KR20140103393A - Deuterated organic compounds for organic light-emitting diode and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by chemical formula A and an organic light emitting device comprising the same. The substituents Y, R1-R17, m, n, L1, and L2 are same as defined in detailed description of the present invention.

Description

[0001] The present invention relates to a deuterated organic light emitting diode (OLED) and an organic light emitting diode (OLED)

The present invention relates to a deuterated organic light emitting compound and an organic light emitting device including the same. More particularly, the present invention relates to a deuterated organic light emitting compound capable of lowering a driving voltage while having a long life, And an organic light emitting device including the same.

Recently, as the size of a display device has been increased, a demand for a display device or a bendable display device having little space occupation due to a flat plate structure has been increasing. The liquid crystal display, which is a typical flat display device, is lighter than a conventional CRT However, it is disadvantageous in that a viewing angle is limited and a back light is necessarily required. In contrast, an organic light emitting diode (OLED), a new flat display device, is a display using an auto-luminescent phenomenon and has advantages such as a large viewing angle, a light weight and a small size compared to a liquid crystal display, In recent years, application to a full-color display or illumination is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layered structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as the light emitting material, there arises a problem that the maximum light emitting wavelength shifts to a long wavelength due to intermolecular interaction, the color purity drops, or the efficiency of the device decreases due to the light emission attenuating effect. A host-dopant system can be used as a light emitting material to increase the efficiency of light emission through the transition.

When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the light of the desired wavelength can be obtained according to the type of the dopant used.

In order for the organic light emitting device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material Should be preceded.

When 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 respective hole transporting layers and electron transporting layers to form luminescent excitons. The thus formed luminescent excitons emit light while transitioning to the ground state. The light may be divided into fluorescence using a singlet exciton and phosphorescent triplet exciton according to a light emitting mechanism, and the fluorescence and phosphorescence may be used as a light source of an organic light emitting device.

On the other hand, fluorescence using only singlet excitons has a limit of luminous efficiency because the probability of occurrence of singlet excitons is 25%, while phosphorescence using triplet excitons is superior to fluorescence in many cases Is continuing.

As a host material of the phosphorescent light emitting material, CBP is the most widely known to date, and an organic light emitting device using a hole blocking layer such as BCP and BAlq is known.

However, in the case of a conventional material such as BAlq or CBP used as a host of a phosphorescent material, a device using a conventional phosphorescent material has a higher driving voltage than a device using a fluorescent material, There is no significant advantage in terms of power efficiency (lm / w), and it is disadvantageous in terms of life span. In addition, in order to use such a phosphorescent material as a light emitting device, the aromatic heterocycle is bonded to the skeleton of a 6-membered aromatic ring or a 6-membered heteroaromatic ring in Published Patent Application No. 10-2011-0013220 (2011.02.09) Japanese Patent Laid-Open Publication No. 2010-166070 (2010.7.29) discloses an organic compound in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton .

However, in spite of efforts to manufacture the organic light emitting diode material as described above, it is still not long enough to develop a material for low driving voltage and high luminous efficiency, so that the luminous efficiency is excellent, The necessity of developing a light emitting material having characteristics is continuously required.

Japanese Patent Application Laid-Open No. 10-2011-0013220 (Feb., 2011)

Japanese Unexamined Patent Publication No. 2002-166070 (2010.7.29)

Accordingly, a first technical object of the present invention is to provide a novel organic compound having low-voltage driving characteristics, excellent luminous efficiency, and particularly long life characteristics, which can be used in a light emitting layer of an organic light emitting device.

A second object of the present invention is to provide an organic light emitting device including the organic compound.

In order to achieve the first technical object, the present invention provides a compound represented by the following formula (A).

(A)

In the above formula (A)

이고, The substituent Y is

ego,

R ₁ to R ₁₇ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a carbon having a substituted or unsubstituted heteroatom, O, N or S A heteroaryl group having 2 to 50 carbon atoms, a cyano group, a nitro group, and a halogen group, and may be connected with adjacent substituents to form a monocyclic or polycyclic ring of alicyclic or aromatic, , The carbon atom of the single aromatic ring or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O;

R ₁₈ is a substituent as defined above to R ₁ to R ₁₇ or Y;

Wherein x in the substituent Y is an integer of 1 to 4;

Wherein L ₁ and L ₂ are a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

M and n are each independently an integer of 1 to 3, and when m and n are 2 or more, each L ₁ may be the same or different and each L ₂ may be the same or different from each other ;

The substituent of one of R ₅ to R ₈ and one of R ₁₀ to R ₁₃ is a single bond bonded to L ₂ which is the linking group, respectively.

According to another aspect of the present invention, there is provided a plasma display panel comprising a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, An organic light emitting device including at least one organic light emitting compound of the present invention is provided.

According to the present invention, the organic electroluminescent compound for a phosphorescent host represented by the formula [A] has a long-life characteristic as compared with the existing materials, has advantages of low voltage driving characteristics and excellent luminous efficiency, Lt; / RTI >

1 is a schematic view of an organic light emitting device according to an embodiment of the present invention.
FIG. 2 is a graph showing the life evaluation results of organic light emitting devices according to an embodiment of the present invention and a comparative example.

Hereinafter, the present invention will be described in more detail.

The present invention provides an organic luminescent compound which can be used for the luminescent layer of an organic luminescent device, which comprises a compound represented by the following formula (A).

