）、に記載の意味を有し、二環／多環は１以上の置換基Ｒを有していてもよく、Ｒは上記、特に式（ＩＩ）、に記載の意味を有する。式（Ｖ）で示される二環／多環は活性アルケン由来であり、詳細は式（Ｖ）の化合物に関連して適用することもできる。同様のことが、Ｒ^ａ、Ｒ^ｂ，およびＲ^ｃラジカルに適用される。 Preferred compounds include structures that can be represented by the formula (V).

Here, the symbols R ^a , R ^b and R ^c have the meanings described above, particularly in formula (I), and the bicyclic / polycyclic ring may have one or more substituents R. R has the meaning described above, in particular, in formula (II). The bicyclic / polycyclic represented by the formula (V) is derived from the active alkene, and the details can also be applied in connection with the compound of the formula (V). The same applies to the ^Ra , R ^b , and R ^c radicals.

ここで、点線は、二環／多環が縮合される式（Ｖ）に示されるピペリジン構造への二環／多環の結合を示す。式（Ｎ−１）〜（Ｎ−１４）に示される副構造は、１以上のＲラジカルによって置換されていてもよく、ここで、Ｒは、上記、特に式（Ｉ）、に記載のとおりである。 Preferably, the bicyclic / polycyclic represented by formula (II) or (V) is a non-aromatic or non-heteroaromatic polycyclic ring system having at least two, preferably at least three rings. Specifically, the bicyclic / polycyclic represented by the formula (II) or (V) forms a substructure of the formulas (N-1) to (N-14).

Here, the dotted line indicates the binding of the bicyclic / polycyclic to the piperidine structure represented by the formula (V) in which the bicyclic / polycyclic is condensed. The substructures represented by formulas (N-1) to (N-14) may be substituted with one or more R radicals, where R is as described above, in particular formula (I). Is.

In a preferred embodiment, there may be no additional ring system to condense to the pyridine structure represented by formula (V) where the bicyclic / polycyclic is condensed. Therefore, the R ^b and R ^c radicals preferably do not form any ring system. This also includes the formation of a fused ring system with ^{any substituent R 1} , R ² that may be attached to the R ^b or R ^{c radical.}

Further, the compound may be a case having at least two structures represented by the formula (V). In a preferred embodiment, these compounds may ^{be represented such that one of the Ra} , R ^b and R ^c radicals constitutes a binding or linking group. Here, the linking group is preferably, L ¹ groups have the meanings given above, in particular of formula (QL), as described. These compounds, preferably having two structures represented by formula (V), are preferably symmetric and preferably symmetric from the linking group or bond that binds at least two structures represented by formula (V). ..

In a preferred embodiment, the compound obtained by the present invention, preferably the compound having the structure of formula (V), is phenyl, halogenated phenyl, biphenyl, terphenyl, quarterphenyl, fluorene, indenofluorene, spirobifluorene, carbazole, and the like. Indenocarbazole, indolocarbazole, spirocarbazole, pyrimidine, triazine, lactam, triarylamine, dibenzofuran, dibenzothien, dibenzothiophene, imidazole, benzoimidazole, benzoxazole, benzothiazole, 5-arylphenanthridin-6-one , 9,10-Dihydrophenanthrene, fluorene, anthracene, pyrene, perylene, borane, triarylborane, heteroarylborane, borazane, benzanthracene, fluorene.

In a preferred embodiment, the compound obtained by the present invention, preferably the compound having the structure of formula (V), can be represented by the structure of formula (V). Preferably, the compound obtained by the present invention, preferably the compound having the structure of the formula (V), is 5000 g / mol or less, preferably 4000 g / mol or less, particularly preferably 3000 g / mol or less, and particularly preferably 2000 g / mol. Hereinafter, it most preferably has a molecular weight of 1200 g / mol or less.

Furthermore, a feature of the preferred compounds of the present invention is that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

In a preferred embodiment, the preferred compound comprises a structure of formula (V) having exactly one structure of formula (V) having the following characteristics:

In the above compounds, the term ^{"R a} include" refers, ^{R a} group in the structure (V) is the corresponding formula (e.g. the formula ^{(R 1 -1) ~ (R} 1 -92), (H-1) ~ It means that it contains a radical of (H-26) and / or one of (Q-1) to (Q-44), where this radical is directly expressed in formula (V). Alternatively, they may be bonded via a linking group, where the linking radical preferably has the meaning described above, in particular the formula (QL). This is a radical of the formula ^{(R 1 -1) ~ (R} 1 -92) and / or (Q-1) ~ (Q -44), particularly true. More preferably, the formula ^{(R 1 -1) ~ (R} 1 -92), the radicals (H-1) ~ (H -26) and / or (Q-1) ~ (Q -44), coupled, or a group of the formula ^{(L 1 -1) ~ (L} 1 -108), more preferably ^{(L 1 -1) ~ (L} 1 -5) and / or ^{(L 1 -92) ~ (L} 1 -103) Is attached to the pyridine structure represented by the formula (V). The same applies to the terms "R ^b inclusion" and "R ^{c inclusion".}

In a preferred embodiment, the preferred compound comprises a structure of formula (V) having exactly two structures of formula (V) having the following characteristics:

In the above compounds, the term ^{"R a} include" refers, ^{R a} group in the structure (V) is the corresponding formula (e.g. the formula ^{(R 1 -1) ~ (R} 1 -92), (H-1) ~ It means that it contains a radical of (H-26) and / or one of (Q-1) to (Q-44), where this radical is directly expressed in formula (V). Alternatively, they may be bonded via a linking group, where the linking radical preferably has the meaning described above, in particular the formula (QL). This is a radical of the formula ^{(R 1 -1) ~ (R} 1 -92) and / or (Q-1) ~ (Q -44), particularly true. More preferably, the formula ^{(R 1 -1) ~ (R} 1 -92), the radicals (H-1) ~ (H -26) and / or (Q-1) ~ (Q -44), coupled, or a group of the formula ^{(L 1 -1) ~ (L} 1 -108), more preferably ^{(L 1 -1) ~ (L} 1 -5) and / or ^{(L 1 -92) ~ (L} 1 -103) Is attached to the pyridine structure represented by the formula (V). The same applies to the terms "R ^b inclusion" and "R ^{c inclusion".} The term ^{"(L 1 -1) ~ (L} 1 -108), preferably ^{(L 1 -1) ~ (L} 1 -5) and / or ^{(L 1 -92) ~ (L} 1 -103) " is corresponding ^R a, ^{R b} or ^{R c} radical, comprises a group of the formula ^{(L 1 -1) ~ (L} 1 -108), in which, or through which, the formula two of (V) That the structure is bound and the compound comprising the two structures of formula (V) comprises exactly one ^Ra , R ^b or R ^c through which the rest of the substructure is attached. means. The term ^{"(R 1 -1) ~ (R} 1 -92), preferably connected via a coupling in ^{(R 1 -1) ~ (R} 1 -4), each case;" in each case, corresponding ^R a, ^{R b} or ^{R c} radical, comprises a group of the formula ^{(R 1 -1) ~ (R} 1 -92), wherein the formula ^{(R 1 -1) ~ (R} 1 -92 ) Are bonded via a bond in each case, meaning that the two structures of formula (V) are connected. In this case, the compound comprising the two structures of formula (V) has exactly two ^Ra , R ^b or R ^c radicals through which the remaining substructures are attached. Similar terms have corresponding meanings. The term "bond" refers to the corresponding R ^a , R ^b or R ^c radicals indicating a bond, through which the two structures of formula (V) are connected and include the two structures of formula (V). It means that the compound consisting of contains exactly one ^Ra , R ^b or R ^c radical indicating a bond, through which the remaining substructures are connected.

The compounds obtained by the present invention, preferably compounds having the structure of formula (V), are also suitable substituents, such as relatively long alkyl groups (about 4-20 carbon atoms), particularly branched alkyl groups. Alternatively, it may have optionally substituted aryl groups such as xylene, mesityl, or branched, terphenyl or quarterphenyl groups, which are standard to allow the compound to be treated from the solution. Dissolve in toluene or xylene at room temperature at sufficient concentrations, for example, to give solubility in organic solvents. These soluble compounds are particularly suitable for treatment from solution, for example by printing. Furthermore, it should be noted that the compounds obtained by the present invention, preferably the compounds having the structure of formula (V), have already been enhanced in solubility in these solvents.

