JP2016135775A - Novel heterocyclic compound and organic light-emitting element containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a novel heterocyclic compound which can be used for an electron transport layer or a luminous layer of an organic light-emitting element, has a long life and a low-voltage drive characteristic, and is excellent in luminous efficacy; and an organic light-emitting element containing the same.SOLUTION: The heterocyclic compound is represented by the chemical formula in the figure.SELECTED DRAWING: None

Description

  The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer disposed therebetween.
Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer often has a multilayer structure composed of different materials, for example, a hole injection layer, a hole transport layer, a light emitting layer. , An electron transport layer, an electron injection layer, and the like. When a voltage is applied between both electrodes in such an organic light emitting device structure, holes are injected from the anode and electrons are injected from the cathode into the organic material layer, and the injected holes and electrons meet. Excitons are formed in the light, and light is emitted when the excitons fall back to the ground state.
In an organic light emitting device, a light emitting material is classified into a fluorescent material derived from an electron singlet excited state and a phosphorescent material derived from an electron triplet excited state according to a light emission mechanism.

On the other hand, when only one substance is used as the light emitting material, the maximum emission wavelength shifts to a long wavelength due to intermolecular interaction, and the color purity is lowered, and the efficiency of the device is reduced due to the light emission attenuation effect. Thus, a host-dopant system can be used as the luminescent material in order to increase color purity and increase luminous efficiency due to energy transfer.
When an electric current is applied to the organic light emitting device, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons recombine in the light emitting layer through the hole transport layer and the electron transport layer, respectively. Form photoexcitons. The luminescent excitons thus formed emit light while transitioning to the ground state. The light is divided into fluorescence using singlet excitons and phosphorescence using triplet excitons according to a light emission mechanism, and the fluorescence and phosphorescence can be used as a light emitting source of an organic light emitting device.

  Fluorescence using only singlet excitons has a singlet exciton generation probability of 25%, and there is a limit in light emission efficiency. However, phosphorescence that can use triplet excitons has a light emission efficiency. Much research has been continued since is significantly more significant than fluorescence.

To date, CBP is the most widely known host material for the phosphorescent emitter, and organic light-emitting devices to which a hole blocking layer such as BCP or BAlq is applied are known.
However, although the element using the existing phosphorescent light emitting material is higher in efficiency than the element using the fluorescent light emitting material, the conventional material such as BAlq or CBP used as the host of the phosphorescent light emitting material is used. Since the driving voltage is higher than that of an element using a fluorescent material, there is a disadvantage that there is no great advantage in terms of power efficiency (lm / w) and that it should not be satisfied in terms of life. In order to use such a phosphorescent material as a light-emitting element, Korean Published Patent No. 10-2011-0013220 (2011.02.09) discloses a 6-membered aromatic ring or a 6-membered hetero ring. An organic compound in which an aromatic heterocycle is introduced into the skeleton of an aromatic ring is disclosed. In Japanese Unexamined Patent Application Publication No. 2010-166070 (2010.7.29), a substituted or unsubstituted pyrimidine or quinazoline skeleton is disclosed. Organic compounds having aryl or heteroaryl rings attached are disclosed.

  In the organic light emitting device, the charges injected from both electrodes recombine in the light emitting layer to obtain light emission, but the hole moving speed is faster than the electron moving speed, so that a part of the holes are in the light emitting layer. Decrease in efficiency due to exiting is a problem. Therefore, an electron transport material having a high electron moving speed is demanded.

In order to produce an organic compound having excellent electron transport ability and hole blocking ability, and excellent luminous efficiency and high stability in a thin film state, Korean Patent Application Publication No. 10-2012-0104204 (2012.9.20) ) Discloses an organic compound in which a pyridoindole derivative is bonded to a substituted anthracene ring structure. In Japanese Unexamined Patent Application Publication No. 2010-168363 (2011.08.05), external quantum efficiency and driving voltage are disclosed. An anthracene derivative having a pyridine naphthyl group having excellent properties is disclosed.
However, despite the efforts to manufacture the light-emitting material or electron transport material for organic light-emitting elements as described above, it can still be said that the development of materials for lowering the drive voltage or higher light emission efficiency is still sufficient. Therefore, there is a continuous need for the development of a light emitting material or an electron transport layer material that is capable of being driven at a low voltage but has excellent light emission efficiency.

Korean Published Patent No. 10-2011-0013220 (2011.02.09) Japanese Unexamined Patent Application Publication No. 2010-166070 (2010.7.29) Korean Published Patent No. 10-2012-0104204 (2012.9.20) Japanese Unexamined Patent Publication No. 2010-168363 (2011.08.05)

The first technical problem to be solved by the present invention is a novel heterocyclic compound that can be used in a light emitting layer or an electron transport layer of an organic light emitting device, has a long life and low voltage driving characteristics, and is excellent in luminous efficiency. Is to provide.
The second technical problem to be solved by the present invention is to provide an organic light emitting device containing the organic compound.

前記化学式Ａにおいて、
Ｘは、Ｓ、Ｏ、ＮＲ_１、ＣＲ_２Ｒ_３、ＳｉＲ_４Ｒ_５、ＧｅＲ_６Ｒ_７、Ｓｅ、Ｔｅ、及びＢＲ_８よりなる群から選択され、前記Ｒ_２とＲ_３、Ｒ_４とＲ_５、Ｒ_６とＲ_７は、それぞれ互いに連結されて環を形成することができ、
Ｔ_１はＮ又はＣＲ’であり、Ｔ_２はＮ又はＣＲ’’であり、Ｔ_３はＮ又はＣＲ’’’であるが、Ｔ_１からＴ_３の少なくとも一つはＮであり、
Ｂ_１はＮ又はＣＲ_１５であり、Ｂ_２はＮ又はＣＲ_１６であり、Ｂ_３はＮ又はＣＲ_１７であり、Ｂ_４はＮ又はＣＲ_１８であり、
前記Ｒ、Ｒ’からＲ’’’、Ｒ_１からＲ_８、Ｒ_１１からＲ_１８は、それぞれ同一又は異なり、互いに独立して、水素、重水素、置換もしくは無置換の炭素数１〜３０のアルキル基、置換もしくは無置換の炭素数２〜３０のアルケニル基、置換もしくは無置換の炭素数２〜３０のアルキニル基、置換もしくは無置換の炭素数３〜３０のシクロアルキル基、置換もしくは無置換の炭素数２〜３０のヘテロシクロアルキル基、置換もしくは無置換の炭素数５〜３０のシクロアルケニル基、置換もしくは無置換の炭素数１〜３０のアルコキシ基、置換もしくは無置換の炭素数６〜３０のアリールオキシ基、置換もしくは無置換の炭素数１〜３０のアルキルチオキシ基、置換もしくは無置換の炭素数５〜３０のアリールチオキシ基、置換もしくは無置換の炭素数１〜３０のアルキルアミン基、置換もしくは無置換の炭素数５〜３０のアリールアミン基、置換もしくは無置換の炭素数５〜５０のアリール基、置換もしくは無置換の炭素数３〜５０のヘテロアリール基、置換もしくは無置換の炭素数１〜３０のシリル基、置換もしくは無置換の炭素数１〜３０のカルボキシル基、チオール基、シアノ基、ヒドロキシ基、ニトロ基、ハロゲン基、セレン基、テルル基、アミノ基、置換もしくは無置換の炭素数１〜３０のエーテル基、置換もしくは無置換の炭素数１〜３０のエステル基の中から選択され、
前記Ｒ_１１からＲ_１８のうちのそれぞれが互いに隣接している場合、隣接する官能基は互いに連結されて脂環族又は芳香族の単環又は多環を形成することができ、
前記Ｒ_１１からＲ_１４のうちの互いに隣接している二つは、前記構造式Ｑの＊に連結されて縮合環を形成する単結合であり、
連結基Ｙは、単結合、置換もしくは無置換の炭素数１〜２０のアルキレン基、置換もしくは無置換の炭素数３〜２０のシクロアルキレン基、置換もしくは無置換の炭素数１〜２０のヘテロシクロアルキレン基、置換又は無置換の炭素数３〜２０のシクロアルケニレン基、置換もしくは無置換の炭素数１〜２０のヘテロシクロアルケニレン基、置換もしくは無置換の炭素数６〜６０のアリーレン基、置換もしくは無置換の炭素数１〜６０のヘテロアリーレン基の中から選択され、
前記Ｒ、Ｒ’からＲ’’’のうちのいずれか一つは、連結基Ｙに結合する単結合であり、
ｎは０〜２の整数であり、
Ｚは置換もしくは無置換の炭素数６〜５０のアリール基又は置換もしくは無置換の炭素数２〜５０のヘテロアリール基であるが、前記アリール基又はヘテロアリール基内の芳香族環のそれぞれの炭素は追加の縮合環を形成してさらに脂環族単環又は多環を形成することができ、前記さらに形成された脂環族の単環又は多環の炭素原子は、Ｎ、Ｓ、Ｏ、Ｓｅ、Ｔｅ、Ｓｉ及びＧｅの中から選択される少なくとも一つのヘテロ原子で置換でき、
前記「置換もしくは無置換の」における「置換」は、重水素、シアノ基、ハロゲン基、ヒドロキシ基、ニトロ基、炭素数１〜２４のアルキル基、炭素数１〜２４のハロゲン化アルキル基、炭素数１〜２４のアルケニル基、炭素数１〜２４のアルキニル基、炭素数１〜２４のヘテロアルキル基、炭素数６〜２４のアリール基、炭素数６〜２４のアリールアルキル基、炭素数２〜２４のヘテロアリール基、又は炭素数２〜２４のヘテロアリールアルキル基、炭素数１〜２４のアルコキシ基、炭素数１〜２４のアルキルアミノ基、炭素数１〜２４のアリールアミノ基、炭素数１〜２４のヘテロアリールアミノ基、炭素数１〜２４のアルキルシリル基、炭素数１〜２４のアリールシリル基、及び炭素数１〜２４のアリールオキシ基よりなる群から選ばれた１つ以上の置換基で置換されることを意味する。 In order to achieve the first technical problem, the present invention provides a heterocyclic compound represented by the following [Chemical Formula A].
[Chemical Formula A]

In the chemical formula A,
X is selected from the group consisting of S, O, NR ₁ , CR ₂ R ₃ , SiR ₄ R ₅ , GeR ₆ R ₇ , Se, Te, and BR ₈ , and R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ can be connected to each other to form a ring,
T ₁ is N or CR ′, T ₂ is N or CR ″, T ₃ is N or CR ′ ″, but at least one of T ₁ to T ₃ is N;
B ₁ is N or CR ₁₅ ; B ₂ is N or CR ₁₆ ; B ₃ is N or CR ₁₇ ; B ₄ is N or CR ₁₈ ;
R, R ′ to R ′ ″, R ₁ to R ₈ , R ₁₁ to R ₁₈ are the same or different, and independently of each other, hydrogen, deuterium, substituted or unsubstituted C 1-30. Alkyl group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted A heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 6 to 6 carbon atoms. 30 aryloxy groups, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or unsubstituted arylthioxy groups having 5 to 30 carbon atoms, substituted or unsubstituted A prime alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl amine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero group having 3 to 50 carbon atoms Aryl group, substituted or unsubstituted silyl group having 1 to 30 carbon atoms, substituted or unsubstituted carboxyl group having 1 to 30 carbon atoms, thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium Selected from a group, an amino group, a substituted or unsubstituted ether group having 1 to 30 carbon atoms, a substituted or unsubstituted ester group having 1 to 30 carbon atoms,
When each of R ₁₁ to R ₁₈ is adjacent to each other, adjacent functional groups may be linked to each other to form an alicyclic or aromatic monocyclic or polycyclic ring;
Two of R ₁₁ to R ₁₄ that are adjacent to each other are single bonds that are connected to * in the structural formula Q to form a condensed ring;
The linking group Y is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycle having 1 to 20 carbon atoms. An alkylene group, a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, substituted or Selected from unsubstituted C 1-60 heteroarylene groups;
Any one of R, R ′ to R ′ ″ is a single bond bonded to the linking group Y;
n is an integer from 0 to 2,
Z is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and each carbon of the aromatic ring in the aryl group or heteroaryl group. Can form an additional condensed ring to further form an alicyclic monocyclic or polycyclic ring, and the further formed alicyclic monocyclic or polycyclic carbon atoms include N, S, O, Can be substituted with at least one heteroatom selected from Se, Te, Si and Ge;
“Substitution” in the above “substituted or unsubstituted” means deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, carbon C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C2 24 heteroaryl group, or C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C1 Selected from the group consisting of ˜24 heteroarylamino groups, C1-C24 alkylsilyl groups, C1-C24 arylsilyl groups, and C1-C24 aryloxy groups It means substituted with one or more substituents.