(A)

In the above formula (A)

이고, The substituent Y is

ego,

R ₁ to R ₁₇ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a carbon having a substituted or unsubstituted heteroatom, O, N or S A heteroaryl group having 2 to 50 carbon atoms, a cyano group, a nitro group, and a halogen group, and may be connected with adjacent substituents to form a monocyclic or polycyclic ring of alicyclic or aromatic, , The carbon atom of the single aromatic ring or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O;

R ₁₈ is a substituent group as defined above to R ₁ to R ₁₇ , or Y;

Wherein x in the substituent Y is an integer of 1 to 4;

Wherein L ₁ and L ₂ are a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

M and n are each independently an integer of 1 to 3, and when m and n are 2 or more, each L ₁ may be the same or different and each L ₂ may be the same or different from each other ;

The substituent of one of R ₅ to R ₈ and one of R ₁₀ to R ₁₃ is a single bond bonded to the linking group L 2,

The 'substituted' in the above 'substituted or unsubstituted' means a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, , An alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms , An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, Group, and an aryloxy group having 1 to 24 carbon atoms.

In consideration of the range of the alkyl or aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms" and "substituted or unsubstituted aryl group having 5 to 50 carbon atoms", it is preferable that the number of carbon atoms is 1 to 30 And the number of carbon atoms of the aryl group having 5 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl moiety or aryl moiety when it is considered that the substituent is not substituted without considering the substituted moiety. For example, a phenyl group substituted with a butyl group at the para position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having a carbon number of 4.

The present invention relates to a compound represented by the above formula (A), wherein an organic light emitting compound in which deuterium is substituted at a specific position in the quinazoline has characteristics of low voltage driving of the organic light emitting device, better luminescence efficiency and long life And thus it is possible to manufacture a stable and excellent device.

The deuterium-substituted compound exhibits a lower zero energy and lower vibration energy level because the atomic mass of deuterium is two times greater than that of hydrogen, as compared to a compound bonded with hydrogen. In addition, physicochemical properties such as chemical bond lengths related to deuterium appear to be different from hydrogen, and in particular, the CD bond elongation amplitude is smaller than that of CH bonds, so that the van der Waals radius of deuterium is smaller than hydrogen, Indicating that the bond is shorter and stronger than the CH bond.

In addition, when substituted with deuterium, the energy of the bottom state is lowered. As the bond length of deuterium and carbon becomes shorter, the molecular hardcore volume is reduced, and thus, the electro polar polarizability can be reduced, It is known that the thin film volume can be increased by weakening the intermolecular interaction. Such characteristics can make the effect of lowering the crystallinity of the thin film, that is, amorphous state, and can generally be effective for increasing the lifetime and driving characteristics of the organic light emitting device, and the heat resistance can be further improved.

In the formula [B-1], an organic luminescent compound containing a quinazoline group according to an embodiment of the present invention is shown. In the formula B-2, an organic luminescent compound represented by the formula The electron distribution showing the excited state of FIG.

      [Formula B-1] [Formula B-2]

As shown in the above formula (B-2), the organic luminescent compound of the present invention combines the holes and electrons injected into the organic material layer in the structure of the organic luminescent device to recombine to form luminescent excitons, And emits light. In this case, as shown in the above formula (B-2), when the deuterium is substituted for the quinazoline moiety having a large amount of electrons, it is presumed that the deuterium substitution effect mentioned above is maximized.

On the other hand, the aryl group used in the compound of the present invention includes an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and includes a single or fused ring system containing 5 to 7 atoms, preferably 5 or 6 atoms, When a substituent is present in the aryl group, the adjacent substituent may be fused with each other to form a ring.

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluororan And the like, but are not limited thereto.

At least one hydrogen atom of the aryl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ' R 'and R "are independently an alkyl group having 1 to 10 carbon atoms, and in this case, they are referred to as" alkylamino group "), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, , A halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, A heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

The heteroaryl group which is a substituent used in the compounds of the present invention is a heteroaromatic radical having from 2 to 24 carbon atoms which may contain, in each ring in the aryl group, from 1 to 4 heteroatoms selected from N, O, P or S, , And the rings may be fused to form a ring. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the aryl group.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. The atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, At least one hydrogen atom in the alkoxy group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the silyl group used as the substituent in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, Butylsilyl, dimethylpurylsilyl and the like, and at least one hydrogen atom of the silyl group may be substituted with the same substituent as the aryl group.

In the present invention, the linking groups L < _{1 >} and L < ₂ > in the above formula (A) are the same or different and each independently a single bond or any one selected from the following Structural Formulas 1 to 8.

[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural formula 5] [Structural formula 6] [Structural formula 7] [Structural formula 8]

Here, the carbon of the aromatic ring in the substituents L ₁ and L ₂ may be bonded to hydrogen or deuterium.

In the present invention, the substituents R ₁ to R ₁₈ in the above-mentioned formula (A) are the same or different and each independently hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 heteroaryl group; And m and n may be one or two.

In the present invention, the substituents R ₁ to R ₁₇ may be combined with adjacent substituents to provide a compound which does not form a ring. That is, in the present invention, the compound represented by the above-mentioned formula (A) means that each carbazole group bonded to the linking group L ₂ can be formed with only three rings without forming any additional ring.

In the present invention, the substituents R ₁ to R ₁₇ may be combined with adjacent substituents to form a ring.

In this case, the above-mentioned formula (A) may further comprise a fused 1 to 3 aromatic rings by bonding the substituents adjacent to each other (R ₁ to R ₄ ) and / or (R ₁₄ to R ₁₇ ) And may be exemplarily represented by the following formulas (1) to (24), but the present invention is not limited thereto.