The compounds obtained by the present invention can also be mixed with polymers. Similarly, these compounds can be conjugated and coupled into the polymer. This is particularly possible for compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid esters, or with reactive polymerizable groups such as olefins or oxetane. They can also be used as monomers to produce the corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization is preferably carried out via a halogen functional group or a boronic acid functional group, or via a polymerizable group. Furthermore, it is also possible to crosslink the polymer via such groups. The compounds and polymers of the present invention can be used in the form of crosslinked or non-crosslinked layers.

Accordingly, the present invention further provides an oligomer, a polymer or a dendrimer having the structure of one or more of the above formula (V) or containing a compound obtained by the present invention, to a polymer, an oligomer or a dendrimer. There is one or more bonds of the compounds of the invention or of the structure of formula (V). By binding the structure or compound of formula (V), they thus form side chains of oligomers or polymers, or are bonded in the backbone. The polymer, oligomer or dendrimer may be conjugated, partially conjugated, or unconjugated. The oligomer or polymer can be linear, branched or dendritic. The same priorities as described above apply to the repeating units of the compounds of the invention in oligomers, dendrimers and polymers.

To prepare oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with other monomers. Preferably, the unit of the formula (V), or of the preferred form described above or below, is 0.01-99.9 mol%, preferably 5-9 mol%, more preferably 20-80 mol%. It is a copolymer that exists in the range. Suitable and preferred comonomer forming the polymer backbone are fluorene (eg, EP842208, or WO2000 / 022026), spirobifluorene (eg, EP707020, EP894107, or WO2006 / 061181), paraphenylene (eg, WO92). / 18552), carbazole (eg, WO2004 / 070772, or WO2004 / 11468), thiophene (eg, according to EP1028136), dihydrophenanthrene (eg, according to WO2005 / 014689), cis- and trans-indenofluorene (eg, according to WO2005 / 014689). It is selected from WO2004 / 041901, or WO2004 / 113412), ketones (eg, according to WO2005 / 040302), phenanthrene (eg, according to WO2005 / 104264, or WO2007 / 017066), or a plurality of these units. Polymers, oligomers and dendrimers may still contain, for example, hole transport units, particularly those based on triarylamines and / or other units such as electron transport units.

Of particular interest are the compounds of the invention, which are characterized by a high glass transition temperature. In this regard, glass at least 70 ° C., more preferably at least 110 ° C., even more preferably at least 125 ° C., and particularly preferably at least 150 ° C., as measured according to DIN 51005 (2005-08). Compounds obtained by the present invention having a transition temperature, preferably a structure of the formula (V), or a compound comprising the above-mentioned or preferred forms described below are particularly preferred.

For example, in order to treat a compound of the present invention from a liquid phase by spin coating or by a printing method, a formulation of the compound of the present invention is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it is preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetraline, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3 -Phenoxytoluene, (-)-Fencon, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2 -Pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, Decalin, dodecylbenzene, ethyl benzoate, indan, methyl benzoate, NMP, p-simene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, Triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis (3,4-dimethylphenyl) ethane , Hexamethylindan, or a mixture of these solvents.

Accordingly, the invention further provides a formulation comprising the compound of the invention and at least one additional compound. This additional compound may be, for example, a solvent, in particular one of the above solvents, or a mixture of these solvents. Alternatively, the additional compound may be at least one additional organic or inorganic compound also used for electronic devices, which may be, for example, a luminescent compound, such as a fluorescent dopant, a phosphorescent dopant, or Compounds exhibiting TADF (Thermal Activated Delayed Fluorescence), in particular phosphorescent dopants and / or additional matrix materials. This additional compound may also be polymeric.

Accordingly, the invention still provides compositions comprising the compounds of the invention and at least one additional organic functional material. The functional material is generally an organic or inorganic material introduced between the anode and the cathode. Preferably, the organic functional material is a fluorescent emitter, a light emitter showing TADF (thermally activated delayed fluorescence), a phosphorescent emitter, a host material, an electron transport material, an electron injection material, a hole conduction material, a hole injection material, and the like. It is selected from the group consisting of electron blocking materials, hole blocking materials, wide bandgap materials, and n-type dopants.

Therefore, the invention also comprises at least one compound obtained by the present invention, preferably a compound comprising the structure of formula (V) or the preferred embodiments described above and below, and at least one additional matrix material. Regarding the composition. According to a particular embodiment of the invention, the additional matrix material has hole transport properties.

Further, the present invention comprises at least one compound obtained by the present invention, preferably a compound having a structure of formula (V) or a preferred form described above or below, and at least one wide bandgap material (wide bandgap). The material is understood to mean the material for the purposes of the disclosure of US7,294,849). These systems exhibit excellent and advantageous properties in electronic devices.

Preferably, the additional compound can have a bandgap of 2.5 eV or higher, preferably 3.0 eV or higher, and very preferably 3.5 eV or higher. One method of calculating the bandgap is by energy levels of the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO).

Materials, molecular orbital, particularly also the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), their energy levels, as well as the energy of the lowest triplet state T ₁ and the lowest excited singlet state S ₁ Is determined by quantum chemistry calculations. To calculate metal-free organic matter, first use the "ground state / semi-empirical / default spin / AM1 / charge 0 / spin singlet" method to geometries. Optimize. Then, the energy calculation is performed based on the optimized geometric arrangement. This is done using the "TD-SCF / DFT / default spin / B3PW91" method using the "6-31G (d)" basis set (charge 0, spin singlet). For metal-containing compounds, the geometry is optimized by the "ground state / Hartree-Fock / default spin / LanL2MB / charge 0 / spin singlet" method. The energy calculation is performed in the same manner as the method for organic substances described above, except that the "LanL2DZ" basis set is used for the metal atom and the "6-31G (d)" basis set is used for the ligand. It is different to do. The HOMO energy level HEh or LUMO energy level LEh is obtained in Hartley units by energy calculation. It is used to determine the HOMO and LUMO energy levels adjusted by cyclic voltammetry measurements with electron volts as follows:
HOMO (eV) = ((HEh ^* 27.212) -0.9899) /1.1206
LUMO (eV) = ((LEh ^* 27.212) -2.041) /1.385

In the spirit of the present invention, these values shall be regarded as the HOMO and LUMO energy levels of the material.

The lowest triplet state T ₁ is defined as the energy of the triplet state with the lowest energy, which is evident from the quantum chemistry calculations described.

Lowest excited singlet state S ₁ is defined as the energy of the excited singlet state having the lowest energy, which will be apparent from the description quantum chemical calculations.

The methods described herein always produce the same results, independent of the software package used. Frequently used examples for this purpose are "Gaussian 09W" (Gaussian) and "Q-Chem 4.1" (Q-Chem). Is.

The present invention also comprises a compound obtained by the present invention, preferably at least one of the compounds of formula (V), or a compound comprising the preferred embodiment described above or below, and at least one phosphorescent luminescent material. Regarding. The term "phosphorescent emitter" is understood to include a phosphorescent dopant.

Dopants in a system comprising a matrix material and a dopant are understood to mean components having a smaller ratio in the mixture. Correspondingly, the matrix material in the system comprising the matrix material and the dopant is understood to mean a component having a larger ratio in the mixture.

Preferred phosphorescent dopants for use in matrix systems, preferably mixed matrix systems, are the preferred phosphorescent dopants specifically shown below.

The term "phosphorescent dopant" usually includes compounds in which the emission is caused by a spin-forbidden transition, eg, from an excited triplet state, or a state with a higher spin quantum number, eg, a transition from a quintuple state. ..

A suitable phosphorescent compound is that (= triplet illuminant) emits light preferably in the visible region, especially when properly excited, and is also greater than 20, preferably greater than 38 84. Less than, more preferably, a compound comprising at least one atom having an atomic number greater than 56 and less than 80, particularly a metal having this atomic number. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, renium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above metals are considered to be phosphorescent compounds.