  In order to achieve the second object, the present invention provides a first electrode, a second electrode facing the first electrode, and an organic intervening between the first electrode and the second electrode. Provided is an organic light-emitting device including a layer, wherein the organic layer includes at least one heterocyclic compound of the present invention.

  The heterocyclic compound according to the present invention has long life and low voltage drive characteristics when used as a phosphorescent host or electron transport layer material, and has excellent light emission efficiency. It can be used for the manufacture of special and excellent devices.

It is the schematic of the organic light emitting element which concerns on one specific example of this invention.

Hereinafter, the present invention will be described in more detail.
In the description of the substituent in the compound of the present invention, the alkyl group in the above-mentioned “substituted or unsubstituted alkyl group having 1 to 30 carbon atoms”, “substituted or unsubstituted aryl group having 5 to 50 carbon atoms” or the like, When considering the range of the aryl group, the ranges of the carbon number of the alkyl group having 1 to 30 carbon atoms and the aryl group having 5 to 50 carbon atoms are not considered without considering the portion where the substituent is substituted. The total number of carbon atoms constituting the alkyl or aryl moiety when viewed as a substituted one. For example, a phenyl group in which a butyl group is substituted at the para position should be regarded as corresponding to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

The aryl group used in the compound of the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a monocyclic or fused group containing 5 to 7 members, preferably 5 or 6 members. Includes ring systems. When the aryl group has a substituent, it can be fused with an adjacent substituent to further form a ring.
Specific examples of the aryl include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.
One or more hydrogen atoms of the aryl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (—NH ₂ , —NH (R), —N (R ') (R "), R' and R" are each independently an alkyl group having 1 to 10 carbon atoms, in this case, referred to as "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group , Sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms, alkynyl group having 1 to 24 carbon atoms, carbon number 1 It can be substituted with a -24 heteroalkyl group, an aryl group with 6-24 carbon atoms, an arylalkyl group with 6-24 carbon atoms, a heteroaryl group with 2-24 carbon atoms, or a heteroarylalkyl group with 2-24 carbon atoms.

  The heteroaryl group as a substituent used in the compound of the present invention is 1 to 4 selected from N, O, P, Se, Te, Si, Ge or S in each ring in the aryl group. A heteroaromatic organic radical having 2 to 24 carbon atoms that can contain a heteroatom, and the rings can be fused to form a ring. One or more hydrogen atoms of the heteroaryl group can be substituted with the same substituent as in the aryl group.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. In addition, one or more hydrogen atoms in the alkyl group may be substituted with the same substituent as in the aryl group.
Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy and the like. In the alkoxy group, one or more hydrogen atoms can be substituted with the same substituent as in the aryl group.
Specific examples of the silyl group which is a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methyl Examples thereof include cyclobutylsilyl and dimethylfurylsilyl. One or more hydrogen atoms in the silyl group can be substituted with the same substituent as in the aryl group.

The present invention is a compound represented by the chemical formula A, which has a structure in which two condensed ring structures including the T ₁ to T ₃ and two condensed ring structures including the structural formula Q are condensed with each other. The present invention is characterized by having a form in which a linking group Y is bonded to an aromatic ring carbon containing T ₁ to T ₃ .
In the present invention, in the case of a heterocyclic compound having such a structure, this is a phosphorescent host and can be used not only as a light emitting layer but also as an electron transport layer or electron injection layer material. As an example, in Formula A, T ₁ and T ₃ are each a nitrogen atom, T ₂ is CR ″, and the substituent R ″ is a single bond connected to the linking group Y. . That is, an aromatic ring carbon positioned between two nitrogen atoms in a structure having a quinazoline ring can be linked to the linking group Y.

ここで、前記構造式１から構造式９における芳香族環の炭素位は水素又は重水素が結合できる。 The linking groups Y in the chemical formula A of the present invention are the same or different and are each independently a single bond, or are any one selected from the following structural formulas 1 to 9. Can do.

Here, hydrogen or deuterium can be bonded to the carbon position of the aromatic ring in the structural formulas 1 to 9.

More preferably, in the present invention, the substituents R, R ′ to R ′ ″ and R ₁₁ to R ₁₈ in the chemical formula A are the same or different and independently of one another, hydrogen, deuterium, substituted or unsubstituted. A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; a substituted or unsubstituted aryl group having 5 to 20 carbon atoms; a substituted or unsubstituted carbon group having 2 to 20 carbon atoms; A heteroaryl group; one selected from
The n is 0 or 1, respectively.

前記構造式ＡからＥにおいて
ＷはＮＲ_２４であるが、Ｒ_２４は、単結合；又は置換もしくは無置換の炭素数５〜２０のアリーレン基；置換もしくは無置換の炭素数２〜２０のヘテロアリーレン基；の中から選ばれる１つであり、
Ｒ_２１からＲ_２３は、それぞれ同一又は異なり、互いに独立して、水素、重水素；置換もしくは無置換の炭素数１〜２０のアルキル基；置換もしくは無置換の炭素数３〜２０のシクロアルキル基；置換もしくは無置換の炭素数５〜２０のアリール基；置換もしくは無置換の炭素数２〜２０のヘテロアリール基；の中から選ばれる１つであり、
前記構造式Ａから構造式Ｅにおいて、
前記＊は、連結基Ｙに結合される結合サイトを意味し、
前記環状基ＡからＤは、それぞれ互いに同一又は異なり、５員環又は６員環の脂環族又は芳香族単環、又は多環を形成することが可能な炭素数４〜２０の炭化水素環基とすることができる。
本発明において、前記［化学式Ａ］におけるＺは置換もしくは無置換の炭素数６〜５０のアリール基とすることができる。 In the present invention, any one of B1 to B4 in [Chemical Formula A] may not be a nitrogen atom. That is, the aromatic ring constituting the hexagonal ring in the structural formula Q may be composed of only hydrocarbons.
In the present invention, Z in [Chemical Formula A] may be a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.
That is, the compound represented by [Chemical Formula A] may be composed of two heteroaryl groups sandwiching the linking group Y. In this case, in the heteroaryl group on the upper side of the linking group Y, is a hexagonal ring not containing T1 to T3 condensed with a 5-membered ring containing X and a 6-membered hydrocarbon ring containing B1 to B4? Or a 5-membered ring containing X and a 6-membered heterocycle containing B1 to B4.
More specifically, Z in [Chemical Formula A] can be a heteroaryl group represented by any one selected from Structural Formula A to Structural Formula E below.

In the structural formulas A to E, W is NR ₂₄ , but R ₂₄ is a single bond; or a substituted or unsubstituted arylene group having 5 to 20 carbon atoms; a substituted or unsubstituted heteroarylene having 2 to 20 carbon atoms; One selected from the group;
R ₂₁ to R ₂₃ are the same or different and independently of each other, hydrogen, deuterium; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms;
In Structural Formula A to Structural Formula E,
* Means a binding site bonded to the linking group Y;
The cyclic groups A to D are the same as or different from each other, and a hydrocarbon ring having 4 to 20 carbon atoms capable of forming a 5-membered or 6-membered alicyclic or aromatic monocyclic or polycyclic ring. It can be based.
In the present invention, Z in [Chemical Formula A] can be a substituted or unsubstituted aryl group having 6 to 50 carbon atoms.

As an example, the heterocyclic compound of the present invention can be selected from the group represented by the following [Chemical Formula 1] to [Chemical Formula 249].

The present invention includes a first electrode; a second electrode facing the first electrode; an organic layer interposed between the first electrode and the second electrode; and the organic layer is the hetero in the present invention. Provided is an organic light-emitting device containing at least one cyclic compound.
In the present invention, “(the organic layer) contains one or more organic compounds” means “(the organic layer) is one organic compound belonging to the category of the present invention or two different organic compounds belonging to the category of the organic compound”. It can be interpreted that the above-mentioned compounds can be included.
The organic layer may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. . At this time, the organic layer interposed between the first electrode and the second electrode includes a light emitting layer, the light emitting layer is composed of a host and a dopant, and the heterocyclic compound in the present invention is used as a host. it can.
In the present invention, a dopant material can be used for the light emitting layer together with the host. When the light emitting layer includes a host and a dopant, the dopant content can be selected from a range of about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

When the heterocyclic compound according to the present invention is used as a host, the organic layer may further include a hole blocking layer or an electron blocking layer.
In the present invention, the organic layer interposed between the first electrode and the second electrode includes an electron transport layer, and the heterocyclic compound in the present invention can be used for the electron transport layer.

In the present invention, as the electron transport layer material of the organic light emitting device, it functions to stably transport electrons injected from an electron injection electrode (Cathode), and a known electron transport material can be used. it can. Examples of known electron transporting materials include quinoline derivatives, particularly tris (8-quinolinolato) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10-noate) (beryllium bis (benzoquinolin-10-olate: Bebq2) , ADN, Compound 201, Compound 202, and materials such as PBD, BMD, and BND which are oxadiazole derivatives can be used, but are not limited thereto.

Hereinafter, the organic light emitting device of the present invention will be described with reference to FIG.
FIG. 1 is a cross-sectional view showing the structure of the organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode 80, and further includes a hole injection layer 30 and an electron injection layer 70 as necessary. In addition, one or two intermediate layers can be further formed, and a hole blocking layer or an electron blocking layer can be further formed.

With reference to FIG. 1, the organic light emitting device of the present invention and the manufacturing method thereof will be described.
First, an anode 20 is formed by coating an anode electrode material on the substrate 10. Here, as the substrate 10, a substrate used in a normal organic EL element is used, but an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproofness is preferable. As the anode electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.
A hole injection layer material is formed on the anode 20 electrode by vacuum thermal evaporation or spin coating. Next, a hole transport layer 40 is formed on the hole injection layer 30 by vacuum thermal deposition or spin coating with a hole transport layer material.
The material of the hole injection layer can be used without particular limitation as long as it is usually used in the art. For example, 2-TNATA [4,4 ′, 4 ″ -tris (2- naphthylphenyl-phenylamino) -triphenylamine], NPD [N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine)], TPD [N, N′-diphenyl-N, N′-bis (3-methyl) ) -1,1′-biphenyl-4,4′-diamine], DNTPD [N, N′-diphenyl-N, N′-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl -4,4'-diamin] etc. can be used. However, the present invention is not necessarily limited to this.

The material for the hole transport layer is not particularly limited as long as it is usually used in the art. For example, N, N′-bis (3-methylphenyl) -N, N′-diphenyl- [ 1,1-biphenyl] -4,4′-diamine (TPD) or N, N′-di (naphthalen-1-yl) -N, N′-diphenylbenzidine (a-NPD) or the like can be used. . However, the present invention is not necessarily limited to this.
Next, an organic light emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method. Can be formed as The hole blocking layer uses a material having a very low HOMO (High Occupied Molecular Orbital) level because the lifetime and efficiency of the device is reduced when holes pass through the organic light emitting layer and flow into the cathode. This serves to prevent such problems. At this time, the hole blocking material to be used is not particularly limited, but it must have an ionization potential higher than that of the light emitting compound while having an electron transport capability, and typically BAlq, BCP, TPBI, etc. are used. it can.

As the material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and any one selected from Chemical Formula 1001 to Chemical Formula 1007 can be used. It is not limited to this.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is vacuum thermal deposited on the electron injection layer 70. By forming the cathode 80 electrode, the organic EL element is completed. Here, as a metal for cathode formation, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- Silver (Mg—Ag) or the like can be used, and a transmissive cathode using ITO or IZO can be used to obtain a front light emitting element.
The light emitting layer may comprise a host and a dopant.

According to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 angstroms.
At this time, as a phosphorescence dopant used when a light emitting layer utilizes phosphorescence, it can be set as 1 or more types of compounds chosen from the compounds represented by the following general formula (A-1). .
[General Formula A-1]
ML ₁ L ₂ L ₃
Here, M is selected from the group consisting of metals of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, Group 15, Group 16, and Group 16, preferably Is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag. L ₁ , L ₂ and L ₃ are ligands which are the same or different from each other, and include any one independently selected from the following structural formula D, but are not limited thereto. “*” In the following structural formula D represents a site coordinated to the metal ion M.
[Structural Formula D]

In the structural formula D, the R's are the same or different from each other, and each independently represents hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted carbon. An aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms Group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted Or an arylamino group having 6 to 30 carbon atoms and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms. It can be;
Each R is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, Can be further substituted with one or more substituents selected from among halogen groups, deuterium and hydrogen;
R may be linked to each adjacent substituent with alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
L may be linked to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

As an example, the dopant represented by [General Formula A-1] may be any one selected from the following compounds.