[Chemical Formula 1] < EMI ID =

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

[Chemical Formula 23]

The Formula 1 to the substituents Y and the substituents R ₁ to R ₁₈ is coupled within the polycyclic ring in the [formula 24] are the same as R ₁ to R ₁₇ defined respectively in the above-mentioned [Chemical Formula A], each of the substituents R _a and R _b is the same as R ₁ to R ₁₇ defined above, and each of p is independently an integer of 1 to 6,

In the present invention, when the substituents R ₁ to R ₁₇ are connected to adjacent substituents to form a ring or form a ring, x of the substituent Y may be 3 or 4.

In the present invention, when the substituents R ₁ to R ₁₇ are connected to adjacent substituents to form a ring or form a ring,

또는

이고, m 및 n 은 각각 1일 수 있다. The linking groups L ₁ and L ₂ may be the same or different and each independently a single bond,

or

, And m and n may be 1, respectively.

In the present invention, when the substituents R ₁ to R ₁₇ are connected to adjacent substituents to form a ring or not to form a ring, R ₉ in the substituent Y is deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 heteroaryl group; And in this case, the linking groups L ₁ and L ₂ may each be a single bond.

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer may include one or more of the organic light emitting compounds of the present invention in the present invention.

In the present invention, the phrase "(organic layer) contains at least one organometallic compound" means that one kind of organometallic compound (organic layer) belonging to the category of the present invention or two kinds of organometallic compounds May contain the above compounds. "

The organic layer containing the organic luminescent compound of the present invention may include at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, have. At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, and the light emitting layer may be composed of a host and a dopant, and the organic light emitting compound of the present invention may be used as a phosphorescent host.

In the present invention, a dopant material may be used for the light emitting layer in addition to the host. When the light emitting layer includes a host and a dopant, the dopant may be selected from the range of about 0.01 to about 20 parts by weight based on 100 parts by weight of the host, but is not limited thereto.

In the present invention, as the electron transporting layer material, a known electron transporting material can be used as a material that stably transports electrons injected from an electron injection electrode (cathode). Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, compound 201, compound 202, oxadiazole derivative PBD, BMD, BND and the like may be used, but the present invention is not limited thereto.

TAZ BAlq

Compound 201 Compound 202 BCP

In addition, the electron transporting layer used in the present invention can be used alone or in combination with the electron transporting layer material as the organometallic compound represented by the formula (C).

 ≪ RTI ID = 0.0 &

In the above formula (C)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M A ligand chelated by coordination bond with the single bond, and

Wherein M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination bond with M,

O is oxygen,

A represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted C2 to C20 Substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, and substituted or unsubstituted hetero atoms having 2 to 50 carbon atoms having O, N or S, An aryl group,

M is 1 and n is 0 when M is a metal selected from an alkali metal,

M = 1, n = 1, or m = 2 and n = 0 when M is a metal selected from alkaline earth metals,

M is from 1 to 3 when M is boron or aluminum, and n is any of from 0 to 2, and m + n = 3;

The 'substituted' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, heteroarylamino, alkylsilyl, An aryl group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

In the present invention, Y may be the same or different and independently of each other may be any one selected from the following formulas [C1] to [C39], but is not limited thereto.

[Structural formula C1] [Structural formula C2] [Structural formula C3]

[Structural formula C4] [Structural formula C5] [Structural formula C6]

[Structural formula C7] [Structural formula C8] [Structural formula C9] [Structural formula C10]

[Structural formula C11] [Structural formula C12] [Structural formula C13]

[Structural formula C14] [Structural formula C15] [Structural formula C16]

[Structural formula C17] [Structural formula C18] [Structural formula C19] [Structural formula C20]

[Structural formula C21] [Structural formula C22] [Structural formula C23]

[Structural formula C24] [Structural formula C25] [Structural formula C26]

[Structural formula C27] [Structural formula C28] [Structural formula C29] [Structural formula C30]

[Structural formula C31] [Structural formula C32] [Structural formula C33]

[Structural formula C34] [Structural formula C35] [Structural formula C36]

[Structural formula C37] [Structural formula C38] [Structural formula C39]

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

Hereinafter, the organic light emitting device of the present invention will be described with reference to FIG.

1 is a cross-sectional view showing the structure of an 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, An injection layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic light emitting device of the present invention and a method of manufacturing the same will be described below. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, 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 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

The hole injection layer material is not particularly limited as long as it is conventionally used in the art. For example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- ], Etc. However, the present invention is not limited thereto.

The material for the hole transport layer is not particularly limited as long as it is commonly used in the art and includes, for example, N, N'-bis (3-methylphenyl) -N, N'- -Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine (a-NPD). However, the present invention is not necessarily limited thereto.

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 to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

As a material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq _2, OXD-7, Liq, and although any one can be selected from any of formulas 101) to (107, but not limited to, .

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

(101)

≪ RTI ID = 0.0 >

Formula 107

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 deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

The light emitting layer may be made of a host and a dopant.

Further, according to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM.

At this time, the dopant used in the light emitting layer may be at least one compound selected from compounds represented by the following formulas (A-1) to (J-1).

[General Formula A-1]

Wherein M is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. The ligands L ₁ , L ₂ and L ₃ are the same or different from each other and independently selected from the following structural formulas D, but are not limited thereto.

In the following structural formula D, " * " represents a site coordinated to the metal ion M. [

[Structural formula D]

Wherein R is different from or the same as each other and is independently selected from the group consisting of hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, Or a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2- A substituted or unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylamino group, and a substituted or unsubstituted C6- An arylsilyl group having 1 to 30 carbon atoms;

Each R is independently selected from 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, a halogen group, deuterium and hydrogen Which may be further substituted with one or more substituents;

And R may be linked to each adjacent substituent by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

The L may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

As one example, the dopant represented by the above-mentioned [formula A-1] may be any one selected from the following compounds.