Examples of the above illuminants include: WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, US2005 / 0258742, WO2009 / 146770, WO2010 / 015307. , WO2010 / 031485, WO2010 / 054731, WO2010 / 054728, WO2010 / 086089, WO2010 / 099852, WO2010 / 102709, WO2011 / 032626, WO2011 / 066898, WO2011 / 1573339, WO2012 / 007082, WO2014 / 000882, WO2014 / 023377. / 094941, WO2014 / 09460, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, WO2016 / 015815, WO2016 / 124304, WO2016 / 124304, WO2017 / 032439, WO2018 / 019687, WO2018 / 019688, WO2018 / 0417769, WO2018 , WO2018 / 069196, WO2018 / 069197, WO2018 / 069273.
In general, all phosphorescent complexes, such as those used in phosphorescent OLEDs by prior art and well known to those of skill in the art in the field of organic electroluminescence, are suitable, and those of skill in the art are of inventionual ingenuity. Further phosphorescent complexes can be used without the need for skill in the art.

The above-mentioned compound obtained by the present invention, preferably a compound having the structure of the formula (V) or the above-mentioned preferable form, can be preferably used as an active ingredient in an electronic device. An electronic device is meant to mean any device comprising an anode, a cathode and at least one layer between the anode and the cathode, which layer comprises at least one of an organic or organometallic compound. To be solved. The electronic device of the present invention is therefore a layer comprising at least one compound comprising at least one intermediate layer comprising at least one compound comprising an anode, a cathode, and a structure of formula (I). It is equipped with. Here, the preferred electronic device is an organic electroluminescence device (OLED, PLED), an organic integrated circuit (O-IC), wherein at least one layer contains at least one compound comprising the structure of the formula (I). ), Organic electric field effect transistor (O-FET), organic thin film (OTT), organic light emitting transistor (O-LET), organic solar cell (O-SC), organic light detector, organic photoreceiver, organic electric field. Extinguishing element (O-FQD), organic electric sensor, light emitting electrochemical cell (LEC), organic laser diode (O-laser) and organic plasmon light emitting device (DM Koller et al., Nature Transistors 2008, 1-4. ), Which are preferably organic electroluminescence devices (OLEDs, PLEDs), particularly phosphorescent OLEDs. Particularly preferred is an organic electroluminescence device. The active ingredient is generally an organic or inorganic material introduced between the anode and cathode, such as charge injection, charge transport or charge blocking materials, especially luminescent and matrix materials.

A preferred embodiment of the present invention is an organic electroluminescence device. The organic electroluminescence device comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it is still another layer, eg, one or more in each case, a hole injection layer, a hole transport layer, a hole block layer, an electron transport layer, an electron injection layer, excitons. It can also include a block layer, an electron block layer, a charge generation layer and / or an organic or inorganic p / n type junction. At the same time, the one or more hole transport layers are _{p-type doped with, for example, a metal oxide such as MoO 3} or WO ₃ , or with a (super) fluorinated electron deficient aromatic system, and / or. One or more electron transport layers can be n-type doped. Similarly, intermediate layers can be introduced between the two light emitting layers, which have, for example, exciton blocking function and / or control charge balance in the electroluminescence device. However, it is pointed out that none of these layers need to be present.

In this case, the organic electroluminescence device may include one light emitting layer or may include a plurality of light emitting layers. When a plurality of light emitting layers are present, they preferably have a plurality of emission maxima over the entire 380 nm to 750 nm, resulting in a variety of white emission as a whole, i.e., capable of emitting fluorescence or phosphorescence. Luminescent compounds are used in the light emitting layer. Particularly preferred is a three-layer system in which the three layers emit blue, green and orange or red light (see, for example, WO2005 / 011013 for the basic configuration), or a system with more than three light emitting layers. be. Further preferred is also a tandem OLED. This system may be a hybrid system in which one or more layers emit fluorescence and one or more other layers emit phosphorescence.

In a preferred embodiment of the invention, the organic electroluminescence element is combined with one or more light emitting layers, preferably in combination with another matrix material, preferably with a hole conduction matrix material, preferably with an electron conduction matrix material. A compound of the present invention, preferably a compound comprising the structure of formula (V) or the preferred form described above. In a more preferred embodiment of the invention, the additional matrix material is an electron transport material. In a more preferred form, the further matrix material is a compound with a large bandgap that is, but is not substantially, involved in the transport of holes and electrons in the layer. The light emitting layer comprises at least one light emitting compound.

In a further particularly preferred embodiment of the present invention, the organic electroluminescence device of the present invention conducts hole conduction of a compound obtained by the present invention, preferably a compound having the structure of the formula (V) or a compound containing the above and the preferred embodiments described below. It is included in a layer or an electron conduction layer.

Suitable matrix materials that can be used in combination with the compounds obtained by the present invention, preferably compounds comprising a structure of formula (V) or preferred form, are aromatic ketones, aromatic phosphinid oxides, or aromatics. Group sulfoxides or sulfones (eg, by WO2004 / 013080, WO2004 / 093207, WO2006 / 005627 or WO2010 / 00280), triarylamines, in particular monoamines (eg, by WO2014 / 015935), carbazole derivatives (eg, CBP (N,). By N-biscarbazolylbiphenyl, or carbazole derivatives disclosed in WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527, or WO2008 / 086851), indolocarbazole derivatives (eg, WO2007 / 063754 or WO2008 / 056746). ), Indenocarbazole derivatives (eg, according to WO2010 / 136109 and WO2011 / 00455), azacarbazole derivatives (eg, according to EP1617710, EP1617711, EP1731584, JP2005 / 347160), bipolar matrix materials (eg, according to WO2007 / 137725). ), Silane (eg, according to WO2005 / 111172), azabolol or boronic acid ester (eg, according to WO2006 / 117052), triazine derivatives (eg, according to WO2010 / 015306, WO2007 / 063754, or WO2008 / 056746), zinc complexes (eg, according to WO2008 / 056746). , EP652273 or WO2009 / 062578), diazacilol or tetraazacilol derivatives (eg, by WO2010 / 054729), diazaphosphor derivatives (eg, by WO2010 / 054730), crosslinked carbazole derivatives (eg, US2009 / 0136779, WO2010 / 050778, WO2011). / 042107, WO2011 / 088877 or WO2012 / 143080), triphenylene derivatives (eg, according to WO2012 / 048781), lactams (eg, according to WO2011 / 116865, WO2011 / 13951 or WO2013 / 064206), 4-spirocarbazole derivatives. (For example, according to WO2014 / 099463 or WO2015 / 192939) or dibenzofuran derivatives (eg, according to WO2015 / 169412, WO2016 / 015810, WO2016 / 023608, or unpublished applications, EP16158460.2 and EP16159829.7). Similarly, additional phosphorescent light emitters that emit light at shorter wavelengths than the actual light emitters can exist as co-hosts in the mixture.

Preferred co-host materials are triarylamine derivatives, in particular monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.

Further, it is preferable to use a mixture of a plurality of different matrix materials, particularly at least one electron conduction matrix material and at least one hole conduction matrix material. Similarly, preferred are the charge transport matrix materials and the electrically inert, eg, as described in WO2010 / 108579, which are involved in, if not substantially, involved in charge transport. The use of mixtures with matrix materials.

Further, it is preferable to use a mixture of two or more triplet illuminants together with the matrix. In this case, the triplet emitter with the shorter wavelength emission spectrum acts as a co-matrix for the triplet emitter with the longer wavelength emission spectrum.

More preferably, the compound obtained in the present invention, preferably the compound containing the structure of the formula (V), emits light in a preferred form of an organic electronic device, particularly an organic electroluminescence device, for example, OLED or OLEC. It can be used as a matrix material in the layer. In this case, the matrix material comprising the compound obtained in the present invention, preferably a compound having the structure of formula (V) or the preferred form described above or below, together with one or more dopants, preferably phosphorescent dopants. It exists in the electronic element.

In this case, the proportion of the matrix material in the light emitting layer is 50.0 to 99.9% by volume, preferably 80.0 to 99.5% by volume, and more preferably 92.0 to 92.0 to 92.0% by volume for the fluorescent light emitting layer. It is 99.5% by volume, and 85.0 to 97.0% by volume for the phosphorescent layer.

Correspondingly, the proportion of dopant is 0.1 to 50.0% by volume, preferably 0.5 to 20.0% by volume, and more preferably 0.5 to 8.0 for the fluorescent layer. The volume is 3.0 to 15.0% by volume, and the phosphorescent layer is 3.0 to 15.0% by volume.