  The light emitting layer may further include various hosts and various dopant materials in addition to the dopant and the host.

  In the present invention, the one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer may be a single molecule deposition method or It can be formed by a solution process. Here, the vapor deposition method means a method of forming a thin film by evaporating a substance used as a material for forming each of the layers by heating or the like in a vacuum or low pressure state, and the solution step includes A method of forming a thin film by mixing a substance used as a material for forming each layer with a solvent and using the method such as ink jet printing, roll-to-roll coating, screen printing, spray coating, dip coating, or spin coating. Means.

  The organic light emitting device according to the present invention can be used in any one device selected from a flat display device; a flexible display device; a monochromatic or white flat illumination device; and a monochromatic or white flexible illumination device.

＜１−ａ＞
乾燥した２Ｌの反応器にジベンゾフラン６０ｇ（３５７ｍｍｏｌ）を窒素気流下でテトラヒドロフラン４８０ｍＬに溶かした後、−７８℃で攪拌しながら１．６Ｍｎ−ブチルリチウム２８９ｍＬ（４６４ｍｍｏｌ）をゆっくり滴加する。滴加が完了したら、常温で１２時間撹拌する。その後、再び−７８℃でホウ酸トリメチル４８．２ｇ（４６４ｍｍｏｌ）をゆっくり滴加した後、常温に昇温して１時間撹拌する。反応終了の後、２Ｎ塩酸水溶液２５０ｍＬを常温で滴加した後、ｐＨ２に作り、３０分間撹拌する。その後、酢酸エチルと水で抽出し、有機層を減圧濃縮し、ジクロロメタンとヘプタンで再結晶して＜１−ａ＞６５ｇを得た。（収率８５％） Hereinafter, the present invention will be described in more detail with reference to preferred examples. It will be apparent to those skilled in the art that these examples are intended to illustrate the present invention more specifically and are not intended to limit the scope of the present invention.
(Example)
Synthesis Example 1 Synthesis of [Chemical Formula 1]
Synthesis Example 1-1. <1-a> Synthesis <1-a> was synthesized according to the following Reaction Scheme 1.
[Reaction Formula 1]

<1-a>
In a dry 2 L reactor, 60 g (357 mmol) of dibenzofuran is dissolved in 480 mL of tetrahydrofuran under a nitrogen stream, and then 289 mL (464 mmol) of 1.6 Mn-butyllithium is slowly added dropwise with stirring at −78 ° C. When the addition is complete, stir at ambient temperature for 12 hours. Thereafter, 48.2 g (464 mmol) of trimethyl borate is slowly added again at −78 ° C., and then the mixture is heated to room temperature and stirred for 1 hour. After completion of the reaction, 250 mL of 2N aqueous hydrochloric acid solution is added dropwise at room temperature, and then the pH is adjusted to 2 and stirred for 30 minutes. Thereafter, the mixture was extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized with dichloromethane and heptane to obtain <1-a> 65 g. (Yield 85%)

＜１−ｂ＞
乾燥した２Ｌの反応器に＜１−ａ＞６４ｇ（３０２ｍｍｏｌ）、硝酸ビスマス（ＩＩＩ）五水和物１０２．５ｇ（２１１ｍｍｏｌ）及びトルエン６４０ｍｌを入れ、６時間還流撹拌する。温度を降温した後、固体が生成されると、ジクロロメタンで濾過して除去する。濾液を濃縮してカラムクロマトグラフィーで分離することにより、＜１−ｂ＞４８ｇを得た。（収率７４％） Synthesis example 1-2. Synthesis of <1-b><1-b> was synthesized according to the following reaction formula 2.
[Reaction Formula 2]

<1-b>
<1-a> 64 g (302 mmol), 102.5 g (211 mmol) of bismuth (III) nitrate pentahydrate and 640 ml of toluene are placed in a dry 2 L reactor and stirred at reflux for 6 hours. When the temperature is lowered and a solid is formed, it is removed by filtration with dichloromethane. The filtrate was concentrated and separated by column chromatography to obtain <1-b> 48 g. (Yield 74%)

＜１−ｃ＞
乾燥した２Ｌの反応器にシアン化カリウム１５．８ｇ（２４３ｍｍｏｌ）、水酸化カリウム２４．７ｇ（４４１ｍｍｏｌ）、シアノ酢酸エチル７４．８ｇ（６６１ｍｍｏｌ）及びジメチルホルムアミド３８０ｍｌを入れて攪拌する。２０℃で＜１−ｂ＞４７ｇ（２２０ｍｍｏｌ）をジメチルホルムアミド９０ｍｌに溶かして滴加する。６０℃で１２時間還流撹拌する。５％水酸化ナトリウム２５０ｍｌを入れ、２時間還流撹拌する。反応終了の後、水１５００ｍＬに反応液をゆっくり入れて結晶化し、濾過する。濾過された固体をテトラヒドロフランに溶かしてカラムクロマトグラフィーで分離することにより、＜１−ｃ＞１１ｇを得た。（収率２４％） Synthesis example 1-3. Synthesis of <1-c><1-c> was synthesized according to the following reaction formula 3.
[Reaction Formula 3]

<1-c>
To a dry 2 L reactor, 15.8 g (243 mmol) of potassium cyanide, 24.7 g (441 mmol) of potassium hydroxide, 74.8 g (661 mmol) of ethyl cyanoacetate and 380 ml of dimethylformamide are stirred. At 20 ° C., 47 g (220 mmol) of <1-b> is dissolved in 90 ml of dimethylformamide and added dropwise. Stir at reflux at 60 ° C. for 12 hours. Add 250 ml of 5% sodium hydroxide and stir at reflux for 2 hours. After completion of the reaction, the reaction solution is slowly put into 1500 mL of water to crystallize and filtered. The filtered solid was dissolved in tetrahydrofuran and separated by column chromatography to obtain <1-c> 11 g. (Yield 24%)

＜１−ｄ＞
乾燥した５００ｍｌの反応器に＜１−ｃ＞１１ｇ（４８ｍｍｏｌ）とテトラヒドロフラン５５ｍｌを入れて攪拌する。０℃で３Ｍフェニルマグネシウムブロミド３７ｍｌ（１０１ｍｍｏｌ）及びテトラヒドロフラン３３ｍｌをゆっくり滴加した後、２時間還流撹拌する。０℃で６Ｎ塩酸を滴加した後、１時間還流撹拌する。常温で６Ｎ水酸化ナトリウムを入れてｐＨ８に合わせ、水と酢酸エチルで抽出する。有機層を濃縮した後、ジクロロメタンとヘプタンで再結晶して＜１−ｄ＞１４．５ｇを得た。（収率９６％） Synthesis example 1-4. Synthesis of <1-d><1-d> was synthesized according to the following reaction formula 4.
[Reaction Formula 4]

<1-d>
<1-c> 11 g (48 mmol) and tetrahydrofuran 55 ml are placed in a dry 500 ml reactor and stirred. At 0 ° C., 37 ml (101 mmol) of 3M phenylmagnesium bromide and 33 ml of tetrahydrofuran are slowly added dropwise and stirred at reflux for 2 hours. 6N hydrochloric acid is added dropwise at 0 ° C., and the mixture is stirred at reflux for 1 hour. 6N sodium hydroxide is added at room temperature to adjust to pH 8, and the mixture is extracted with water and ethyl acetate. The organic layer was concentrated and recrystallized with dichloromethane and heptane to obtain 14.5 g of <1-d>. (Yield 96%)

＜１−ｅ＞
３００ｍＬの反応器に＜１−ｄ＞１４ｇ（４９ｍｍｏｌ）、尿素１１．７ｇ（１９５ｍｍｏｌ）及び酢酸７０ｍＬを入れて１２時間還流撹拌する。反応終了の後、過量の水を反応物に入れて析出させた後、濾過する。メタノールで熱くスラリー化した後、濾過・乾燥して＜１−ｅ＞９．３ｇを得た。（収率６１％） Synthesis Example 1-5. Synthesis of <1-e><1-e> was synthesized according to the following reaction formula 5.
[Reaction Formula 5]

<1-e>
<1-d> 14 g (49 mmol), urea 11.7 g (195 mmol), and acetic acid 70 mL are placed in a 300 mL reactor, and stirred at reflux for 12 hours. After completion of the reaction, an excessive amount of water is added to the reaction product to precipitate it, and then filtered. After slurrying hot with methanol, filtration and drying were performed to obtain 9.3 g of <1-e>. (Yield 61%)

＜１−ｆ＞
３００ｍＬの反応器に＜１−ｅ＞９．０ｇ（２９ｍｍｏｌ）及びオキシ塩化リン４５ｍＬを入れて１２時間還流撹拌する。反応終了の後、０℃の過量の水に反応物をゆっくり入れて固体を析出させた後、濾過する。固体をジクロロベンゼンに溶かして熱い状態で減圧濾過した後、再結晶して＜１−ｆ＞７．０ｇを得た。（収率７３％） Synthesis Example 1-6. Synthesis of <1-f><1-f> was synthesized according to the following reaction formula 6.
[Reaction Formula 6]

<1-f>
In a 300 mL reactor, 9.0 g (29 mmol) of <1-e> and 45 mL of phosphorus oxychloride are added and stirred at reflux for 12 hours. After completion of the reaction, the reaction product is slowly put into an excessive amount of water at 0 ° C. to precipitate a solid, followed by filtration. The solid was dissolved in dichlorobenzene, filtered under reduced pressure in a hot state, and recrystallized to obtain 7.0 g of <1-f>. (Yield 73%)

＜化学式１＞
乾燥した５００ｍＬの反応器にカルバゾール５ｇ（３０ｍｍｏｌ）とジメチルホルムアミド５０ｍＬを入れて攪拌した後、６０％水素化ナトリウム３．９ｇ（１００ｍｍｏｌ）を入れ、１時間撹拌する。＜１−ｆ＞１２．９ｇ（３９ｍｍｏｌ）をジメチルホルムアミド４０ｍＬに溶かして反応物に１時間滴加した後、３時間撹拌する。反応終了の後、水３００ｍＬに反応液を注いで結晶化し、濾過する。ジクロロメタンと酢酸エチルで再結晶して＜化学式１＞８．０ｇを得た。（収率５８％）
ＭＳ［Ｍ］^＋ ４６１．１５ Synthesis Example 1-7. Synthesis of <Chemical Formula 1><Chemical Formula 1> was synthesized according to Reaction Formula 7 below.
[Reaction Scheme 7]

<Chemical Formula 1>
Carbazole 5 g (30 mmol) and dimethylformamide 50 mL are added to a dry 500 mL reactor, and then 3.9 g (100 mmol) of 60% sodium hydride is added and stirred for 1 hour. <1-f> 12.9 g (39 mmol) is dissolved in 40 mL of dimethylformamide and added dropwise to the reaction for 1 hour, followed by stirring for 3 hours. After completion of the reaction, the reaction solution is poured into 300 mL of water to crystallize and filter. Recrystallization from dichloromethane and ethyl acetate gave 8.0 g of <Chemical Formula 1>. (Yield 58%)
MS [M] ⁺ 461.15

＜２−ａ＞
合成例１−３で＜１−ｂ＞の代わりに２−ニトロジベンゾチオフェンを使用した以外は同様の方法で合成して＜２−ａ＞１４ｇを得た。（収率１５％） Synthesis Example 2 Synthesis of Chemical Formula 28
Synthesis Example 2-1. Synthesis of <2-a><2-a> was synthesized according to the following reaction formula 8.
[Reaction Formula 8]

<2-a>
Synthesis was performed in the same manner except that 2-nitrodibenzothiophene was used instead of <1-b> in Synthesis Example 1-3 to obtain <2-a> 14 g. (Yield 15%)

＜２−ｂ＞
合成例１−４で＜１−ｃ＞の代わりに＜２−ａ＞を使用した以外は同様の方法で合成して＜２−ｂ＞１８ｇを得た。（収率９５％） Synthesis example 2-2. Synthesis of <2-b><2-b> was synthesized according to the following reaction formula 9.
[Reaction Scheme 9]

<2-b>
<2-b> 18 g was obtained by synthesizing in the same manner except that <2-a> was used instead of <1-c> in Synthesis Example 1-4. (Yield 95%)

＜２−ｃ＞
合成例１−５で＜１−ｄ＞の代わりに＜２−ｂ＞を使用した以外は同様の方法で合成して＜２−ｃ＞１１．７ｇを得た。（収率６０％） Synthesis example 2-3. Synthesis of <2-c><2-c> was synthesized according to the following reaction formula 10.
[Reaction Scheme 10]