[Formula B-1]

In the general formula B-1,

M ^A1 represents the same metal ion as defined in the general formula (A1), also, Y ^{A11, A14} Y, Y and Y ^{A15 A18} each independently represent a carbon atom or a nitrogen atom, Y ^{A12, A13} Y, Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom, and L ^A11 , L ^A12 , L ^A13 and L ^A14 each represent a linking group And Q ^A11 and Q ^A12 represent a partial structure containing an atom bonding to M ^A1 .

Exemplary structures of the compound represented by the general formula B-1 include, but are not limited to, the following.

[Formula C-1]

In the general formula C-1,

M ^B1 represents the same metal ion as defined in the general formula A-1, Y ^B11, Y ^B14, Y ^B15 and Y ^B18 represents a carbon atom or a nitrogen atom, each independently, Y ^B12, Y ^B13, Y ^B16 and Y ^B17 each independently represents a substituted or unsubstituted carbon atoms, a substituted or unsubstituted nitrogen atom, an oxygen atom, a sulfur atom, a, L ^B11, L ^B12, L ^B13, L ^B14 represents a linking group, Q ^B11, Q ^B12 is ^Represents a partial structure containing an atom bonding to M ^B1 .

Exemplary structures of the compound represented by the general formula C-1 include, but are not limited to, the following.

[Formula D-1]

In the general formula D-1,

M ^C1 represents a metal ion the same as defined in formula A-1,

R ^C11 and R ^C12 are each independently a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, or a substituent which is not connected to each other,

R ^C13 and R ^C14 each independently represent a hydrogen atom, a substituent which is mutually connected to form a 5-membered ring or a substituent which is not connected to each other, G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom , L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonding to M ^C1 .

Exemplary structures of the compound represented by the general formula D-1 include, but are not limited to, the following.

      [Formula E-1]

In the general formula E-1,

M ^D1 represents the same metal ion as defined in formula (A-1), G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and J ^D11 , J ^D12 , J ^D13 , J ^D14 each independently represents an atomic group necessary for forming a five-membered ring, and L ^D11 and L ^D12 represent a linking group.

Exemplary structures of the compound represented by the general formula E-1 include, but are not limited to, the following.

   [Formula F-1]

In the general formula F-1,

M ^E1 represents the same metal ion as defined in formula A-1, J ^E11 and J ^E12 each independently represent an atomic group necessary for forming a five-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 represent Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and the like.

Exemplary structures of the compound represented by the general formula F-1 include, but are not limited to, the following.

        [Formula G-1]

In the general formula G-1,

M ^F1 represents the same metal ion as defined in formula A-1,

L ^F11, L ^F12 and L ^F13 represents a linking ^{group, R F11, R F12, R} F13 and R ^F14 represents a substituent, R ^F11 and R ^F12, R ^F12 and R ^F13, R ^F13 and R ^F14 are connected to each other And the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. And Q ^F11 and Q ^F12 represent a partial structure containing an atom bonding to M ^F1 .

Exemplary structures of the compound represented by the general formula G-1 include, but are not limited to, the following.

[Formula H-1] [Formula H-2] [Formula H-3]

In the general formula H-1,

R ¹¹ and R ¹² are substituents of alkyl, aryl or heteroaryl; And q11 and q12 may be an integer of 0 to 4, preferably 0 to 2, and may form a fused ring with substituents adjacent to each other.

When q11 and q12 are 2 to 4, a plurality of R11 and R12 are the same or different,

L ¹ is a ligand which binds to platinum and is preferably a ligand capable of forming an ortho metal platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand or a halogen ligand, more preferably an ortho metal ) Ligand forming a platinum complex, a bipyridyl ligand, or a phenanthroline ligand.

n ¹ is an integer of 0 to 3, preferably 0, m ¹ is 1 or 2, and preferably 2.

It is preferable that n ¹ and m ¹ denote the metal complex represented by the general formula H-1 as a neutral complex.

R ²¹ , R ²² , n ² , m ² , q ²² and L ² are the same as R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² and L ¹ in the general formula H-2, q ²¹ is an integer of 0 to 2, preferably 0.

Wherein R ³¹ , n ³ , m ³ and L ³ are the same as R ¹¹ , n ¹ , m ¹ and L ¹ , q ³¹ is an integer of 0 to 8, 2 is preferable, and 0 is more preferable.

Examples of the specific compounds of the above-mentioned general formulas H-1 to H-3 are as follows, but are not limited thereto.

[Formula I-1]

    [Formula I-1]

In the general formula I-1,

Ring A, ring B, ring C, and ring D represent a nitrogen-containing heterocyclic ring which may have a substituent, and the remaining two rings are an aryl ring or heteroaryl which may have a substituent A condensed ring can be formed by ring A and ring B, ring A and ring C, and / or ring B and ring D, respectively. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which two of them coordinate to a platinum atom, and the remaining two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (or a bond), but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. ^{Two of} Z ¹ , Z ² , Z ³ and Z ⁴ represent coordinate bond, and the remaining two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of the specific compounds of the general formula I-1 include, but are not limited to, the following.

[Formula J-1]

In the general formula J-1,

M represents the same metal ion as defined in the general formula A-1, Ar1 represents a substituted or unsubstituted cyclic structure, and in the two azomethine bonds (-C = N-) bonded to the M, , And nitrogen atoms (N) are respectively bonded to the M and form a three-terminal ligand which is bonded at the 3-position to the M as a whole.