The light emitting layer of the organic electroluminescence element may also include a system comprising a plurality of matrix materials (mixed matrix system) and / or a plurality of dopants. Again, the dopant is the material that has a smaller proportion in the system, and the matrix material is the material that has a larger proportion in the system. In each case, however, the proportion of individual matrix materials in the system may be less than the proportion of individual dopants.

In a more preferred embodiment of the invention, the compound obtained by the present invention, preferably the compound of formula (V) or comprising the structure of the preferred embodiment described above or below, is used as one component of the mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material having hole transport properties and the other material is a material having electron transport properties. However, the desired electron transport and hole transport properties of the mixed matrix components may also be predominantly or completely integrated into the individual mixed matrix components, in which case the additional mixed matrix components satisfy other functions. .. The two different matrix materials are in a ratio of 1:50 to 1: 1, preferably 1:20 to 1: 1, more preferably 1: 10 to 1: 1, and most preferably 1: 4 to 1: 1. Can exist. It is preferable to use the mixed matrix system in a phosphorescent organic electroluminescence device. One of the more detailed sources of information on mixed matrix systems is the application for WO2010 / 108579.

The invention further comprises an electron-conducting compound in one or more electron conductive layers, comprising one or more of the compounds of the invention and / or at least one of the oligomers, polymers or dendrimers of the invention. The device, preferably an organic electroluminescence device, is provided.

The cathode is preferably of a metal having a low work function, such as an alkaline earth metal, an alkali metal, a main group metal or a lanthanide (eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). It is a metal alloy or a multilayer structure composed of various metals such as. Further, an alloy composed of an alkali metal or an alkaline earth metal and silver, for example, an alloy composed of magnesium and silver is suitable. In the case of a multilayer structure, in addition to the metal, additional metals having a relatively high work function, such as Ag, can also be used, in this case, for example, Mg / Ag, Ca / Ag or. Metal combinations such as Ba / Ag are commonly used. Also, preferably, a thin intermediate layer made of a material having a high dielectric constant can be introduced between the metal cathode and the organic semiconductor. Examples of suitable materials for this purpose are fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (eg, LiF, Li ₂ O, BaF ₂ , MgO, etc.). NaF, CsF, Cs ₂ CO ₃ etc.). Similarly, useful for this purpose are organic alkali metal complexes, such as Liq (lithium quinolinate). The layer thickness of this layer is preferably 0.5 to 5 nm.

The anode is preferably a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV with respect to vacuum. First, metals with high redox potentials, such as Ag, Pt or Au, are suitable for this purpose. Second, metal / metal oxide electrodes (eg, Al / Ni / NiOx, Al / PtOx) are also preferred. At least one of the electrodes is transparent or partially to allow either irradiation of organic material (O-SC) or emission (OLED / PLED, O-laser) for some applications. Must be transparent. Here, the preferred anode material is a conductive mixed metal oxide. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Further preferred are doped, conductive organic materials, in particular doped, conductive polymers such as PEDOT, PANI or derivatives of these polymers. It is even more preferred that a p-type doped hole transport material be applied to the anode as a hole injection layer, in which case the suitable p-type dopant is a metal oxide such as MoO ₃ or WO ₃ or an electron. It is a deficient (excessive) fluorinated aromatic system. A more suitable p-type dopant is HAT-CN (hexacyanohexazatriphenylene) or compound NPD9 manufactured by Novaled. Such layers facilitate hole injection into materials with low HOMO, i.e., large HOMO in size.

In a further layer, any material used in the prior art can generally be used for this layer, and one of ordinary skill in the art, in an electronic device, any of these materials. Can be combined with the materials of the present invention.

Since the life of such devices is significantly shortened by the presence of water and / or air, the devices are correspondingly structured (depending on the application), provided with contacts, and finally sealed.

More preferred is an electronic device, particularly an organic electroluminescence device, characterized in that one or more layers are coated by a sublimation method. In this case, the material is applied by vacuum deposition in a vacuum sublimation system at an initial pressure of less ^{than 10-5} mbar, preferably ^{less than 10-6 mbar.} The initial pressure can be lower or higher, eg less than ^{10-7 mbar.}

Equally preferred are electronic devices, particularly organic electroluminescence devices, characterized in that one or more layers are applied by the OVPD (organic vapor deposition) method or by sublimation of a carrier gas. be. In this case, the material is applied at a pressure of ^{10-5 mb-1b.} A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly by a nozzle and further structured (eg, MS Arnold et al.,. Appl. Phys. Lett. 2008, 92, 053301).

More preferably, one or more layers are, for example, by spin coating, or, for example, screen printing, flexographic printing, offset printing, or nozzle printing, but more preferably LITI (photoinduced thermal imaging, thermal transfer printing). Alternatively, it is an electronic element, particularly an organic electroluminescence element, which is manufactured from a solution by an arbitrary printing method such as inkjet printing. A soluble compound is required for this purpose, which can be obtained, for example, by appropriate substitution.

Electronic devices, particularly organic electroluminescence devices, can also be manufactured as a hybrid system by applying one or more layers from a solution and further applying one or more other layers by vacuum thin film deposition. For example, a light emitting layer containing a compound according to the present invention, preferably a compound having a structure of formula (V), and a matrix material is applied from the solution, and the hole blocking layer and / or the electron transporting layer is put under reduced pressure. , Can be applied by vacuum deposition.

Those skilled in the art will recognize these methods in a general sense and include electronic devices comprising the compounds obtained by the present invention, preferably compounds comprising the structure of formula (V) or the preferred embodiment described above, particularly organic electroluminescence. It can be applied to the element without difficulty.

The electronic devices of the present invention, in particular organic electroluminescence devices, are notable for one or more of the following amazing advantages over prior art:
1. 1. Compounds, oligomers, polymers or dendrimers obtained by the present invention, preferably compounds, oligomers, polymers or dendrimers comprising the structure of formula (V) or the preferred forms described above and below, are used as electron conductive materials and / or positive. Electronic devices, especially organic electroluminescence devices, which are included as a hole conduction material or as a matrix material, have a very good life.
2. 2. The compound, oligomer, polymer or dendrimer obtained by the present invention, preferably a compound, oligomer, polymer or dendrimer comprising the structure of formula (V) or the preferred form described above and below, is an electron transport material, hole conduction. Electronic devices, particularly organic electroluminescence devices, which are included as materials and / or as host materials, have excellent efficiency. More specifically, the efficiency is significantly higher when compared to similar compounds that do not contain any non-aromatic or non-heteroaromatic polycyclic ring system with at least two rings. In this context, the compounds, oligomers, polymers or dendrimers obtained by the present invention, preferably comprising the structure of formula (V) or the preferred forms described above and below, are used in electronic devices. When used, it results in a low working voltage. In this context, these compounds result in low roll-off, i.e., a small reduction in power efficiency of the device at high brightness.
3. 3. The compound, oligomer, polymer or dendrimer obtained by the present invention, preferably a compound, oligomer, polymer or dendrimer comprising the structure of formula (V) or the preferred form described above and below, is an electron transport material, hole conduction. Electronic devices, particularly organic electroluminescence devices, which are included as materials and / or as host materials, have excellent color purity.
4. The compounds, oligomers, polymers or dendrimers obtained by the present invention, preferably comprising the structure of formula (V) or the preferred forms described above and below, are very high thermal and photochemical. It is a compound that exhibits stability and has a very long life.
5. With the compound, oligomer, polymer or dendrimer obtained by the present invention, preferably with a compound, oligomer, polymer or dendrimer comprising the structure of formula (V) or the preferred forms described above and below, electronic devices, in particular. , The formation of optical loss channels in organic electroluminescence devices, can be suppressed. As a result, these devices are characterized by high PL efficiency and hence high EL efficiency of the emitter, and excellent energy transfer from the matrix to the dopant.
6. The compounds, oligomers, polymers or dendrimers obtained by the present invention, preferably comprising the structure of formula (V) or the preferred forms described above and below, have excellent glass film formation. ..
7. The compounds, oligomers, polymers or dendrimers obtained by the present invention, preferably comprising the structure of formula (V) or the preferred forms described above and below, are very good membranes from solution. To form.
These above-mentioned advantages are not accompanied by deterioration of other electronic properties.

The compounds and mixtures of the present invention are suitable for use in electronic devices. Here, the electronic device is understood to mean a device containing at least one layer, which comprises at least one organic compound. The device, however, can include a layer made of an inorganic material or an entirely inorganic material.