<2-c>
Synthesis was performed in the same manner as in Synthesis Example 1-5 except that <2-b> was used instead of <1-d> to obtain <2-c> 11.7 g. (Yield 60%)

＜２−ｄ＞
合成例１−６で＜１−ｅ＞の代わりに＜２−ｃ＞を使用した以外は同様の方法で合成して＜２−ｄ＞８．８ｇを得た。（収率７２％） Synthesis Example 2-4. <2-d> Synthesis <2-d> was synthesized according to the following Reaction Scheme 11.
[Reaction Formula 11]

<2-d>
Synthesis was performed in the same manner as in Synthesis Example 1-6 except that <2-c> was used instead of <1-e> to obtain <2-d> 8.8 g. (Yield 72%)

＜化学式２８＞
合成例１−７でカルバゾールと＜１−ｆ＞の代わりに３−フェニルカルバゾールと＜２−ｄ＞を使用した以外は同様の方法で合成して＜化学式２８＞５．４ｇを得た。（収率４８％）
ＭＳ［Ｍ］^＋ ５５３．１６ Synthesis Example 2-5. Synthesis of <Chemical Formula 28><Chemical Formula 28> was synthesized according to the following Reaction Formula 12.
[Reaction Scheme 12]

<Formula 28>
Synthesis was performed in the same manner as in Synthesis Example 1-7 except that 3-phenylcarbazole and <2-d> were used instead of carbazole and <1-f> to obtain 5.4 g of <Chemical Formula 28>. (Yield 48%)
MS [M] ⁺ 553.16

＜３−ａ＞
乾燥した１Ｌの反応器に４−ブロモジベンゾチオフェン５０ｇ（１９０ｍｍｏｌ）とトルエン５００ｍｌを入れて溶かした後、アセトアミド２２．１ｇ（３８０ｍｍｏｌ）、炭酸カリウム５２．５ｇ（３８０ｍｍｏｌ）、銅ヨウ化物５４．３ｇ（２８５ｍｍｏｌ）、シス −トランス−１，２−ジアミンシクロヘキサン６５．１ｇ（５７０ｍｍｏｌ）をゆっくり入れる。１２時間還流撹拌する。反応終結の後、カラムクロマトグラフィーで分離して＜３−ａ＞７．２ｇを得た。（収率１６％） Synthesis Example 3 Synthesis of Chemical Formula 64
Synthesis Example 3-1. Synthesis of <3-a><3-a> was synthesized according to the following reaction formula 13.
[Reaction Formula 13]

<3-a>
After dissolving 50 g (190 mmol) of 4-bromodibenzothiophene and 500 ml of toluene in a dry 1 L reactor, 22.1 g (380 mmol) of acetamide, 52.5 g (380 mmol) of potassium carbonate, 54.3 g of copper iodide ( 285 mmol), 65.1 g (570 mmol) of cis-trans-1,2-diaminecyclohexane are slowly added. Stir at reflux for 12 hours. After completion of the reaction, it was separated by column chromatography to obtain 7.2 g of <3-a>. (Yield 16%)

＜３−ｂ＞
３００ｍＬの反応器に＜３−ａ＞７．２ｇ（３ｍｍｏｌ）と酢酸１００ｍｌを入れて溶した後、臭素４．８ｇ（３ｍｍｏｌ）をゆっくり滴加する。１２時間撹拌する。反応終結の後、反応物を水に注いで固体を析出させた後、濾過する。水で固体を十分に洗浄し、乾燥して＜３−ｂ＞９．０ｇを得た。（収率９４％） Synthesis Example 3-2. Synthesis of <3-b><3-b> was synthesized according to the following reaction formula 14.
[Reaction Scheme 14]

<3-b>
After dissolving 7.2 g (3 mmol) of <3-a> and 100 ml of acetic acid in a 300 mL reactor, 4.8 g (3 mmol) of bromine is slowly added dropwise. Stir for 12 hours. After completion of the reaction, the reaction product is poured into water to precipitate a solid, and then filtered. The solid was washed thoroughly with water and dried to obtain 9.0 g of <3-b>. (Yield 94%)

＜３−ｃ＞
５００ｍＬの反応器に＜３−ｂ＞９．０ｇ（２８ｍｍｏｌ）、水酸化カリウム１２．６ｇ（２２５ｍｍｏｌ）、エタノール７０ｍｌ、テトラヒドロフラン３０ｍｌ及び水３０ｍｌを入れ、１２時間還流撹拌する。反応終結の後、減圧濃縮し、反応物を水に注いで固体を析出させた後、濾過する。再結晶した後、＜３−ｃ＞７．２ｇを得た。（収率９２％） Synthesis Example 3-3. Synthesis of <3-c><3-c> was synthesized according to the following reaction formula 15.
[Reaction Scheme 15]

<3-c>
In a 500 mL reactor, 9.0 g (28 mmol) of <3-b>, 12.6 g (225 mmol) of potassium hydroxide, 70 ml of ethanol, 30 ml of tetrahydrofuran and 30 ml of water are stirred for 12 hours under reflux. After completion of the reaction, the mixture is concentrated under reduced pressure, and the reaction product is poured into water to precipitate a solid, followed by filtration. After recrystallization, 7.2 g of <3-c> was obtained. (Yield 92%)

＜３−ｄ＞
３００ｍＬの反応器に＜３−ｃ＞１３ｇ（４９ｍｍｏｌ）とハイポリン酸２００ｍｌを入れて攪拌する。１００℃で加熱して３０分撹拌する。常温から０℃に降温した後、亜硝酸ナトリウムをゆっくり入れる。０℃で４時間攪拌した後、水を注いで固体を析出し、濾過する。カラムクロマトグラフィーで分離して＜３−ｄ＞１１．６ｇを得た。（収率９４％） Synthesis Example 3-4. Synthesis of <3-d><3-d> was synthesized according to the following reaction formula 16.
[Reaction Scheme 16]

<3-d>
<3-c> 13 g (49 mmol) and 200 ml of hypopolynic acid are placed in a 300 mL reactor and stirred. Heat at 100 ° C. and stir for 30 minutes. After cooling from room temperature to 0 ° C, sodium nitrite is slowly added. After stirring at 0 ° C. for 4 hours, water is poured to precipitate a solid, which is filtered. Separation by column chromatography gave <3-d> 11.6 g. (Yield 94%)

＜３−ｅ＞
合成例１−１でジベンゾフランの代わりに＜３−ｄ＞を使用した以外は同様の方法で合成して＜３−ｅ＞３２ｇを得た。（収率８２％） Synthesis Example 3-5. Synthesis of <3-e><3-e> was synthesized according to the following reaction formula 17.
[Reaction Scheme 17]

<3-e>
Synthesis was performed in the same manner except that <3-d> was used instead of dibenzofuran in Synthesis Example 1-1 to obtain <3-e> 32 g. (Yield 82%)

＜３−ｆ＞
合成例１−２で＜１−ａ＞の代わりに＜３−ｅ＞を使用した以外は同様の方法で合成して＜３−ｆ＞２３．１ｇを得た。（収率７１％） Synthesis Example 3-6. Synthesis of <3-f> <3-f> was synthesized according to the following reaction formula 18.
[Reaction Scheme 18]

<3-f>
Synthesis was performed in the same manner as in Synthesis Example 1-2 except that <3-e> was used instead of <1-a> to obtain <3-f> 23.1 g. (Yield 71%)

＜３−ｇ＞
合成例１−３で＜１−ｂ＞の代わりに＜３−ｆ＞を使用した以外は同様の方法で合成して＜３−ｇ＞６．４ｇを得た。（収率２８％） Synthesis Example 3-7. Synthesis of <3-g><3-g> was synthesized according to the following reaction formula 19.
[Reaction Scheme 19]

<3-g>
Synthesis was performed in the same manner except that <3-f> was used in place of <1-b> in Synthesis Example 1-3 to obtain <3-g> 6.4 g. (Yield 28%)

＜３−ｈ＞
合成例１−４で＜１−ｃ＞の代わりに＜３−ｇ＞を使用した以外は同様の方法で合成して＜３−ｈ＞６．９ｇを得た。（収率８０％） Synthesis Example 3-8. Synthesis of <3-h><3-h> was synthesized according to the following reaction formula 20.
[Reaction Scheme 20]

<3-h>
Synthesis was performed in the same manner as in Synthesis Example 1-4 except that <3-g> was used instead of <1-c> to obtain <3-h> 6.9 g. (Yield 80%)

＜３−ｉ＞
合成例１−５で＜１−ｄ＞の代わりに＜３−ｈ＞を使用した以外は同様の方法で合成して＜３−ｉ＞６．６ｇを得た。（収率８８％） Synthesis Example 3-9. Synthesis of <3-i><3-i> was synthesized according to the following reaction formula 21.
[Reaction formula 21]

<3-i>
Synthesis was performed in the same manner as in Synthesis Example 1-5, except that <3-h> was used instead of <1-d> to obtain 6.6 g of <3-i>. (Yield 88%)

＜３−ｊ＞
合成例１−６で＜１−ｅ＞の代わりに＜３−ｉ＞を使用した以外は同様の方法で合成して＜３−ｊ＞６．２ｇを得た。（収率８９％） Synthesis Example 3-10. Synthesis of <3-j><3-j> was synthesized according to the following reaction formula 22.
[Reaction Scheme 22]

<3-j>
Synthesis was performed in the same manner as in Synthesis Example 1-6 except that <3-i> was used instead of <1-e> to obtain <3-j> 6.2 g. (Yield 89%)

＜３−ｊ＞ ＜化学式６４＞
乾燥した２５０ｍＬの反応器に３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸５ｇ（１７ｍｍｏｌ）、＜３−ｊ＞６ｇ（１７ｍｍｏｌ）、炭酸カリウム４．８ｇ（３５ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム０．４ｇ（０．３ｍｍｏｌ）、水１０ｍＬ、トルエン２５ｍＬ及び１，４−ジオキサン２５ｍＬを入れ、１２時間還流撹拌する。反応終結の後、反応物を層分離して有機層を減圧濃縮する。カラムクロマトグラフィーで分離して＜化学式６４＞５．７ｇを得た。（収率５９％）
ＭＳ［Ｍ］^＋ ５５３．１６ Synthesis Example 3-11. Synthesis of <Chemical Formula 64><Chemical Formula 64> was synthesized according to the following Reaction Formula 23.
[Reaction Scheme 23]

<3-j><Chemical formula 64>
In a dry 250 mL reactor, 5 g (17 mmol) 3- (9H-carbazol-9-yl) phenylboronic acid, 6 g (17 mmol) <3-j>, 4.8 g (35 mmol) potassium carbonate, tetrakistriphenylphosphine palladium 0.4 g (0.3 mmol), 10 mL of water, 25 mL of toluene and 25 mL of 1,4-dioxane are added and stirred at reflux for 12 hours. After completion of the reaction, the reaction product is separated into layers, and the organic layer is concentrated under reduced pressure. Separation by column chromatography gave 5.7 g of <chemical formula 64>. (Yield 59%)
MS [M] ⁺ 553.16

＜４−ａ＞
合成例１−３で＜１−ｂ＞の代わりに３−ニトロジベンゾフランを使用した以外は同様の方法で合成して＜４−ａ＞１８．２ｇを得た。（収率２７％） Synthesis Example 4 Synthesis of Chemical Formula 96
Synthesis Example 4-1. Synthesis of <4-a><4-a> was synthesized according to the following reaction formula 24.
[Reaction Scheme 24]

<4-a>
Synthesis was performed in the same manner as in Synthesis Example 1-3 except that 3-nitrodibenzofuran was used instead of <1-b> to obtain <4-a> 18.2 g. (Yield 27%)

＜４−ｂ＞
合成例１−４で＜１−ｃ＞の代わりに＜４−ａ＞を使用した以外は同様の方法で合成して＜４−ｂ＞２２ｇを得た。（収率８８％） Synthesis example 4-2. Synthesis of <4-b><4-b> was synthesized according to the following reaction formula 25.
[Reaction Scheme 25]

<4-b>
<4-b> 22g was obtained by the same synthesis except that <4-a> was used instead of <1-c> in Synthesis Example 1-4. (Yield 88%)

＜４−ｃ＞
合成例１−５で＜１−ｄ＞の代わりに＜４−ｂ＞を使用した以外は同様の方法で合成して＜４−ｃ＞１７．１ｇを得た。（収率７２％） Synthesis Example 4-3. <4-c> Synthesis <4-c> was synthesized according to the following Reaction Scheme 26.
[Reaction Formula 26]