Further, in Ar 1, C represents a carbon atom constituting a ring structure represented by Ar 1. R 1 and R 2 may be the same or different and each represents a substituted or unsubstituted alkyl group or aryl group, and L represents a one-dimensional ligand.

In the general formula J-1, M is preferably Pt. The above-mentioned Ar1 is preferably selected from a 5-membered ring, a 6-membered ring and condensed ring group thereof.

Examples of the specific compounds of the general formula J-1 include, but are not limited to, the following.

The light emitting layer may further include various dopants and various hosts as well as the dopant and the host.

In the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular deposition method or a solution process. Here, the deposition method refers to a method of forming a thin film by evaporating a material used as a material for forming each of the layers through heating or the like under vacuum or low pressure, Refers to a method of mixing a material used as a material with a solvent and forming the thin film by a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating or the like.

Further, the organic light emitting device of the present invention may be a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a single-color or white-colored flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

 (Example)

Synthesis Example 1. Synthesis of [Compound 1]

Synthesis Example 1-1) Synthesis of [Intermediate 1-a]

[Reaction Scheme 1-1]

                    [Intermediate 1-1-a] [Intermediate 1-a]

To a round bottom flask was added bromobenzene-d5 (500 g, 3085 mmol), copper iodide (117.5 g, 615 mmol), trans-4-hydroxy-L-proline (162 g, 1235 mmol), potassium carbonate (1279.5 g, 9255 mmol) 2500 mL of sulfoxide was added thereto and stirred. After the gas trap was installed, 2900 mL of ammonia water (28%) was slowly added dropwise. The mixture was stirred overnight at 80 ° C. After completion of the reaction, the reaction mixture was extracted several times with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and then subjected to column chromatography using ethyl acetate and heptane to obtain 185 g (yield: 61.1%) of [intermediate 1-1-a] as a liquid phase. (185 g, 1887 mmol), trichloroacetonitrile (326.6 g, 2257 mmol) and 1850 mL of dichloromethane, and then tin (IV) chloride (491.2 g, 1887 mmol) was added. After placing the flask in an ice-bath, boron trichloride 1M in dichloromethane (243.3 g, 2072 mmol) was slowly added dropwise, and the mixture was refluxed and stirred for 24 hours. After completion of the reaction, the flask was placed in an ice-bath. Potassium carbonate (3126.5 g, 22616 mmol) was dissolved in methanol in a beaker and slowly added dropwise. After the dropwise addition, the mixture was heated to remove dichloromethane, and the mixture was refluxed and stirred for about 3 hours. After cooling to room temperature, the insoluble solid was filtered off. The filtrate was concentrated under reduced pressure, dissolved in ethyl acetate, and washed with a 2-normal aqueous hydrochloric acid solution and water. The organic layer was treated with magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography using ethyl acetate and hexane to obtain 41.6 g of [intermediate 1-a]. (Yield: 18.1%)

Synthesis Example 1-2) Synthesis of [Intermediate 1-b]

 [Reaction Scheme 1-2]

                                                    [Intermediate 1-b]

[Intermediate 1-a] (20.0 g, 164 mmol) obtained in [Scheme 1-1] and 140 mL of tetrahydrofuran were added to a round bottom flask under a nitrogen atmosphere at room temperature and stirred. 109.1 mL (327 mmol) of phenylmagnesium bromide (3.0 M in Et ₂ O) was added dropwise. After reflux stirring for about 1 hour, the temperature was set to 0 캜. Ethyl chloroformate (15.5 g, 143 mmol) was added dropwise thereto, followed by reflux stirring for about 1 hour. The aqueous ammonium chloride solution was added until it became slightly acidic, and the resulting solid was filtered off and washed with water and heptane. 30.2 g of Intermediate 1-b, which was a yellow solid, was obtained. (Yield: 81.5%)

Synthesis Example 1-3) [Synthesis of intermediate 1-c]

 [Reaction 1 - 3]

                                   [Intermediate 1-c]

[Intermediate 1-b] (30.0 g, 133 mmol) obtained in [Scheme 1-2] and about 80 mL of phosphorus oxychloride were added to a round bottom flask under a nitrogen atmosphere at room temperature and stirred. After refluxing overnight, the temperature was cooled to -20 캜 on the next day, and water was slowly dropped about 400 mL. The resulting solid was filtered and washed with water, methanol and heptane. And recrystallized with toluene and heptane to obtain 15.2 g of [white solid 1-c]. (Yield: 46.8%)

Synthesis Example 1-4) Synthesis of [Intermediate 1-d]

 [Reaction Scheme 1-4]

                                                  [Intermediate 1-d]

At room temperature, 2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a round bottom flask under a nitrogen stream and stirred for about 30 minutes. 10.0 g (41 mmol) of 4-bromo-9H-carbazole and 100 mL of dimethylformamide were added dropwise thereto, followed by stirring for about 1 hour. 12.9 g (53 mmol) of Intermediate 1-c obtained from the above Scheme 1-3 and 100 mL of dimethylformamide were added and stirred overnight. 600 mL of distilled water was added to the flask, and the resulting solid was filtered. And recrystallized with toluene to obtain 14.6 g of [intermediate 1-d]. (Yield: 79.1%)

Synthesis Example 1-5) Synthesis of [Intermediate 1-e]

 [Reaction Scheme 1-5]

                        [Intermediate 1-e]