Accordingly, the invention further provides the use of the compounds or mixtures of the invention in electronic devices, especially in organic electroluminescence devices.

The invention further comprises a fluorescent emitter, a light emitter exhibiting TADF (heat-activated delayed fluorescence), a host material, in an electronic element of the compound of the invention and / or the oligomer, polymer or dendrimer of the invention. Electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron block materials, hole block materials and / or wide gap materials, preferably fluorescent emitters (singlet emitters), host materials, positive Provided for use as a hole conduction material and / or an electron transport material.

The invention further provides an electronic device comprising at least one of the compounds or mixtures of the invention described in detail above. In this case, the priorities previously detailed for the compound also apply to the electronic device. More preferably, the electronic element includes an organic electroluminescence element (OLED, PLED), an organic integrated circuit (O-IC), an organic electric field effect transistor (O-FET), an organic thin film (O-TFT), and an organic light emitting transistor (O). -LET), organic solar cell (O-SC), organic light detector, organic photoreceiver, organic electric field extinguishing element (O-FQD), organic electric sensor, light emitting electrochemical cell (LEC), organic laser diode (O) -Laser) and organic plasmon light emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), preferably selected from the group consisting of organic electroluminescence devices (OLEDs, PLEDs), especially phosphorescent OLEDs. be.

In a further embodiment of the invention, the organic electroluminescence device of the invention does not include a separated hole injection layer and / or hole transport layer and / or hole block layer and / or electron transport layer. Means, for example, as described in WO2005 / 053051, that the light emitting layer is directly bonded to the hole injection layer or anode and / or the light emitting layer is directly bonded to the electron transport layer or electron injection layer or cathode. do. Further, for example, as described in WO2009 / 030981, the same or similar metal complex as the metal complex in the light emitting layer may be used as a hole transporting or hole injecting material for directly bonding to the light emitting layer. can.

In a further layer of the organic electroluminescence device of the present invention, any material commonly used according to prior art can be used. Therefore, the person skilled in the art may use any material known for the organic electroluminescence device as a compound, oligomer, polymer or dendrimer obtained by the present invention, preferably the formula (V) or preferably, without making any inventive device. It can be used in combination with compounds, oligomers, polymers or dendrimers comprising morphological structures.

The compounds of the present invention generally have very good properties when used in organic electroluminescence devices. In particular, when the compound of the present invention is used in an organic electroluminescence device, the life is significantly better than that of similar compounds according to the prior art. Here, other properties of the organic electroluminescence device, in particular efficiency and voltage, are similarly better or at least equivalent.

It should be noted that the variants of the forms described in the present invention are included within the scope of the present invention. Each feature disclosed in the present invention may be exchanged for an alternative feature that serves the same or equivalent or similar purpose, unless expressly excluded. Therefore, each feature disclosed in the present invention is considered to be an example of a general series, or an equivalent or similar feature, unless otherwise specified.

All features of the invention can be combined in any way with each other, unless the special features and / or procedures are mutually exclusive. This is especially true of the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (and uncombined).

It should be noted that many features, and in particular the features of the preferred embodiments of the invention, should be considered in themselves as inventive and not only as part of the embodiments of the invention. Should be. For these features, independent protection may be sought in addition to or in lieu of the inventions currently described in the claims.

The technical teachings disclosed with the present invention can be extracted and combined with other examples.

The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto.

A person skilled in the art can further manufacture the electronic device of the present invention using the following details without any inventive device, whereby the present invention can be carried out over the entire scope of claims.

Examples The following synthesis is carried out in a dry solvent and in a protective gas atmosphere unless otherwise specified. Metal complexes are further treated in the dark or under yellow light. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The numbers in square brackets or the numbers given for individual compounds relate to the CAS numbers of known compounds in the literature. In the case of compounds that can display multiple tautomers, one tautomer is typically shown.

General methods of enamine synthesis:
A well-stirred mixture of 6.0 equal volumes of secondary amine in n-heptane (0.3 ml / mmol) cooled to 0 ° C. to 1.2 in n-heptane (2 ml / mmol). An equal amount of titanium chloride (IV) is added dropwise. Suitable secondary amines are particularly cyclic secondary amines such as pyrrolidine [123-75-1], piperidine [110-89-4] and morpholine [110-91-8]. The mixture is premixed with 1.0 equal amount of ketone and heated under reflux for 24 hours. After cooling, the titanium dioxide is filtered and washed 3 times with n-heptane. n-Heptane is distilled off and enamine is purified by Kugelrohr distillation under reduced pressure.

０℃に冷却された、２００ｍｌのｎ−ヘプタン中の５０．２ｍｌ（６００ｍｍｏｌ）のピロリジン［１２３−７５−１］のよく攪拌された混合物に、２４０ｍｌのｎ−ヘプタン中の１３．２ｍｌ（１２０ｍｍｏｌ）の塩化チタン（ＩＶ）が滴下される。混合物は、１６．４ｇ（１００ｍｍｏｌ）のホモアダマンタノン［２４６６９−５６−５］と予め混合され、そして還流下で２４時間加熱される。冷却後、二酸化チタンはろ過され、１００ｍｌのｎ−ヘプタンで３回洗浄される。ｎ−ヘプタンは留去され、エナミンは、減圧下で、クーゲルロール蒸留によって精製される。収率：１６．７ｇ（７７ｍｍｏｌ）、７７％。純度：約９７％^１Ｈ ＮＭＲによる。 Example E1:

13.2 ml (120 mmol) in 240 ml n-heptane to a well-stirred mixture of 50.2 ml (600 mmol) pyrrolidine [123-75-1] in 200 ml n-heptane cooled to 0 ° C. Titanium chloride (IV) is dropped. The mixture is premixed with 16.4 g (100 mmol) of homoadamantanone [24669-56-5] and heated under reflux for 24 hours. After cooling, the titanium dioxide is filtered and washed 3 times with 100 ml n-heptane. n-Heptane is distilled off and enamine is purified by Kugelrohr distillation under reduced pressure. Yield: 16.7 g (77 mmol), 77%. Purity: Approximately 97% ^{1 by 1} H NMR.

The following compounds may be prepared in the same manner:

General method of pyridine synthesis:

Step 1 and Step 2:
Steps 1 and 2 are performed sequentially, preferably time is strictly adhered to in formamide razone formation.
1.0 equal amount of hydrazine hydrate [7803-57-] in a well-stirred solution of 1.0 equal amount of formamidinium acetate [3473-63-0] in methanol (3.5 ml / mmol). 8] is added and the mixture is stirred at room temperature for 5 minutes. This solution is poured into a solution or suspension of 1.0 equal volume of glyoxal or glyoxal hydrate in methanol (7 ml / mmol), and immediately 1.0 equal volume of triethylamine is added. The reaction mixture is stirred at room temperature for 60 hours. Methanol is removed at 30 ° C. under reflux, the residue is collected in 5N aqueous hydrochloric acid solution (2 ml / eq) and the aqueous phase is extracted 3 times with methyl tert-butyl ether (1 ml / eq). The aqueous phase in hydrochloric acid is adjusted to pH> 10 with ice-cold 1N sodium hydroxide while cooling with ice, and is extracted three times with dichloromethane (DCM) (2 ml / eq). The combined organic phases are dried over magnesium sulphate. The desiccant is filtered using an aluminum oxide bed in the form of a dichloromethane slurry (aluminum oxide, basic, activity level 1 (according to Woolm)) and the filtrate is dried and concentrated under reduced pressure. Further purification may be performed with a suitable solvent or solvent mixture (typical solvents include: heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, dioxane, acetone, ethyl acetate, butyl acetate, acetonitrile, isopropanol, ethanol, methanol and the like. ) By crystallization or by chromatography / flash chromatography on silica gel.