<4-c>
Synthesis was performed in the same manner as in Synthesis Example 1-5 except that <4-b> was used instead of <1-d> to obtain <1-c> 17.1 g. (Yield 72%)

＜４−ｄ＞
合成例１−６で＜１−ｅ＞の代わりに＜４−ｃ＞を使用した以外は同様の方法で合成して＜４−ｄ＞１４．３ｇを得た。（収率７９％） Synthesis Example 4-4. Synthesis of <4-d><4-d> was synthesized according to the following reaction formula 27.
[Reaction Formula 27]

<4-d>
Synthesis was performed in the same manner as in Synthesis Example 1-6 except that <4-c> was used instead of <1-e> to obtain <4-d> 14.3 g. (Yield 79%)

＜４−ｅ＞
合成例１−１でジベンゾフランの代わりに２−ブロモジベンゾチオフェンを使用した以外は同様の方法で合成して＜４−ｅ＞５０ｇを得た。（収率８２％） Synthesis Example 4-5. <4-e> Synthesis <4-e> was synthesized according to the following reaction formula 28.
[Reaction formula 28]

<4-e>
<4-e> 50 g was obtained by synthesizing in the same manner except that 2-bromodibenzothiophene was used instead of dibenzofuran in Synthesis Example 1-1. (Yield 82%)

＜４−ｆ＞
合成例３−１１で＜３−ｊ＞、３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸の代わりに＜４−ｅ＞、３−ブロモカルバゾールを使用した以外は同様の方法で合成して＜４−ｆ＞３２ｇを得た。（収率８４％） Synthesis Example 4-6. <4-f> Synthesis <4-f> was synthesized according to the following reaction formula 29.
[Reaction Formula 29]

<4-f>
Synthesis was performed in the same manner as in Synthesis Example 3-11 except that <4-e> and 3-bromocarbazole were used instead of <3-j> and 3- (9H-carbazol-9-yl) phenylboronic acid. <4-f> was obtained 32 g. (Yield 84%)

＜４−ｆ＞ ＜化学式９６＞
合成例１−７でカルバゾールと＜１−ｆ＞の代わりに＜４−ｆ＞と＜４−ｄ＞を使用した以外は同様の方法で合成して＜化学式９６＞４．３ｇを得た。（収率３３％）
ＭＳ［Ｍ］^＋ ６４３．１７ Synthesis Example 4-7. Synthesis of <Chemical Formula 96><Chemical Formula 96> was synthesized according to Reaction Formula 30 below.
[Reaction Scheme 30]

<4-f><Chemical formula 96>
Synthesis was performed in the same manner as in Synthesis Example 1-7 except that <4-f> and <4-d> were used instead of carbazole and <1-f> to obtain 4.3 g of <chemical formula 96>. (Yield 33%)
MS [M] ⁺ 643.17

＜５−ａ＞
合成例１−２で＜１−ａ＞の代わりに＜４−ｅ＞を使用した以外は同様の方法で合成して＜５−ａ＞３１．２ｇを得た。（収率６２％） Synthesis Example 5 Synthesis of Chemical Formula 125
Synthesis example 5-1. Synthesis of <5-a><5-a> was synthesized according to the following reaction formula 31.
[Reaction Formula 31]

<5-a>
Synthesis was performed in the same manner as in Synthesis Example 1-2 except that <4-e> was used instead of <1-a> to obtain <5-a> 31.2 g. (Yield 62%)

＜５−ｂ＞
合成例１−３で＜１−ｂ＞の代わりに＜５−ａ＞を使用した以外は同様の方法で合成して＜５−ｂ＞８．０ｇを得た。（収率２６％） Synthesis example 5-2. <5-b> Synthesis <5-b> was synthesized according to the following reaction formula 32.
[Reaction formula 32]

<5-b>
<5-b> 8.0 g was obtained by synthesizing in the same manner except that <5-a> was used instead of <1-b> in Synthesis Example 1-3. (Yield 26%)

＜５−ｃ＞
合成例１−４で＜１−ｃ＞の代わりに＜５−ｂ＞を使用した以外は同様の方法で合成して＜５−ｃ＞８．２ｇを得た。（収率７６％） Synthesis Example 5-3. Synthesis of <5-c><5-c> was synthesized according to the following reaction formula 33.
[Reaction Scheme 33]

<5-c>
<5-c> 8.2 g was obtained by synthesizing in the same manner except that <5-b> was used instead of <1-c> in Synthesis Example 1-4. (Yield 76%)

＜５−ｄ＞
合成例１−５で＜１−ｄ＞の代わりに＜５−ｃ＞を使用した以外は同様の方法で合成して＜５−ｄ＞７．６ｇを得た。（収率８６％） Synthesis Example 5-4. Synthesis of <5-d><5-d> was synthesized according to the following reaction formula 34.
[Reaction formula 34]

<5-d>
Synthesis was performed in the same manner as in Synthesis Example 1-5 except that <5-c> was used instead of <1-d> to obtain 7.6 g of <5-d>. (Yield 86%)

＜５−ｅ＞
合成例１−６で＜１−ｅ＞の代わりに＜５−ｄ＞を使用した以外は同様の方法で合成して＜５−ｅ＞６．７ｇを得た。（収率８４％） Synthesis Example 5-5. Synthesis of <5-e><5-e> was synthesized according to the following reaction formula 35.
[Reaction formula 35]

<5-e>
<5-e> 6.7 g was obtained by synthesizing in the same manner except that <5-d> was used instead of <1-e> in Synthesis Example 1-6. (Yield 84%)

＜５−ｆ＞
２Ｌの反応器に３，３−ジメチル−２，３−ジヒドロ−１Ｈ−インデン−１−オン６０ ｇ（３７５ｍｍｏｌ）、フェニルヒドラジン塩酸塩８７．５ｇ（４５０ｍｍｏｌ）、酢酸６００ｍＬ及び塩酸３０ｍＬを入れて１２時間還流撹拌する。反応終了の後、ジクロロメタンと水で抽出した後、有機層を減圧濃縮し、カラムクロマトグラフィーで分離して＜５−ｆ＞５７ｇを得た。（収率５２％） Synthesis Example 5-6. Synthesis of <5-f><5-f> was synthesized according to the following reaction formula 36.
[Reaction formula 36]

<5-f>
A 2 L reactor was charged with 60 g (375 mmol) of 3,3-dimethyl-2,3-dihydro-1H-inden-1-one, 87.5 g (450 mmol) of phenylhydrazine hydrochloride, 600 mL of acetic acid, and 30 mL of hydrochloric acid. Stir at reflux for hours. After completion of the reaction, the mixture was extracted with dichloromethane and water, and then the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain <5-f> 57 g. (Yield 52%)

＜化学式１２５＞
乾燥した１００ｍＬの反応器に＜５−ｆ＞３．５ｇ（１５ｍｍｏｌ）、＜５−ｅ＞６．２ｇ（１８ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム０．３ｇ（０．３ｍｍｏｌ）、トリ−ｔ−ブチルホスホニウムテトラフルオロボレート０．４ｇ（２．０ｍｍｏｌ）、ナトリウムｔ−ブトキシド２．９ｇ（３０ｍｍｏｌ）及びキシレン１８ｍＬを入れ、窒素下で１２時間還流撹拌する。反応終結の後、熱い状態で減圧濾過する。溶液を減圧乾燥した後、カラムクロマトグラフィーで分離して＜化学式１２５＞３．３ｇを得た。（収率４１％）
ＭＳ［Ｍ］^＋ ５４３．１８ Synthesis Example 5-7. Synthesis of <Chemical Formula 125><Chemical Formula 125> was synthesized according to Reaction Formula 37 below.
[Reaction formula 37]

<Chemical formula 125>
<5-f> 3.5 g (15 mmol), <5-e> 6.2 g (18 mmol), tris (dibenzylideneacetone) dipalladium 0.3 g (0.3 mmol), tri- Add 0.4 g (2.0 mmol) of t-butylphosphonium tetrafluoroborate, 2.9 g (30 mmol) of sodium t-butoxide and 18 mL of xylene, and stir to reflux under nitrogen for 12 hours. After completion of the reaction, it is filtered under reduced pressure while hot. The solution was dried under reduced pressure and then separated by column chromatography to obtain 3.3 g of <Chemical Formula 125>. (Yield 41%)
MS [M] ⁺ 543.18

＜６−ａ＞
合成例５−６でフェニルヒドラジン塩酸塩の代わりに２−ナフチルヒドラジン塩酸塩を使用した以外は同様の方法で合成して＜６−ａ＞１３ｇを得た。（収率４９％） Synthesis Example 6 Synthesis of Formula 177
Synthesis Example 6-1. Synthesis of <6-a><6-a> was synthesized according to the following reaction formula 38.
[Reaction formula 38]

<6-a>
Synthesis was performed in the same manner as in Synthesis Example 5-6 except that 2-naphthylhydrazine hydrochloride was used instead of phenylhydrazine hydrochloride to obtain <6-a> 13 g. (Yield 49%)

＜化学式１７７＞
合成例５−７で＜５−ｅ＞、＜５−ｆ＞の代わりに＜６−ａ＞、＜１−ｆ＞を使用した以外は同様の方法で合成して＜化学式１７７＞３．１ｇを得た。（収率３０％）
ＭＳ［Ｍ］^＋ ５７７．２２ Synthesis Example 6-2. Synthesis of <Chemical Formula 177><Chemical Formula 177> was synthesized according to Reaction Formula 39 below.
[Reaction formula 39]

<Chemical formula 177>
Synthesis was performed in the same manner as in Synthesis Example 5-7 except that <6-a> and <1-f> were used instead of <5-e> and <5-f>. Got. (Yield 30%)
MS [M] ⁺ 577.22

＜７−ａ＞
合成例１−１でジベンゾフランの代わりに２−ブロモジベンゾフランを使用した以外は同様の方法で合成して＜７−ａ＞５０ｇを得た。（収率８３％） Synthesis Example 7 Synthesis of Chemical Formula 181
Synthesis Example 7-1. Synthesis of <7-a><7-a> was synthesized according to the following reaction formula 40.
[Reaction formula 40]

<7-a>
Synthesis was performed in the same manner except that 2-bromodibenzofuran was used instead of dibenzofuran in Synthesis Example 1-1 to obtain <7-a> 50 g. (Yield 83%)

＜７−ｂ＞
合成例１−２で＜１−ａ＞の代わりに＜７−ａ＞を使用した以外は同様の方法で合成して＜７−ｂ＞３２．２ｇを得た。（収率６４％） Synthesis Example 7-2. Synthesis of <7-b><7-b> was synthesized according to the following reaction formula 41.
[Reaction formula 41]

<7-b>
Synthesis was performed in the same manner as in Synthesis Example 1-2 except that <7-a> was used instead of <1-a> to obtain <7-b> 32.2 g. (Yield 64%)

＜７−ｃ＞
合成例１−３で＜１−ｂ＞の代わりに＜７−ｂ＞を使用した以外は同様の方法で合成して＜７−ｃ＞７．７ｇを得た。（収率２５％） Synthesis Example 7-3. Synthesis of <7-c><7-c> was synthesized according to the following reaction formula 42.
[Reaction formula 42]

<7-c>
<7-c> 7.7g was obtained by the same synthesis except that <7-b> was used instead of <1-b> in Synthesis Example 1-3. (Yield 25%)

＜７−ｄ＞
合成例１−４で＜１−ｃ＞の代わりに＜７−ｃ＞を使用した以外は同様の方法で合成して＜７−ｄ＞８．０ｇを得た。（収率７７％） Synthesis Example 7-4. Synthesis of <7-d><7-d> was synthesized according to the following reaction formula 43.
[Reaction formula 43]

<7-d>
<7-d> 8.0 g was obtained by the same method except that <7-c> was used instead of <1-c> in Synthesis Example 1-4. (Yield 77%)

＜７−ｅ＞
合成例１−５で＜１−ｄ＞の代わりに＜７−ｄ＞を使用した以外は同様の方法で合成して＜７−ｅ＞７．５ｇを得た。（収率８６％） Synthesis Example 7-5. <7-e> Synthesis <7-e> was synthesized according to the following reaction formula 44.
[Reaction formula 44]

<7-e>
Synthesis was performed in the same manner as in Synthesis Example 1-5 except that <7-d> was used instead of <1-d> to obtain <7-e> 7.5 g. (Yield 86%)

＜７−ｆ＞
合成例１−６で＜１−ｅ＞の代わりに＜７−ｅ＞を使用した以外は同様の方法で合成して＜７−ｆ＞６．９ｇを得た。（収率８７％） Synthesis Example 7-6. Synthesis of <7-f><7-f> was synthesized according to the following reaction formula 45.
[Reaction formula 45]