A mixture of 20.0 g (81.3 mmol) 4-bromo-9H-carbazole, 33.2 g (162.5 mmol) 2-iodobenzene, 10.3 g (162.5 mmol) copper powder, 4.3 g (16.3 mmol) Potassium carbonate (33.7 g, 243.9 mmol) were added in this order, 200 ml of 1,2-dichlorobenzene was added thereto, and the mixture was refluxed and stirred at 180 ° C for 1 day. After the completion of the reaction, the solution was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 21.0 g of [intermediate 1-e]. (Yield: 88%)

 Synthesis Example 1-6) Synthesis of [Intermediate 1-f]

 [Reaction Scheme 1-6]

                        [Intermediate 1-f]

21.0 g (65.0 mmol) of Intermediate 1-e obtained in the above Reaction Scheme 1-5 was dissolved in 210 ml of tetrahydrofuran in a nitrogen stream and 49 ml (78.0 mmol) of 1.6 M n-butyllithium was added thereto while stirring at -78 ° C. ) Was slowly added dropwise, followed by stirring for 1 hour while maintaining the temperature at -78 ° C. Thereafter, trimethylborate (8.1 g, 78.0 mmol) was slowly added dropwise, and then the mixture was stirred at room temperature for 2 hours. After completion of the reaction, 100 ml of 2 M hydrochloric acid aqueous solution was added at room temperature and stirred for 30 minutes. The mixture was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to obtain 12.5 g of [intermediate 1-f]. (Yield 67%)

Synthesis Example 1-7) Synthesis of [Compound 1]

 [Reaction Scheme 1-7]

                                                [Compound 1]

14.6 g (32 mmol) of the compound represented by [Intermediate 1-d] obtained from the above Scheme 1-4 and 11.2 g (39 mmol) of the compound represented by [Intermediate 1-f] ), 0.7 g (0.64 mmol) of tetrakis (triphenylphosphine) palladium, 8.9 g (64 mmol) of potassium carbonate, 80 ml of 1,4-dioxane, 80 ml of toluene and 30 ml of distilled water. When the reaction was completed, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and acetone to obtain 4.7 g of a pale yellow solid [Compound 1]. (Yield: 24%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

130.4, 136.8, 144.4, 145.4, 150, 155.8, 161 [44C], 178.5,

Synthesis Example 2. Synthesis of [Compound 2]

Except that 3-bromo-9H-carbazole was used instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, the same procedure as Synthesis Example 1-1 to Synthesis Example 1-7 was used To obtain 7.5 g of [Compound 2]. (Yield: 31%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

118.4, 109.5, 111.6, 116.8, 118.9, 119.4, 119.8, 121.4, 125.5, 125.6, 126.6, 127, 127.5, 128, 128.6, 128.7, 129, 129.2, 129.3, 131.8, 133, 133.1, 134, 136.8, 143.7, 144.4, 145.9, 150, 44C]

Synthesis Example 3. Synthesis of [Compound 3]

Except that 2-bromo-9H-carbazole was used instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, the same procedure as Synthesis Example 1-1 to Synthesis Example 1-7 was used To obtain 6 g of [Compound 3]. (Yield: 25%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.4, 109.9, 118.9, 119.3, 119.8, 121.4, 125.5, 125.6, 126.6, 127, 127.5, 128, 128.6, 128.7, 129, 129.2, 129.3, 131.8, 133, 133.1, 134, 136.8, 141.6, 144.4, 145.9, 150, 44C]

Synthesis Example 4. Synthesis of [Compound 4]

Carbazole instead of the 4-bromo-9H-carbazole used in the above Synthesis Example 1-5 was used in the above Synthesis Example 1 (1) except that 3-bromo-9H- -1 to Synthesis Example 1-7, 6.7 g of [Compound 4] was obtained. (Yield: 28%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

118.4, 110.8, 117.6, 118.9, 119.4, 119.8, 121.4, 125.5, 125.6, 126.6, 127, 127.5, 128, 128.5, 128.6, 128.7, 129, 129.2, 129.3, 131.4, 131.8, 133, 134, 136.8, 143.7, 144.3, 144.4, 150, 161 [44C]

Synthesis Example 5. Synthesis of [Compound 5]

Bromo-9H-carbazole was used in place of 4-bromo-9H-carbazole used in Synthesis Example 1-4, and 3-bromo-9H- -Bromo-9H-carbazole, the compound [5] was synthesized in the same manner as in [Synthesis Example 1-1], except that [ g. (Yield: 26%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119C, 143.9, 144.3, 144.4, 150, 155.8, 161 [44C]

Synthesis Example 6. Synthesis of [Compound 6]

Bromo-9H-carbazole was used in place of 4-bromo-9H-carbazole used in Synthesis Example 1-4, and 3-bromo-9H- -Bromo-9H-carbazole, the compound [6] was synthesized in the same manner as in Synthesis Example 1-1 to Synthesis Example 1-7, except that [ g. (Yield: 28%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119C, 143.9, 144.3, 144.4, 150, 155.8, 161 [44C]

SYNTHESIS EXAMPLE 7 Synthesis of [Compound 7]

Carbazole was used instead of 4-bromo-9H-carbazole used in the above Synthesis Example 1-5, the compound obtained in Synthesis Example 1 -1 to Synthesis Example 1-7, 8.6 g of [Compound 7] was obtained. (Yield: 36%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128.4, 128.9, 44C]

Synthesis Example 8. Synthesis of [Compound 8]