Step 3:
1,2,4-triazine and enamin in a ratio of 1.0: 1.0 to typically 1.0: 1.2 in a four-necked flask equipped with a distillation system, a built-in thermometer and a precision glass stirrer. , First put in under an argon atmosphere. The mixture is heated at 150 ° C. to 200 ° C., typically 160 ° C. to 180 ° C., generating nitrogen for 30-60 minutes with stirring. The secondary amine formed is distilled off in a distillation system. When a solid or high melting point reactant is reacting, a high boiling point inert solvent (typical solvents such as: chlorobenzene, benzonitrile, nitrobenzene, DMSO, DMAC, NMP, di, try, tetraethylene glycol dimethyl ether, etc.) Oligo- / polyether etc.) can be added. Further, a solvent / solvent mixture having a boiling point <150 ° C. (typical solvents such as: heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, dioxane, acetone, ethyl acetate, butyl acetate, acetonitrile) can also be used. can. In this case, the reaction takes place in a stirred autoclave. The progress of the reaction can be monitored by increasing pressure in this case.
After the generation of nitrogen ends or the pressure rise stops, stirring is continued for an additional 30-60 minutes. The conversion reaction can be monitored, for example, by ¹ H NMR spectroscopy. After cooling, the crude product is a suitable solvent or solvent mixture (typical solvents such as: heptane, cyclohexane, toluene, methyltert-butyl ether, THF, dioxane, acetone, ethyl acetate) under standard pressure or reduced pressure. , Butyl acetate, acetonitrile, isopropanol, ethanol, methanol, etc.), or chromatographed / flash chromatographed on silica gel, or purified by continuous thermal extraction and / or distillation / Googlel roll distillation / sublimation. Will be done. Further converted to OLED material, Synton S has a typical purity of ^{> 95% (according to 1 1 H NMR).} OLED materials, HTMs (hole transport materials), TMMs (triplet matrix materials), ETMs (electron transport materials), SMBs (singlet matrix blue) have typical purity> 99.9% (by HPLC). It is sublimated at least once or heat-treated under high vacuum.

実施例Ｓ１ａ：ステップ１および２

３５０ｍｌのメタノール中の１０．４ｇ（１００ｍｍｏｌ）の酢酸ホルムアミジニウム［３４７３６３−０］のよく撹拌された溶液に、５．０ｇ（１００ｍｍｏｌ）のヒドラジン水和物［７８０３−５７−８］が加えられ、混合物は室温で５分攪拌される。この溶液は、７００ｍｌのメタノール中の１８．７ｇ（１００ｍｍｏｌ）の（ｐ−クロロフェニル）グリオキサール［４９９８−１５−６］溶液に注がれ、そして、１０．２ｇ（１００ｍｍｏｌ）のトリエチルアミンがすぐに加えられる。反応混合物は、室温で６０時間攪拌される。メタノールは減圧下で３０℃で除去され、残留物は、２００ｍｌの５Ｎ塩酸水溶液に採取され、塩酸中の水相は、１００ｍｌのメチルｔｅｒｔ−ブチルエーテルで３回抽出される。塩酸中の水相は、氷で冷却しながら、氷冷１Ｎの水酸化ナトリウム水溶液でｐＨ＞１０に調整され、２００ｍｌのＤＣＭで３回抽出される。集められた有機層は、硫酸マグネシウムで乾燥される。ろ液は、ＤＣＭスラリー（１００ｇの酸化アルミニウム、ｂａｓｉｃ，活性レベル１（Ｗｏｅｌｍによる））の形態の酸化アルミニウム床によってろ過される。さらなる精製は、少量の酢酸エチルを添加し、シクロヘキサンから結晶化される。収率：１０．０ｇ（ｍｍｏｌ）、５２％。純度：約９５％^１ＨＮＭＲによる。 Example S1:

Example S1a: Steps 1 and 2

5.0 g (100 mmol) of hydrazine hydrate [7803-57-8] is added to a well-stirred solution of 10.4 g (100 mmol) of formamidinium acetate [347363-0] in 350 ml of methanol. , The mixture is stirred at room temperature for 5 minutes. This solution is poured into 18.7 g (100 mmol) of (p-chlorophenyl) glyoxal [4998-15-6] solution in 700 ml of methanol, and 10.2 g (100 mmol) of triethylamine is immediately added. .. The reaction mixture is stirred at room temperature for 60 hours. Methanol is removed at 30 ° C. under reduced pressure, the residue is collected in 200 ml of 5N aqueous hydrochloric acid solution and the aqueous phase in hydrochloric acid is extracted 3 times with 100 ml of methyl tert-butyl ether. The aqueous phase in hydrochloric acid is adjusted to pH> 10 with ice-cold 1N aqueous sodium hydroxide solution while cooling with ice, and is extracted three times with 200 ml of DCM. The collected organic layer is dried over magnesium sulfate. The filtrate is filtered through an aluminum oxide bed in the form of a DCM slurry (100 g aluminum oxide, basic, activity level 1 (according to Woolm)). For further purification, a small amount of ethyl acetate is added and crystallized from cyclohexane. Yield: 10.0 g (mmol), 52%. Purity: Approximately 95% ^{1 by} HNMR.

１９．２ｇ（１００ｍｍｏｌ）の１，２，４−トリアジンＳ１ａおよび２１．７ｇ（１０５ｍｍｏｌ）のエナミンＥ１の混合物が、蒸留システム、内蔵温度計および精密ガラススターラーを備えた２５０ｍｌの４口フラスコに、アルゴン雰囲気下で、最初に投入される。混合物は、撹拌しながら、１６０℃に加熱される。窒素の発生は３０分後に完了する。撹拌はさらに３０分間続けられ、そして混合物は冷却される。留去されたピロリジンは廃棄される。粗生成物はシリカゲル状でクロマトグラフされる（１０ｇのメルク シリカゲル６０／１ｇの粗生成物、ｎ−ヘプタン／酢酸エチル２０：１）。収率：２４．３ｇ（７８ｍｍｏｌ）、７８％。純度：約９７％^１Ｈ ＮＭＲによる、図１参照。 Example S1b: Step 3

A mixture of 19.2 g (100 mmol) 1,2,4-triazine S1a and 21.7 g (105 mmol) enamine E1 in a 250 ml four-necked flask equipped with a distillation system, built-in thermometer and precision glass stirrer. In the atmosphere, it is put in first. The mixture is heated to 160 ° C. with stirring. Nitrogen generation is complete after 30 minutes. Stirring is continued for an additional 30 minutes and the mixture is cooled. The distilled pyrrolidine is discarded. The crude product is chromatographed in the form of silica gel (10 g Merck silica gel 60/1 g crude product, n-heptane / ethyl acetate 20: 1). Yield: 24.3 g (78 mmol), 78%. Purity: Approximately 97% 1 See FIG. 1 by ^{1 H NMR.}

The following compounds may be prepared in the same manner:

ＷＯ２０１６／１２４３０４による調製。最初に、Ｓ１が実施例２１、変形Ｂ（１１６頁参照）と同様にボロン酸エステルを調製するために使用される。この後、ボロン酸エステルは、例Ｌ１（１６０頁参照）と同様に、１，３，５−トリス（２−ブロモフェニル）ベンゼン［３８０６２６−５６−２］と反応させる。２つのステージの後の収率：５６％；純度：約９７％（^１Ｈ ＮＭＲによる）。 Synthesis of tripod-type ligand TL:
A: Synthesis Example of a tripod-type ligand having three identical bidentate subligands TL1

Prepared by WO2016 / 124304. First, S1 is used to prepare the boronic acid ester as in Example 21, variant B (see page 116). After this, the boronic acid ester is reacted with 1,3,5-tris (2-bromophenyl) benzene [380626-56-2] in the same manner as in Example L1 (see page 160). Yield after 2 stages: 56%; Purity: Approximately 97% (according to ^{1 1} H NMR).

The following compounds may be prepared in the same manner:

ＷＯ２０１６／１２４３０４による調製。最初に、Ｓ１が実施例２１、変形Ｂ（１１６頁参照）と同様にボロン酸エステルを調製するために使用される。この後、ボロン酸エステルは、例１２０１（３７４頁参照）と同様に、２，２’−［５’’−（２−ブロモフェニル）［１，１’：２’，１’’：３’’，１’’’：２’’’，１’’’’−キンキフェニル］−４，４’’’’−ジイル］ビスピリジン［１９８９６０５−０４−０］と反応させる。２つのステージの後の収率：６７％；純度：約９７％（^１Ｈ ＮＭＲによる）。 B: Synthesis of tripod-type ligands with different bidentate subligands Example TL4:

Prepared by WO2016 / 124304. First, S1 is used to prepare the boronic acid ester as in Example 21, variant B (see page 116). After this, the boronic acid ester was added to 2,2'-[5''-(2-bromophenyl) [1,1': 2', 1'': 3', as in Example 1201 (see page 374). ', 1''': 2''', 1''''-kinkiphenyl] -4,4''''-diyl] Bispyridine [1989605-04-0] is reacted. Yield after 2 stages: 67%; Purity: Approximately 97% (according to ^{1 1} H NMR).