<7-f>
Synthesis in the same manner as in Synthesis Example 1-6 except that <7-e> was used instead of <1-e> to obtain 6.9 g of <7-f>. (Yield 87%)

＜化学式１８１＞
合成例５−７で＜５−ｆ＞、＜５−ｅ＞の代わりに＜６−ａ＞、＜７−ｆ＞を使用した以外は同様の方法で合成して＜化学式１８１＞２．３ｇを得た。（収率２５％）
ＭＳ［Ｍ］^＋ ５７７．２２ Synthesis Example 7-7. Synthesis of <Chemical Formula 181><Chemical Formula 181> was synthesized according to Reaction Formula 46 below.
[Reaction formula 46]

<Formula 181>
Synthesis was performed in the same manner as in Synthesis Example 5-7, except that <6-a> and <7-f> were used instead of <5-f> and <5-e>. Got. (Yield 25%)
MS [M] ⁺ 577.22

＜８−ａ＞
合成例４−１と同様の方法で合成して＜８−ａ＞１２．１ｇを得た。（収率１８％） Synthesis Example 8 Synthesis of Formula 182
Synthesis Example 8-1. Synthesis of <8-a><8-a> was synthesized according to the following reaction formula 47.
[Reaction formula 47]

<8-a>
Synthesis in the same manner as in Synthesis Example 4-1 gave <8-a> 12.1 g. (Yield 18%)

＜８−ｂ＞
合成例１−４で＜１−ｃ＞の代わりに＜８−ａ＞を使用した以外は同様の方法で合成して＜８−ｂ＞１４ｇを得た。（収率８４％） Synthesis Example 8-2. Synthesis of <8-b><8-b> was synthesized according to the following reaction formula 48.
[Reaction Formula 48]

<8-b>
Synthesis was performed in the same manner as in Synthesis Example 1-4 except that <8-a> was used instead of <1-c> to obtain <8-b> 14 g. (Yield 84%)

＜８−ｃ＞
合成例１−５で＜１−ｄ＞の代わりに＜８−ｂ＞を使用した以外は同様の方法で合成して＜８−ｃ＞１１．７ｇを得た。（収率７７％） Synthesis Example 8-3. Synthesis of <8-c><8-c> was synthesized according to the following reaction formula 49.
[Reaction formula 49]

<8-c>
Synthesis was performed in the same manner as in Synthesis Example 1-5, except that <8-b> was used instead of <1-d> to obtain <8-c> 11.7 g. (Yield 77%)

＜８−ｄ＞
合成例１−６で＜１−ｅ＞の代わりに＜８−ｃ＞を使用した以外は同様の方法で合成して＜８−ｄ＞８．８ｇを得た。（収率７１％） Synthesis Example 8-4. Synthesis of <8-d><8-d> was synthesized according to the following reaction formula 50.
[Reaction Formula 50]

<8-d>
Synthesis was performed in the same manner as in Synthesis Example 1-6 except that <8-c> was used instead of <1-e> to obtain <8-d> 8.8 g. (Yield 71%)

＜８−ｅ＞
乾燥した１Ｌの反応器にジベンゾチオフェン５０ｇ（２７１ｍｍｏｌ）とテトラヒドロフラン４００ｍｌを入れた後、−７８℃で１．６Ｍｎ−ブチルリチウム１７８ｍＬ（２８５ｍｍｏｌ）をゆっくり滴加し、１時間後にヨウ素６９ｇ（２７１ｍｍｏｌ）をゆっくり入れた後、常温で２４時間撹拌する。その後、チオ硫酸ナトリウム水溶液を入れる。抽出して有機層を集めて減圧蒸留した。ヘプタンで再結晶して生成された固体を濾過した後、乾燥して＜８−ｅ＞５２ｇを得た。（収率６０％） Synthesis Example 8-5. Synthesis of <8-e><8-e> was synthesized according to the following reaction formula 51.
[Reaction Formula 51]

<8-e>
After adding 50 g (271 mmol) of dibenzothiophene and 400 ml of tetrahydrofuran to a dry 1 L reactor, 178 mL (285 mmol) of 1.6Mn-butyllithium was slowly added dropwise at −78 ° C., and 69 g (271 mmol) of iodine was added after 1 hour. Stir slowly and then stir at room temperature for 24 hours. Thereafter, an aqueous sodium thiosulfate solution is added. The organic layer was collected by extraction and distilled under reduced pressure. The solid produced by recrystallization with heptane was filtered and then dried to obtain <8-e> 52 g. (Yield 60%)

＜８−ｆ＞
１Ｌの反応器に＜８−ｅ＞５２ｇ（１６８ｍｍｏｌ）、ヨウ化銅６．５ｇ（３４ｍｍｏｌ）、トランス−４−ヒドロキシ−Ｌ−プロリン８．９ｇ（６８ｍｍｏｌ）、炭酸カルシウム６９．６ｇ（５０４ｍｍｏｌ）及びジメチルスルホキシド２６０ｍＬを入れ、２８％アンモニア水溶液１６７．９ｇをゆっくり入れる。１００℃で１２時間攪拌する。反応が終了すると、常温に冷ました後、酢酸エチルと蒸留水を用いて抽出する。有機層を減圧濃縮し、カラムクロマトグラフィーで分離して＜８−ｆ＞１０ｇを得た。（収率３０％） Synthesis Example 8-6. Synthesis of <8-f><8-f> was synthesized according to the following reaction formula 52.
[Reaction Formula 52]

<8-f>
<8-e> 52 g (168 mmol), copper iodide 6.5 g (34 mmol), trans-4-hydroxy-L-proline 8.9 g (68 mmol), calcium carbonate 69.6 g (504 mmol) and 1 L reactor Add 260 mL of dimethyl sulfoxide and slowly add 167.9 g of 28% aqueous ammonia solution. Stir at 100 ° C. for 12 hours. When the reaction is completed, the mixture is cooled to room temperature and extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain <8-f> 10 g. (Yield 30%)

＜８−ｇ＞
１Ｌの反応器に＜８−ｆ＞１０ｇ（５０ｍｍｏｌ）と塩酸１００ｍＬを入れ、５℃に合わせる。亜硝酸ナトリウム３．４５ｇ（５０ｍｍｏｌ）と水２０ｍＬを混ぜてゆっくり入れる。５℃で２時間を維持した後、塩化スズ（ＩＩ）二水和物５６．６ｇ（２５１ｍｍｏｌ）と塩酸２００ｍＬを混ぜた溶液をゆっくり入れる。常温で３時間攪拌した後、濾過して＜８−ｇ＞８ｇを得た。（収率６３％） Synthesis Example 8-7. <8-g> Synthesis <8-g> was synthesized according to the following reaction scheme 53.
[Reaction formula 53]

<8-g>
<8-f> 10 g (50 mmol) and hydrochloric acid 100 mL are put into a 1 L reactor and adjusted to 5 ° C. Mix slowly 3.45 g (50 mmol) of sodium nitrite and 20 mL of water. After maintaining at 5 ° C. for 2 hours, a solution of 56.6 g (251 mmol) of tin (II) chloride dihydrate and 200 mL of hydrochloric acid is slowly added. After stirring at room temperature for 3 hours, it was filtered to obtain <8-g> 8 g. (Yield 63%)

＜８−ｈ＞
合成例５−６でフェニルヒドラジン塩酸塩の代わりに＜８−ｇ＞を使用した以外は同様の方法で合成して＜８−ｈ＞４．９ｇを得た。（収率５４％） Synthesis Example 8-8. <8-h> Synthesis <8-h> was synthesized according to the following reaction formula 54.
[Reaction formula 54]

<8-h>
Synthesis in the same manner as in Synthesis Example 5-6 except that <8-g> was used instead of phenylhydrazine hydrochloride to obtain <8-h> 4.9 g. (Yield 54%)

＜化学式１８２＞
合成例５−７で＜５−ｆ＞、＜５−ｅ＞の代わりに＜８−ｈ＞、＜８−ｄ＞を使用した以外は同様の方法で合成して＜化学式１８２＞３．２ｇを得た。（収率３４％）
ＭＳ［Ｍ］^＋ ６３３．１９ Synthesis Example 8-9. Synthesis of <Chemical Formula 182><Chemical Formula 182> was synthesized according to Reaction Formula 55 below.
[Reaction formula 55]

<Formula 182>
Synthesis was carried out in the same manner as in Synthesis Example 5-7 except that <8-h> and <8-d> were used instead of <5-f> and <5-e>. Got. (Yield 34%)
MS [M] ⁺ 633.19

＜９−ａ＞
合成例１−１でジベンゾフランの代わりにジベンゾチオフェンを使用した以外は同様の方法で合成して＜９−ａ＞５４ｇを得た。（収率８７％） Synthesis Example 9 Synthesis of Chemical Formula 183
Synthesis Example 9-1. Synthesis of <9-a><9-a> was synthesized according to the following reaction formula 56.
[Reaction formula 56]

<9-a>
<9-a> 54 g was obtained by synthesizing in the same manner except that dibenzothiophene was used instead of dibenzofuran in Synthesis Example 1-1. (Yield 87%)

＜９−ｂ＞
合成例１−２で＜１−ａ＞の代わりに＜９−ａ＞を使用した以外は同様の方法で合成して＜９−ｂ＞４４ｇを得た。（収率８１％）
合成例９−３．＜９−ｃ＞の合成
下記反応式５８によって＜９−ｃ＞を合成した。
［反応式５８］

＜９−ｃ＞
合成例１−３で＜１−ｂ＞の代わりに＜９−ｂ＞を使用した以外は同様の方法で合成して＜９−ｃ＞１２．８ｇを得た。（収率３０％）
合成例９−４．＜９−ｄ＞の合成
下記反応式５９によって＜９−ｄ＞を合成した。
［反応式５９］

＜９−ｄ＞
合成例１−４で＜１−ｃ＞の代わりに＜９−ｃ＞を使用した以外は同様の方法で合成して＜９−ｄ＞１３．７ｇを得た。（収率７９％） Synthesis Example 9-2. Synthesis of <9-b><9-b> was synthesized according to the following reaction formula 57.
[Reaction Formula 57]

<9-b>
Synthesis was performed in the same manner as in Synthesis Example 1-2 except that <9-a> was used instead of <1-a> to obtain <9-b> 44 g. (Yield 81%)
Synthesis Example 9-3. <9-c> Synthesis <9-c> was synthesized according to Reaction Formula 58 below.
[Reaction formula 58]

<9-c>
<9-c> 12.8 g was obtained by synthesizing in the same manner except that <9-b> was used instead of <1-b> in Synthesis Example 1-3. (Yield 30%)
Synthesis Example 9-4. Synthesis of <9-d><9-d> was synthesized according to the following reaction formula 59.
[Reaction formula 59]

<9-d>
<9-d> 13.7 g was obtained by synthesizing in the same manner except that <9-c> was used instead of <1-c> in Synthesis Example 1-4. (Yield 79%)

＜９−ｅ＞
合成例１−５で＜１−ｄ＞の代わりに＜９−ｄ＞を使用した以外は同様の方法で合成して＜９−ｅ＞１２．５ｇを得た。（収率８６％） Synthesis Example 9-5. Synthesis of <9-e><9-e> was synthesized according to the following reaction formula 60.
[Reaction formula 60]

<9-e>
Synthesis was performed in the same manner as in Synthesis Example 1-5 except that <9-d> was used instead of <1-d> to obtain <9-e> 12.5 g. (Yield 86%)

＜９−ｆ＞
合成例１−６で＜１−ｅ＞の代わりに＜９−ｅ＞を使用した以外は同様の方法で合成して＜９−ｆ＞９．６ｇを得た。（収率７２％） Synthesis Example 9-6. Synthesis of <9-f><9-f> was synthesized according to the following reaction formula 61.
[Reaction formula 61]

<9-f>
Synthesis was performed in the same manner as in Synthesis Example 1-6 except that <9-e> was used instead of <1-e> to obtain 9.6 g of <9-f>. (Yield 72%)

＜化学式１８３＞
合成例５−７で＜５−ｆ＞、＜５−ｅ＞の代わりに＜６−ａ＞、＜９−ｆ＞を使用した以外は同様の方法で合成して＜化学式１８３＞４．２ｇを得た。（収率３６％）
ＭＳ［Ｍ］^＋ ５９３．１９ Synthesis Example 9-7. Synthesis of <Chemical Formula 183><Chemical Formula 183> was synthesized according to Reaction Formula 62 below.
[Reaction formula 62]