Bromo-9H-carbazole instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, 2 -Bromo-9H-carbazole, the compound [8] was synthesized in the same manner as in Synthesis Example 1-1 to Synthesis Example 1-7 except that [ g. (Yield: 33%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.9, 110.9, 119.3, 119.4, 119.8, 121.4, 125.5, 126.6, 127, 127.5, 128, 128.7, 129, 129.2, 129.3, 131.8, 133, 133.1, 134, 134.4, 136.8, 141.6, 143.7, 144.4, 145.9, 150, 155.8, 161 [ 44C]

Synthesis Example 9. Synthesis of [Compound 9]

Bromo-9H-carbazole was used in place of 4-bromo-9H-carbazole used in Synthesis Example 1-4, and 2-bromo-9H- -Bromo-9H-carbazole, the compound [9] was synthesized in the same manner as in Synthesis Example 1-1 to Synthesis Example 1-7, except that [ g. (Yield: 30%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.4, 125.9, 112.9, 121.4, 125.5, 126.6, 127, 127.5, 128, 128.7, 129, 129.2, 129.3, 131.8, 133, 133.1, 134, 134.4, 136.8, 141.6, 144.4, 145.9, 150, 155.8, 161 [44C]

Synthesis Example 10. Synthesis of [Compound 10]

Carbazole was used instead of the 4-bromo-9H-carbazole used in the above Synthesis Example 1-5, except that the compound of Synthesis Example 1 -1 >, the same procedure as in Synthesis Example 1-7 was used to obtain 7 g of [Compound 10]. (Yield: 29%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128.4, 128.4, 128.1, 161 [44C]

Synthesis Example 11. Synthesis of [Compound 11]

Bromo-9H-carbazole instead of the 4-bromo-9H-carbazole used in the above Synthesis Example 1-4, except that 1-bromo-9H- -Bromo-9H-carbazole, the compound [11] was synthesized in the same manner as in Synthesis Example 1-1 to Synthesis Example 1-7, except that [ g. (Yield: 37%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129C,

Synthesis Example 12. Synthesis of [Compound 12]

Bromo-9H-carbazole instead of the 4-bromo-9H-carbazole used in the above Synthesis Example 1-4, except that 1-bromo-9H- -Bromo-9H-carbazole, the compound [12] was synthesized in the same manner as in [Synthesis 1-1], except that [ g. (Yield: 31%)

MS (MALDI-TOF): m / z 617 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.6, 161 [44C]

Synthesis Example 13. Synthesis of [Compound 13]

Synthesis Example 13-1) Synthesis of [intermediate 13-a]

 [Reaction Scheme 13-1]

                                                  [Intermediate 13-a]

At room temperature, 2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a round bottom flask under a nitrogen stream and stirred for about 30 minutes. 10.0 g (41 mmol) of 3-bromo-9H-carbazole and 100 mL of dimethylformamide were added dropwise thereto, followed by stirring for about 1 hour. 12.9 g (53 mmol) of Intermediate 1-c obtained from the above Scheme 1-3 and 100 mL of dimethylformamide were added and stirred overnight. 600 mL of distilled water was added to the flask, and the resulting solid was filtered. And recrystallized with toluene to obtain 14.1 g of [intermediate 13-a]. (Yield: 76%)

Synthesis Example 13-2) Synthesis of intermediate 13-b

 [Reaction Scheme 13-2]

                        [Intermediate 13-b]

A mixture of 20.0 g (81.3 mmol) of 3-bromo-9H-carbazole, 33.3 g (162.5 mmol) of 3-iodopyridine, 10.3 g (162.5 mmol) of copper powder, 4.3 g (16.3 mmol) Potassium carbonate (33.7 g, 243.9 mmol) were added in this order, 200 ml of 1,2-dichlorobenzene was added thereto, and the mixture was refluxed and stirred at 180 ° C for 1 day. After the completion of the reaction, the solution was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 22.0 g of [intermediate 13-b]. (Yield: 84%)

 Synthesis Example 13-3) Synthesis of intermediate 13-c

 [Reaction Scheme 13-3]

                        [Intermediate 13-c]

21.0 g (65.0 mmol) of Intermediate 13-b obtained in the above Reaction Scheme 13-2 was dissolved in 210 ml of tetrahydrofuran under a nitrogen stream, and 49 ml (78.0 mmol) of 1.6 M n-butyllithium ) Was slowly added dropwise, followed by stirring for 1 hour while maintaining the temperature at -78 ° C. Thereafter, trimethylborate (8.1 g, 78.0 mmol) was slowly added dropwise, and then the mixture was stirred at room temperature for 2 hours. After completion of the reaction, 100 ml of 2 M hydrochloric acid aqueous solution was added at room temperature and stirred for 30 minutes. The mixture was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to obtain 12.1 g of [intermediate 13-c]. (Yield: 65%)

Synthesis Example 13-4) Synthesis of [Compound 13]

 [Reaction Scheme 13-4]

                                                [Compound 13]

10.3 g (32 mmol) of the compound represented by [Intermediate 13-a] and 11.2 g (39 mmol) of the intermediate [13-c] ), 0.7 g (0.64 mmol) of tetrakis (triphenylphosphine) palladium, 8.9 g (64 mmol) of potassium carbonate, 80 ml of 1,4-dioxane, 80 ml of toluene and 30 ml of distilled water. When the reaction was completed, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and acetone to obtain 5.3 g of a pale yellow solid [Compound 13]. (Yield: 27%)

MS (MALDI-TOF): m / z 618 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.9, 119.4, 119.8, 121.4, 124.4, 125.5, 126.6, 127, 127.4, 127.5, 128, 128.7, 129, 129.2, 131.8, 133, 133.1, 134, 135.5, 141.5, 143.3, 143.7, 144.4, 146.4, 150, 155.8, 161 [ 43C]

Synthesis Example 14. Synthesis of [Compound 14]

[Reaction Scheme 14-1]

                                               [Intermediate 14-a]

[Reaction Scheme 14-2]

                                     [Intermediate 14-b]

[Reaction Scheme 14-3]

                                          [Intermediate 14-c]

[Reaction Scheme 14-4]

                                                 [Intermediate 14-d]

[Reaction Scheme 14-5]

                                           [Compound 14]

Except that 4-pyridinyl magnesium bromide (0.25M in THF) was used in place of the phenylmagnesium bromide (3.0M in Et ₂ O) used in Synthesis Example 1-2. [Reaction Scheme 14-1] to [Reaction Scheme 14-3] to obtain [Intermediate 14-c].