The following compounds may be prepared in the same manner:

ＷＯ２０１６／１２４３０４、Ｉｒ（Ｌ１）変形Ａ、２１８頁参照による調製。ここに記載されるような精製、シリカゲル上のクロマトグラフィ、ＤＣＭ／メタノール（１：１、ｖｖ）を用いる３回およびＤＣＭ／アセトニトリル（２：１、ｖｖ）による３回の熱抽出、およびｐ約１０^−６ｍｂａｒでの昇華／熱処理による。収率：７７％；純度：＞９９．９％ＨＰＬＣによる。 Synthesis of C3- and C1-symmetric tripod iridium complexes:
Example Ir (TL1):

Prepared by referring to WO2016 / 124304, Ir (L1) variant A, page 218. Purification as described herein, chromatography on silica gel, 3 heat extractions with DCM / methanol (1: 1, vv) and 3 heat extractions with DCM / acetonitrile (2: 1, vv), and p about 10. ^By sublimation / heat treatment at -6 mbar. Yield: 77%; Purity:> 99.9% by HPLC.

The following compounds may be prepared in the same manner:

ＷＯ２０１５／１０４０４５による調製、Ｉｒ（ＬＢ７４）_３、１７９頁参照。収率：５７％；純度：＞９９．９％ＨＰＬＣによる。 Synthesis of C3-symmetric iridium complex of bidentate ligand L:
Example Ir (L1) ₃ :

Prepared by WO2015 / 104045, Ir (LB74) ₃ , p. 179. Yield: 57%; Purity:> 99.9% by HPLC.

ＷＯ２０１５／１０４０４５による調製。最初に、Ｃｌ二量体は、［Ｉｒ（Ｌ４２）_２Ｃｌ）_２と同様に調製される（１９３頁参照）。これは、Ｉｒ５３８と同様に、アセチルアセトンと反応する（２１８頁参照）。２つのステージ後の収率：５３％；純度：＞９９．９％ＨＰＬＣによる。 Synthesis of C2-symmetric N, N-trans-iridium complex of bidentate ligand L:
Example Ir (L2) ₂ (acac):

Prepared by WO2015 / 104045. First, the Cl dimer is prepared in the same manner as _{[Ir (L42) 2} Cl) _{2 (see page 193).} It reacts with acetylacetone, similar to Ir538 (see page 218). Yield after two stages: 53%; Purity:> 99.9% by HPLC.

The following compounds may be prepared in the same manner:

Vacuum processed element:
OLEDs according to the present invention and OLEDs according to the prior art are manufactured by the general method described in WO2004 / 058911, which adapts to the situations (layer thickness range, materials used) described herein.

In the following examples, the results of various OLEDs are shown. A washed glass plate (Miele laboratory glass washer, Merck's Extran detergent) coated with 50 nm thick structured ITO (indium tin oxide) is pretreated with UV ozone for 25 minutes (made by UVP). PR-100UV Ozone Generator), within 30 minutes, for improved process, 20 nm PEDOT: PSS (Poly (3,4-ethylenedioxythiophene) Poly (styrene sulfonate), which is Heraeus Precious Metals GmbH. (Purchased as CLEVIOS ™ PVP AI 4083 from (Germany), spin coated from aqueous solution) and baked at 180 ° C. for 10 minutes. These coated glass plates form a substrate to which the OLED is applied.

The OLED basically has the following layer structure: substrate / hole injection layer 1 (HIL1) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm / hole transport. Layer 1 (HTL1) / hole transport layer 2 (HTL2) / light emitting layer (EML) / hole block layer (HBL) / electron transport layer (ETL) / arbitrary electron injection layer (EIL) / and finally the cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm.

First, the vacuum-processed OLED will be described. For this purpose, all materials are applied by thermal deposition in a vacuum chamber. Here, the light emitting layer is always composed of at least one matrix material (host material) and a light emitting dopant (light emitter) that is mixed with the matrix material in a specific volume ratio by co-depositing. Here, the details shown in the form of RTMM1: RTMM2: Ir (L1) (55%: 35%: 10%) are such that the material RTMM1 is present in the layer at a volume ratio of 55% and RTMM2 is 35%. It means that Ir (L1) is present in the layer at a ratio of 10%. Similarly, the electron transport layer may also consist of a mixture of the two materials. The exact structure of the OLED can be seen in Table 1. The materials used in the manufacture of OLEDs are shown in Table 4.

OLEDs are characterized by standard methods. For this purpose, the current / voltage / luminous flux density characteristic line (IUL characteristic line) is assumed, assuming electroluminescence spectrum, current efficiency (measured by cd / A), power efficiency (measured by lm / W) and Lambert emission characteristics. ), External quantum efficiency (EQE, measured as a percentage) as a function of luminous flux density and lifetime are measured. The electroluminescence spectrum is measured at a luminous flux density of 1000 cd / m ² , and the CIE1931x and y color coordinates are calculated from it. The lifetime LT90 is defined as the time required for the initial brightness to decrease to 90% of the initial brightness at 10000 cd / m ^2.

The OLED can even be initially operated with different initial brightness. Then, the life value can be converted into another initial brightness value by a conversion formula known to those skilled in the art.

Use of compounds of the invention as materials in phosphorescent OLEDs The compounds of the invention are used, among other things, as HTMs (hole transport materials), TMMs (triplet matrix materials), ETMs (electron transport materials), and in the light emitting layer of OLEDs. It can be used as a phosphorescent material. The iridium compounds according to Table 4 are used as a comparison of prior art. The results of OLED are summarized in Table 2.

Solution treated device:
A: From low molecular weight soluble functional materials Iridium complexes can also be treated from solution, in this case very good in terms of treatment technology compared to vacuum treated OLEDs while having good properties. Brings a simple OLED to the. The production of such components is based on the production of polymer light emitting diodes (PLEDs) already described many times in the literature (eg WO2004 / 037887). The structure is composed of a substrate / ITO / hole injection layer (60 nm) / intermediate layer (20 nm) / light emitting layer (60 nm) / hole block layer (10 nm) / electron transport layer (40 nm) / cathode. For this purpose, a Technoprint substrate (soda-lime glass) is used, to which an ITO structure (indium tin oxide, transparent conductive anode) is applied. The substrate is washed in a clean room with DI water and detergent (Deconex 15PF) and then activated by UV / ozone plasma treatment. Then, in the same clean room, a 20 nm hole injection layer is applied by spin coating. The required spin rate depends on the degree of dilution and the shape of the particular spin coater. To remove residual water from the layer, the substrate is fired on a hot plate at 200 ° C. for 30 minutes. The intermediate layer used functions for hole transport. In this case, Merck's HL-X is used. The intermediate layer can be replaced with one or more layers, which only needs to satisfy the condition that it will not be desorbed again by the subsequent treatment step of EML deposition from the solution. For the production of the light emitting layer, the triplet light emitter of the present invention is dissolved in toluene or chlorobenzene together with the matrix material. Here, if a typical layer thickness of 60 nm for the device is achieved by spin coating, the typical solid content of the solution is 16-25 g / L. The solution-treated child comprises a light emitting layer composed of RTMM3: RTMM4: Ir (TL) (20%: 58%: 22%). The light emitting layer is applied by spin coating in an inert gas atmosphere, in the case of the present invention, in argon and heated at 160 ° C. for 10 minutes. A hole block layer (10 nm ETM1) and an electron transport layer (40 nm RETM1 (50%) / RETM2 (50%)) are vapor-deposited on the latter (typical vapor deposition pressures such as those manufactured by Lesker are 5 × 10 ^{−. 6} mbar). Finally, an aluminum (100 nm) cathode is applied by thin film deposition (high purity metal from Aldrich). To protect the device from air and atmospheric moisture, the device is finally encapsulated and then its characteristics are determined. The OLED example has not been optimized yet, but Table 3 summarizes the results obtained. The lifetime LT50 is defined as the time until the operating brightness drops to 50% of the initial brightness at an initial brightness of 1000 cd / m ^2.