<Chemical Formula 183>
Synthesis was carried out in the same manner as in Synthesis Example 5-7 except that <6-a> and <9-f> were used instead of <5-f> and <5-e>. Got. (Yield 36%)
MS [M] ⁺ 593.19

＜１０−ａ＞
合成例３−１で４−ブロモジベンゾチオフェンの代わりに４−ブロモジベンゾフランを使用した以外は同様の方法で合成して＜１０−ａ＞１０．７ｇを得た。（収率２０％） Synthesis Example 10 Synthesis of Chemical Formula 191
Synthesis Example 10-1. Synthesis of <10-a><10-a> was synthesized according to the following reaction formula 63.
[Reaction formula 63]

<10-a>
<10-a> 10.7 g was obtained by synthesizing in the same manner except that 4-bromodibenzofuran was used instead of 4-bromodibenzothiophene in Synthesis Example 3-1. (Yield 20%)

＜１０−ｂ＞
合成例３−２で＜３−ａ＞の代わりに＜１０−ａ＞を使用した以外は同様の方法で合成して＜１０−ｂ＞１３ｇを得た。（収率９０％） Synthesis Example 10-2. <10-b> Synthesis <10-b> was synthesized according to the following reaction formula 64.
[Reaction formula 64]

<10-b>
<10-b> 13g was obtained by the same synthesis except that <10-a> was used instead of <3-a> in Synthesis Example 3-2. (Yield 90%)

＜１０−ｃ＞
合成例３−３で＜３−ｂ＞の代わりに＜１０−ｂ＞を使用した以外は同様の方法で合成して＜１０−ｃ＞１０．６ｇを得た。（収率９５％） Synthesis Example 10-3. Synthesis of <10-c><10-c> was synthesized according to the following reaction formula 65.
[Reaction formula 65]

<10-c>
Synthesis was performed in the same manner as in Synthesis Example 3-3 except that <10-b> was used instead of <3-b> to obtain <10-c> 10.6 g. (Yield 95%)

＜１０−ｄ＞
合成例３−４で＜３−ｃ＞の代わりに＜１０−ｃ＞を使用した以外は同様の方法で合成して＜１０−ｄ＞９．５ｇを得た。（収率９５％） Synthesis Example 10-4. Synthesis of <10-d><10-d> was synthesized according to the following reaction formula 66.
[Reaction formula 66]

<10-d>
Synthesis was performed in the same manner as in Synthesis Example 3-4 except that <10-c> was used instead of <3-c> to obtain 9.5 g of <10-d>. (Yield 95%)

＜１０−ｅ＞
合成例１−１でジベンゾフランの代わりに＜１０−ｄ＞を使用した以外は同様の方法で合成して＜１０−ｅ＞７．１ｇを得た。（収率８７％）

合成例１０−６．＜１０−ｆ＞の合成
下記反応式６８によって＜１０−ｆ＞を合成した。
［反応式６８］

＜１０−ｆ＞
合成例１−２で＜１−ａ＞の代わりに＜１０−ｅ＞を使用した以外は同様の方法で合成して＜１０−ｆ＞５．８ｇを得た。（収率８１％） Synthesis Example 10-5. Synthesis of <10-e> <10-e> was synthesized according to the following reaction formula 67.
[Reaction formula 67]

<10-e>
Synthesis was performed in the same manner except that <10-d> was used in place of dibenzofuran in Synthesis Example 1-1 to obtain <10-e> 7.1 g. (Yield 87%)

Synthesis Example 10-6. Synthesis of <10-f><10-f> was synthesized according to the following reaction formula 68.
[Reaction formula 68]

<10-f>
<10-f> 5.8 g was obtained by the same synthesis except that <10-e> was used instead of <1-a> in Synthesis Example 1-2. (Yield 81%)

＜１０−ｇ＞
合成例１−３で＜１−ｂ＞の代わりに＜１０−ｆ＞を使用した以外は同様の方法で合成して＜１０−ｇ＞８．３ｇを得た。（収率２８％） Synthesis Example 10-7. Synthesis of <10-g><10-g> was synthesized according to the following reaction formula 69.
[Reaction Formula 69]

<10-g>
<10-g> 8.3 g was obtained in the same manner as in Synthesis Example 1-3 except that <10-f> was used instead of <1-b>. (Yield 28%)

＜１０−ｈ＞
乾燥した２Ｌの反応器に＜１０−ｇ＞６．９ｇ（３３ｍｍｏｌ）をテトラヒドロフラン１２０ｍＬに溶かした後、攪拌する。０℃でフェニルマグネシウムブロミド２２ｍＬ（６６ｍｍｏｌ）をゆっくり滴加する。滴加が完了すると、４５℃で３時間撹拌する。その後、再び０℃で４−ブロモベンジルクロリド８．７ｇ（４０ｍｍｏｌ）をゆっくり滴加した後、４５℃で１２時間攪拌する。反応終了の後、酢酸エチルと水で抽出し、カラムクロマトグラフィーで分離して＜１０−ｈ＞７．１ｇを得た。（収率４８％） Synthesis Example 10-8. Synthesis of <10-h><10-h> was synthesized according to the following reaction formula 70.
[Reaction formula 70]

<10-h>
<10-g> 6.9 g (33 mmol) is dissolved in 120 mL of tetrahydrofuran in a dry 2 L reactor and stirred. Slowly add dropwise 22 mL (66 mmol) of phenylmagnesium bromide at 0 ° C. When the addition is complete, stir at 45 ° C. for 3 hours. Thereafter, 8.7 g (40 mmol) of 4-bromobenzyl chloride is slowly added again at 0 ° C., and the mixture is stirred at 45 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and water and separated by column chromatography to obtain 7.1 g of <10-h>. (Yield 48%)

＜１０−ｉ＞
２Ｌの反応器に１，２−シクロヘキサンジオン５０ｇ（４４６ｍｍｏｌ）、フェニルヒドラジニウムクロリド１２９ｇ（８９２ｍｍｏｌ）及び酢酸５００ｍｌを入れて２日間還流撹拌する。反応終了の後、過量の水に反応物をゆっくり注いで結晶を濾過して水で数回洗浄する。テトラヒドロフランで溶かし、熱いうちにシリカゲルで濾過し、再結晶して＜１０−ｉ＞７８ｇを得た。（収率６８％） Synthesis Example 10-9. Synthesis of <10-i><10-i> was synthesized according to the following reaction formula 71.
[Reaction formula 71]

<10-i>
Into a 2 L reactor, 50 g (446 mmol) of 1,2-cyclohexanedione, 129 g (892 mmol) of phenylhydrazinium chloride and 500 ml of acetic acid are added and stirred at reflux for 2 days. After the reaction is complete, the reaction is slowly poured into an excess of water and the crystals are filtered and washed several times with water. It was dissolved in tetrahydrofuran, filtered through silica gel while hot, and recrystallized to obtain <10-i> 78 g. (Yield 68%)

＜１０−ｊ＞
２Ｌの反応器に＜１０−ｉ＞７８ｇ（３０４ｍｍｏｌ）、ヨードベンゼン５５．９ｇ（２７４ｍｍｏｌ）、銅１９．３ｇ（３０４ｍｍｏｌ）、１８−クラウン−６−エーテル１６．１ｇ（６１ｍｍｏｌ）、炭酸カリウム８４．１ｇ（６０９ｍｍｏｌ）及びジクロロベンゼン８０ｍｌを入れ、１２時間還流撹拌する。反応終了の後、カラムクロマトグラフィーで分離して＜１０−ｊ＞７０ｇを得た。（収率６９％） Synthesis Example 10-10. <10-j> Synthesis <10-j> was synthesized according to Reaction Formula 72 below.
[Reaction formula 72]

<10-j>
<10-i> 78 g (304 mmol), iodobenzene 55.9 g (274 mmol), copper 19.3 g (304 mmol), 18-crown-6-ether 16.1 g (61 mmol), potassium carbonate 84. 1 g (609 mmol) and 80 ml of dichlorobenzene are added and stirred at reflux for 12 hours. After completion of the reaction, separation by column chromatography gave <10-j> 70 g. (Yield 69%)

＜化学式１９１＞
合成例５−７で＜５−ｆ＞、＜５−ｅ＞の代わりに＜１０−ｊ＞、＜１０−ｈ＞を使用した以外は同様の方法で合成して＜化学式１９１＞４．６ｇを得た。（収率４２％）
ＭＳ［Ｍ］^＋ ７０２．２４ Synthesis Example 10-11. Synthesis of <Chemical Formula 191><Chemical Formula 191> was synthesized according to Reaction Formula 73 below.
[Reaction formula 73]

<Chemical Formula 191>
Synthesis was carried out in the same manner as in Synthesis Example 5-7 except that <10-j> and <10-h> were used instead of <5-f> and <5-e>. Got. (Yield 42%)
MS [M] ⁺ 702.24

＜１１−ａ＞
合成例３−１１で＜３−ｊ＞、３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸の代わりに１−ブロモ−２−ヨードベンゼン、２−トリフェニレニルボロン酸を使用した以外は同様の方法で合成して＜１１−ａ＞３４ｇを得た。（収率８４％） Synthesis Example 11 Synthesis of Chemical Formula 218
Synthesis Example 11-1. <11-a> Synthesis <11-a> was synthesized according to the following reaction formula 74.
[Reaction formula 74]

<11-a>
<Synthesis Example 3-11> except that 1-bromo-2-iodobenzene and 2-triphenylenylboronic acid were used instead of <3-j> and 3- (9H-carbazol-9-yl) phenylboronic acid Synthesis was performed in the same manner to obtain <11-a> 34 g. (Yield 84%)

＜１１−ｂ＞
乾燥した５００ｍＬの反応器に＜１１−ａ＞３４ｇ（８９ｍｍｏｌ）、ビスピナコーラトジボロン３３．８ｇ（１３３ｍｍｏｌ）、パラジウム（ＩＩ）塩化−１，１’−ビス（ジフェニルホスフィノ）フェロセン１．９ｇ（３ｍｍｏｌ）、酢酸カリウム２６．１ｇ（２６６ｍｍｏｌ）及びトルエン３４０ｍｌを入れ、１０時間還流撹拌する。反応終了の後、固体を濾過した後、濾液を減圧して濃縮する。ジクロロメタンとヘプタンでカラムクロマトグラフィーによって分離して＜１１−ｂ＞２８ｇを得た。（収率７３％） Synthesis Example 11-2. <11-b> Synthesis <11-b> was synthesized according to the following reaction formula 75.
[Reaction formula 75]

<11-b>
<11-a> 34 g (89 mmol), bispinacolato diboron 33.8 g (133 mmol), palladium (II) chloride-1,1′-bis (diphenylphosphino) ferrocene 1.9 g in a dry 500 mL reactor (3 mmol), 26.1 g (266 mmol) of potassium acetate and 340 ml of toluene are added and stirred at reflux for 10 hours. After completion of the reaction, the solid is filtered, and the filtrate is concentrated under reduced pressure. Separation by column chromatography with dichloromethane and heptane gave <11-b> 28 g. (Yield 73%)

＜化学式２１８＞
合成例３−１１で＜３−ｊ＞、３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸の代わりに＜１−ｆ＞、＜１１−ｂ＞を使用した以外は同様の方法で合成して＜化学式２１８＞３．４ｇを得た。（収率３８％）
ＭＳ［Ｍ］^＋ ５９８．２０ Synthesis Example 11-3. Synthesis of <Chemical Formula 218><Chemical Formula 218> was synthesized according to Reaction Formula 76 below.
[Reaction formula 76]

<Chemical formula 218>
Synthesis was performed in the same manner as in Synthesis Example 3-11 except that <1-f> and <11-b> were used instead of <3-j> and 3- (9H-carbazol-9-yl) phenylboronic acid. As a result, 3.4 g of <Chemical Formula 218> was obtained. (Yield 38%)
MS [M] ⁺ 598.20

＜１２−ａ＞
合成例１０−８で４−ブロモベンジルクロリドの代わりに３−ブロモベンジルクロリドを使用した以外は同様の方法で合成して＜１２−ａ＞９．７ｇを得た。（収率４５％） Synthesis Example 12 Synthesis of Chemical Formula 220
Synthesis Example 12-1. <12-a> Synthesis <12-a> was synthesized according to the following reaction formula 77.
[Reaction Scheme 77]

<12-a>
<12-a> 9.7 g was obtained in the same manner as in Synthesis Example 10-8 except that 3-bromobenzyl chloride was used instead of 4-bromobenzyl chloride. (Yield 45%)

＜化学式２２０＞
合成例３−１１で＜３−ｊ＞、３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸の代わりに＜１２−ａ＞、１０−フェニルアントラセン−９−ボロン酸を使用した以外は同様の方法で合成して＜化学式２２０＞３．３ｇを得た。（収率２５％）
ＭＳ［Ｍ］^＋ ６２４．２２ Synthesis Example 12-2. Synthesis of <Chemical Formula 220><Chemical Formula 220> was synthesized according to Reaction Formula 78 below.
[Reaction formula 78]

<Chemical formula 220>
The same as in Synthesis Example 3-11 except that <12-a> and 10-phenylanthracene-9-boronic acid were used instead of <3-j> and 3- (9H-carbazol-9-yl) phenylboronic acid In this way, 3.3 g of <Chemical Formula 220> was obtained. (Yield 25%)
MS [M] ⁺ 624.22

＜化学式２２３＞
合成例３−１１で＜３−ｊ＞、３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸の代わりに＜７−ｆ＞、９−フェナントラセニルボロン酸を使用した以外は同様の方法で合成して＜化学式２２３＞４．０ｇを得た。（収率５１％）
ＭＳ［Ｍ］^＋ ４７２．１６ Synthesis Example 13 Synthesis of Formula 223
Synthesis Example 13-1. Synthesis of <Chemical Formula 223><Chemical Formula 223> was synthesized according to Reaction Formula 79 below.
[Reaction Scheme 79]

<Chemical Formula 223>
The same as in Synthesis Example 3-11 except that <7-f> and 9-phenanthracenylboronic acid were used instead of <3-j> and 3- (9H-carbazol-9-yl) phenylboronic acid. By the method, 4.0 g of <Chemical Formula 223> was obtained. (Yield 51%)
MS [M] ⁺ 472.16

＜化学式２２４＞
合成例３−１１で＜３−ｊ＞、３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸の代わりに＜７−ｆ＞、４−（１−ナフチル）フェニルボロン酸を使用した以外は同様の方法で合成して＜化学式２２４＞５．７ｇを得た。（収率６９％）
ＭＳ［Ｍ］^＋ ４９８．１７ Synthesis Example 14 Synthesis of Formula 224
Synthesis Example 14-1. Synthesis of <Chemical Formula 224><Chemical Formula 224> was synthesized according to Reaction Formula 80 below.
[Reaction Formula 80]

<Chemical formula 224>
Except that <7-f> and 4- (1-naphthyl) phenylboronic acid were used instead of <3-j> and 3- (9H-carbazol-9-yl) phenylboronic acid in Synthesis Example 3-11 Synthesis was performed in the same manner to obtain 5.7 g of <Chemical Formula 224>. (Yield 69%)
MS [M] ⁺ 498.17

＜化学式２２７＞
合成例３−１１で＜３−ｊ＞、３−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸の代わりに＜９−ｆ＞、２−トリフェニレニルボロン酸を使用した以外は同様の方法で合成して＜化学式２２７＞３．８ｇを得た。（収率４５％）
ＭＳ［Ｍ］^＋ ５３８．１５ Synthesis Example 15 Synthesis of Chemical Formula 227
Synthesis Example 15-1. Synthesis of <Chemical Formula 227><Chemical Formula 227> was synthesized according to Reaction Formula 81 below.
[Reaction Formula 81]

<Chemical Formula 227>
The same method as in Synthesis Example 3-11 except that <9-f> and 2-triphenylenylboronic acid were used instead of <3-j> and 3- (9H-carbazol-9-yl) phenylboronic acid To obtain 3.8 g of <Chemical Formula 227>. (Yield 45%)
MS [M] ⁺ 538.15

＜ＤＮＴＰＤ＞ ＜α−ＮＰＢ＞

＜ＲＤ−１＞ ＜化合物Ｅ＞ ＜Ｌｉｑ＞ Example
Examples 1 to 10 (use of light emitting layer)
Manufacture of organic light emitting diode It patterned, and it wash | cleaned so that the light emission area of ITO glass might become a size of 2 mm x 2 mm. After the substrate is mounted in the vacuum chamber, the base pressure is set to 1 × 10 ⁻⁶ torr, and the organic material is formed on the ITO by DNTPD (700 Å), NPD (300 Å), and manufactured according to the present invention. Compound + RD-1 (10%) (300 angstrom), Liq (350 angstrom), LiF (5 angstrom), Al (1,000 angstrom) were formed in this order, and the measurement was performed at 0.4 mA.

<DNTPD><α-NPB>

<RD-1><CompoundE><Liq>

＜ＢＡｌｑ＞
前記実施例１から１０、比較例１によって製造された有機電界発光素子に対して電圧、電流密度、輝度、色座標及び寿命を測定し、その結果を下記［表１］に示した。Ｔ_９５は、輝度が初期輝度（３０００ｃｄ／ｍ^２）で９５％に減少するのにかかる時間を意味する。

前記表１に示すように、本発明によって確保された有機化合物は、リン光発光性ホスト材料としてよく使われるＢＡｌｑより高効率、低駆動電圧及び長寿命を示す。 Comparative Example 1
The organic light emitting diode device for Comparative Example 1 was manufactured in the same manner except that BAlq, which is generally used as a phosphorescent host material, was used in place of the compound manufactured according to the invention in the device structure of the above embodiment. did. The structure of the BAlq is as follows.

<BAlq>
The voltage, current density, luminance, color coordinates, and lifetime of the organic electroluminescent devices manufactured in Examples 1 to 10 and Comparative Example 1 were measured, and the results are shown in [Table 1] below. T ₉₅ means the time taken for the luminance to decrease to 95% at the initial luminance (3000 cd / m ² ).

As shown in Table 1, the organic compound secured by the present invention exhibits higher efficiency, lower driving voltage and longer life than BAlq, which is often used as a phosphorescent host material.

Examples 11 to 15 (use of electron transport layer)
Manufacture of organic light emitting diode It patterned, and it wash | cleaned so that the light emission area of ITO glass might become a size of 2 mm x 2 mm. After mounting the substrate in a vacuum chamber and adjusting the base pressure to 1 × 10 ⁻⁶ torr, the organic substance was placed on the ITO with DNTPD (700 Å, NPD (300 Å), CBP + Ir (ppy) ₃ (10% ) (300 angstroms), the compound produced according to the present invention (350 angstroms), LiF (5 angstroms), and Al (1,000 angstroms) were formed in this order, and measurement was performed at 0.4 mA.

前記表２に示すように、本発明によって確保された有機化合物は、電子輸送性材料としてよく使われるＡｌｑ_３に比べて駆動電圧が低く、発光効率に優れる特性を示す。
Comparative Example 2
The organic light emitting diode device for Comparative Example 2 was manufactured in the same manner except that Liq was used instead of the compound manufactured by the invention in the device structure of the above example.

As shown in Table 2, the organic compound ensured by the present invention has a driving voltage lower than that of Alq ₃ which is often used as an electron transporting material, and exhibits excellent light emission efficiency.

Claims (16)

A heterocyclic compound represented by the following [Chemical Formula A].
[Chemical Formula A]

In the chemical formula A,
X is selected from the group consisting of S, O, NR ₁ , CR ₂ R ₃ , SiR ₄ R ₅ , GeR ₆ R ₇ , Se, Te, and BR ₈ , and R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ can be connected to each other to form a ring,
T1 is N or CR ′, T2 is N or CR ″, T3 is N or CR ′ ″, but at least one of T1 to T3 is N;
B1 is N or CR15, B2 is N or CR16, B3 is N or CR17, B4 is N or CR18,
R, R ′ to R ′ ″, R ₁ to R ₈ , R ₁₁ to R ₁₈ are the same or different, and independently of each other, hydrogen, deuterium, substituted or unsubstituted C 1-30. Alkyl group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted A heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 6 to 6 carbon atoms. 30 aryloxy groups, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or unsubstituted arylthioxy groups having 5 to 30 carbon atoms, substituted or unsubstituted A prime alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl amine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero group having 3 to 50 carbon atoms Aryl group, substituted or unsubstituted silyl group having 1 to 30 carbon atoms, substituted or unsubstituted carboxyl group having 1 to 30 carbon atoms, thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium Selected from a group, an amino group, a substituted or unsubstituted ether group having 1 to 30 carbon atoms, a substituted or unsubstituted ester group having 1 to 30 carbon atoms,
When each of R ₁₁ to R ₁₈ is adjacent to each other, adjacent functional groups may be linked to each other to form an alicyclic or aromatic monocyclic or polycyclic ring;
Two of R ₁₁ to R ₁₄ that are adjacent to each other are single bonds that are connected to * in the structural formula Q to form a condensed ring;
The linking group Y is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycle having 1 to 20 carbon atoms. An alkylene group, a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, substituted or Selected from unsubstituted C 1-60 heteroarylene groups;
Any one of R, R ′ to R ′ ″ is a single bond bonded to the linking group Y;
n is an integer from 0 to 2,
Z is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and each of the aromatic rings in the aryl group or heteroaryl group Can form an additional condensed ring to further form an alicyclic monocyclic or polycyclic ring, and the further formed alicyclic monocyclic or polycyclic carbon atoms include N, S, Can be substituted with at least one heteroatom selected from O, Se, Te, Si and Ge;
“Substitution” in the above “substituted or unsubstituted” means deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, carbon C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C2 24 heteroaryl group, or C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C1 Selected from the group consisting of ˜24 heteroarylamino groups, C1-C24 alkylsilyl groups, C1-C24 arylsilyl groups, and C1-C24 aryloxy groups It means substituted with one or more substituents.   The heterocyclic compound according to claim 1, wherein, in the chemical formula A, T1 and T3 are each a nitrogen atom, T2 is CR ", and the substituent R" is a single bond connected to the linking group Y. . 2. The heterocycle according to claim 1, wherein the linking groups Y are the same or different and are each independently a single bond, or one selected from the following structural formulas 1 to 9. Formula compound.

In the structural formulas 1 to 9, hydrogen or deuterium is bonded to the carbon position of the aromatic ring. The substituents R, R ′ to R ′ ″, R ₁₁ to R ₁₈ in [Chemical Formula A] are the same or different, and independently of each other, hydrogen, deuterium, substituted or unsubstituted C 1-20. An alkyl group; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; a substituted or unsubstituted aryl group having 5 to 20 carbon atoms; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; One that is selected,
The heterocyclic compound according to claim 1, wherein each n is 0 or 1.   The heterocyclic compound according to claim 1, wherein none of B1 to B4 in [Chemical Formula A] is a nitrogen atom.   2. The heterocyclic compound according to claim 1, wherein Z in [Chemical Formula A] is a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms. The heterocyclic compound according to claim 6, wherein Z is a heteroaryl group represented by any one selected from Structural Formula A to Structural Formula E below.

In the structural formulas A to E, W is NR ₂₄ , and R ₂₄ is a single bond; or a substituted or unsubstituted aryl group having 5 to 20 carbon atoms; a substituted or unsubstituted heteroaryl having 2 to 20 carbon atoms; One selected from the group;
R ₂₁ to R ₂₃ are the same or different and independently of each other, hydrogen, deuterium; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms;
In Structural Formula A to Structural Formula E,
* Means a binding site bonded to the linking group Y;
The cyclic groups A to D are the same or different from each other, and a hydrocarbon ring group having 4 to 20 carbon atoms capable of forming a 5-membered or 6-membered alicyclic or aromatic monocyclic or polycyclic ring. It is.   The heterocyclic compound according to claim 1, wherein Z in [Chemical Formula A] is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms. The heterocyclic compound according to claim 1, which is represented by any one selected from the following [Chemical Formula 1] to [Chemical Formula 249].

A first electrode,
A second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode,
The organic light emitting element in which the said organic layer contains 1 or more types of the heterocyclic compounds as described in any one of Claims 1-9.   The organic layer includes at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function simultaneously, a light emitting layer, an electron transport layer, and an electron injection layer. The organic light-emitting device described in 1. The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The organic light emitting device according to claim 11, wherein the light emitting layer includes a host and a dopant, and the heterocyclic compound is used as a host.   The organic light emitting device according to claim 12, wherein the organic layer further comprises a hole blocking layer or an electron blocking layer.   The organic light emitting device according to claim 11, wherein one or more layers selected from the respective layers are formed by a vapor deposition process or a solution process.   11. The organic light emitting device according to claim 10, wherein the organic light emitting device is used in any one device selected from a flat display device, a flexible display device, a monochromatic or white flat illumination device, and a single or white flexible illumination device. Organic light emitting device. The organic layer interposed between the first electrode and the second electrode includes an electron transport layer,
The organic light-emitting device according to claim 11, wherein the heterocyclic compound is used for an electron transport layer.

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