Claims (17)

A method for preparing a steric hindrance heteroaromatic nitrogen compound, the following steps:
A) Providing 1,2,4-triazine;
B) To provide an active alkene having a non-aromatic or non-heteroaromatic polycyclic ring system; and C) react the compounds provided in steps A) and B) with a sterically hindered heteroaromatic nitrogen compound. Including getting
The at least one compound provided in steps A) and / or B) is characterized by comprising an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and optionally substituted. And how. The method of claim 1, wherein the active double bond of the alkene provided in step B) is part of a few or oligocyclic rings. The method of claim 1 or 2, wherein the alkene provided in step B) is cyclic enolate and / or enamine, preferably derived from a few or oligocyclic ketones. The method according to any one of claims 1 to 3, wherein the 1,2,4-triazine is obtained by reacting 1,2-dicarbonyl with formamide razone. The method according to any one of claims 1 to 4, wherein the 1,2,4-triazine is obtained by reacting a nitroaromatic or a nitroheteroaromatic with an amidine compound. The method according to any one of claims 1 to 5, wherein the 1,2,4-triazine can be represented by the formula (I).

(Here, the symbols used are:
R ^a , R ^b , R ^c are the same or different, H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , OH, COOH, C (= O). N (R ¹ ) ₂ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S ( = O) ₂ R ¹ , OSO ₂ R ¹ , linear, alkyl, alkoxy or thioalkoxy groups with 1 to 20 carbon atoms or alkenyl or alkynyl groups or 3 to 20 with 2 to 20 carbon atoms. carbon atoms having a branched or cyclic alkyl, wherein the alkoxy or thioalkoxy group (said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group, respectively, substituted by one or more R ¹ radicals well, wherein one or more non-adjacent CH ₂ groups ^{may, R 1 C = CR 1,} C≡C, Si (R 1) 2, C = O, NR 1, O, has been replaced by S or CONR ¹ may be), or a 5 to 40 aromatic ring atoms, which may be substituted by one or more R ¹ radicals in each case, an aromatic or heteroaromatic ring system, or 5 to 40 of It is an aryloxy or heteroaryloxy group that has an aromatic ring atom and may ^{be substituted with one or more R 1} radicals; at the same time, the two ^Ra , R ^b and / or R ^c radicals are both single. It may form a ring or polycyclic, aliphatic or aromatic ring system;
R ¹ is the same or different for each appearance, H, D, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , Si (R ² ) ₃ , B (OR ² ). ₂ , C (= O) R ² , P (= O) (R ² ) ₂ , S (= O) R ² , S (= O) ₂ R ² , OSO ₂ R ² , 1 to 20 carbon atoms A linear, alkyl, alkoxy or thioalkoxy group or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms ( wherein each alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group, respectively, may be optionally substituted by one or more R ² radicals, wherein one or more non-adjacent CH ₂ groups, R ² C = CR ² , C≡C, Si (R ² ) ₂ , C = O, NR ² , may be replaced by O, S or CONR ² ), or having 5-40 aromatic ring atoms. in each case may be substituted by one or more R ² radicals, have aromatic or aromatic ring atom of a heteroaromatic ring system or 5 to 40, optionally substituted by one or more R ² radicals may have aryloxy or heteroaryloxy group or 5 to 40 aromatic ring atoms, it may be substituted by one or more R ² radicals, aralkyl or heteroaralkyl group, or 10 to 40, It has an aromatic ring atoms, optionally substituted by one or more R ² radicals, diarylamino group, a di-heteroarylamino group or aryl heteroarylamino group; simultaneously, two or more R ¹ radicals together , Monocyclic or polycyclic, aliphatic or aromatic ring system may be formed;
R ² is, to or different on each occurrence, identically with H, D, F, or 1 to 20 carbon atoms, aliphatic, aromatic and / or heteroaromatic organic radical, especially hydrocarbyl radicals, (wherein in a one or more hydrogen atoms may be replaced by F), at the same time, two or more substituents R ² are both monocyclic or polycyclic, to form an aliphatic or aromatic ring system May) The method according to any one of claims 1 to 6, wherein the active alkene can be represented by the formula (II).

(Here, the symbols used are:
X is OH, OR ^d or NR ^d ₂ ;
R ^d is a linear, alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or 3 to 20 carbon atoms. having, branched or cyclic, alkyl, alkoxy or thioalkoxy group (wherein said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group, in each case, may be substituted by one or more R ¹ radicals ); At the same time, the two R radicals may together form a ring system, where R ¹ is as described in claim 8;
Here, the bicyclic / polycyclic ring may have one or more substituents R, and R may be the same or different for each appearance, H, D, F, Cl, Br, I. , N (R ¹ ) ₂ , CN, NO ₂ , OH, COOH, C (= O) N (R ¹ ) ₂ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ , OSO ₂ R ¹ , linear, alkyl, alkoxy having 1 to 20 carbon atoms. Alternatively, a branched or cyclic, alkyl, alkoxy or thioalkoxy group having an alkoxy or alkynyl group or 3 to 20 carbon atoms having a thioalkoxy group or 2 to 20 carbon atoms (here, said alkyl, alkoxy, thio). alkoxy, alkenyl or alkynyl group, respectively, may be optionally substituted by one or more ^{R 1} radicals, wherein one or more non-adjacent CH ₂ groups ^{may, R 1 C = CR 1,} C≡C, Si ( _{^{R 1) 2, C = O}} , NR 1, O, may be replaced by S or CONR ^1), or a 5 to 40 aromatic ring atoms, in each case, one or more of ^{R 1} may be substituted by a radical, have aromatic or aromatic ring atom of a heteroaromatic ring system or 5 to 40, in each case, it may be substituted by one or more R ¹ radicals, It is an aryloxy or heteroaryloxy group; at the same time, the two R radicals may both form a monocyclic or polycyclic, aliphatic or aromatic ring system, where R ¹ is claim 8. As described in) The method according to any one of claims 1 to 7, wherein the alkene provided in step B) is derived from a ketone of the formulas (IIa) to (IIo).

(Here, the structure of the indicated formula (IIa) ~ (IIo) may be substituted by one or more of ^{R 1} radicals, wherein, ^{R 1} is as defined in claim 8) The method according to any one of claims 4 to 8, wherein the 1,2-dicarbonyl can be represented by the formula (III).

(Here, the symbols R ^b and R ^c have the meanings described in claim 8). The method according to any one of claims 4 to 9, wherein the formamide razone can be represented by the formula (IV).

(Here, the symbol ^Ra has the meaning described in claim 8). A compound that can be obtained by the method according to claim 1. The additional ring system is a non-aromatic, preferably not fused to the ring via a bicyclic / polycyclic represented by formula (II) or (V), preferably having at least two, preferably at least three rings. The compound according to claim 11, wherein the non-heteroaromatic polycyclic system is condensed. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 10 or 12, wherein the compound has one or more bonds to the polymer, oligomer or dendrimer instead of a hydrogen atom or substituent. Oligomer, polymer or dendrimer. At least one compound according to claim 10 or 12, or the oligomer, polymer or dendrimer according to claim 13, and a fluorescent emitter, a phosphorescent emitter, a light emitter showing TADF (thermally activated delayed fluorescence), a host material. , A composition comprising at least one additional compound selected from the group consisting of electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials and hole blocking materials. A formulation comprising at least one compound of claim 10 or 12, or the oligomer, polymer or dendrimer of claim 13, or the composition of claim 14, and at least one solvent. An electronic element fluorescent emitter, TADF (thermally activated) of at least one compound of claim 10 or 12, or of the oligomer, polymer or dendrimer of claim 13, or of the composition of claim 14. Luminescent material exhibiting delayed fluorescence), host material, electron transport material, electron injection material, hole conduction material, hole injection material, electron block material, hole block material and / or wide bandgap material, preferably a fluorescent light emitter. Use as a (singlet illuminant), host material, hole conduction material and / or electron transport material. An electronic device comprising at least one compound according to claim 10 or 12, the oligomer, polymer or dendrimer according to claim 13, or the composition according to claim 14, wherein the electronic device is preferred. Is an organic electronic luminescence device, an organic integrated circuit, an organic electric field effect transistor, an organic thin film, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceiver, an organic electric field extinguishing element, a light emitting electrochemical cell, or an organic laser. An electronic element selected from diodes.

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