[Intermediate 14-d] was obtained by using 3-bromo-9H-carbazole in the same manner as in Synthesis Example 1-5 to Synthesis Example 1-6, as shown in the above Scheme 14-4.

5.5 g of [Compound 14] was obtained in the same manner as in the above Synthesis Example 1-7, using the intermediate 14-c and the intermediate 14-d as in the above Scheme 14-5. (Yield: 29%)

MS (MALDI-TOF): m / z 618 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

131C,

Synthesis Example 15. Synthesis of [Compound 15]

Synthesis Example 15-1. Synthesis of [intermediate 15-a]

 [Reaction Scheme 15-1]

                              [Intermediate 15-a]

43.2 g (95 mmol) of the synthesized intermediate [13-a] was added to a round bottom flask containing 500 mL of tetrahydrofuran, and the temperature was adjusted to -78 ° C under a nitrogen atmosphere. After 30 minutes, 65 mL (104 mmol) of n-butyllithium was slowly added dropwise. After 1 hour, 26.5 g (104 mmol) of iodine was slowly added dropwise and the temperature was raised to room temperature. After stirring for about 2 hours at room temperature, an aqueous solution of sodium thiosulfate was added. The organic layer was collected and concentrated under reduced pressure. The solid was recrystallized from hexane, and the resulting solid was filtered and dried to obtain [Intermediate 15-a] (38.6 g, yield 81%).

 [Reaction Scheme 15-2]

                               [Intermediate 15-b]

26.8 g (53.5 mmol) of the synthesized intermediate 15-a, 12.9 g (61.2 mmol) of 4-bromophenylboronic acid, 1.2 g (1.1 mmol) of tetrakis (triphenylphosphine) palladium, g (107 mmol), 1,4-dioxane (100 ml), toluene (100 ml) and distilled water (50 ml), and the mixture was stirred at 100 ° C for 12 hours. When the reaction was completed, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from dichloromethane and acetone to obtain 19.3 g of [intermediate 15-b]. (Yield: 68%)

Synthesis Example 15-3. Synthesis of [Compound 15]

[Reaction Scheme 15-3]

                                               [Compound 15]

[Compound 15] was obtained in the same manner as in Synthesis Example 14-4, except that [Intermediate 15-b] synthesized above was used instead of [Intermediate 14-c] used in the above Reaction Scheme 14-4 . (Yield: 28%)

MS (MALDI-TOF): m / z 693 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

130C, 134.9, 143.7, 144.3, 144.4, 150, 155.8, 161 [50C]

Synthesis Example 16. Synthesis of [Compound 16]

Synthesis Example 16-1) Synthesis of [Intermediate 16-a]

 [Reaction Scheme 16-1]

                                                 [Intermediate 16-a]

110 mL (331 mmol) of phenylmagnesium bromide (3.0 M in Et ₂ O) and 600 mL of tetrahydrofuran were added to a round bottom flask under a nitrogen stream, and the mixture was stirred at 45 ° C for about 30 minutes. 20.2 g (165 mmol) of the intermediate [1-a] obtained in the above Reaction Scheme-1 and 175 mL of tetrahydrofuran were added dropwise, followed by stirring for about 2 hours. After cooling to 0 占 폚, 43.6 g (199 mmol) of 4-bromobenzoyl chloride and 350 mL of tetrahydrofuran were added dropwise, and the mixture was heated to 45 占 폚 and stirred for about 2 hours. After cooling to 0 ° C, the ammonium chloride aqueous solution was added until it became slightly acidic. After stirring at room temperature, the resulting solid was filtered and rinsed with methanol to obtain 29g of [intermediate 16-a]. (Yield: 47%)

Synthesis Example 16-2) Synthesis of [Intermediate 16-b]

 [Reaction Scheme 16-2]

                                           [Intermediate 16-b]

Except that (5,8-dimethyl-9H-carbazol-3-yl) boronic acid was used instead of 4-bromo-9H-carbazole used in [Reaction Formula 1-5] Using the same method, 24 g of [intermediate 16-b] was obtained. (Yield: 85%)

Synthesis Example 16-3) Synthesis of intermediate [16-c]

 [Reaction Scheme 16-3]

                                               [Intermediate 16-c]

A round bottom flask was charged with 8.4 g (34 mmol) of the above 3-bromo-9H-carbazole, 11.7 g (37 mmol) of the intermediate 16-b prepared in the above Scheme 16-2, Pyridine 1.6 g (1 mmol) of palladium, 14.0 g (101 mmol) of potassium carbonate, 45 ml of 1,4-dioxane, 45 ml of toluene and 20 ml of distilled water were added and the mixture was refluxed overnight. When the reaction was completed, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, adsorbed on silica gel, and separated by column chromatography using dichloromethane and acetone to obtain 7.1 g of intermediate [16-c]. (Yield: 48%)

Synthesis Example 16-4) Synthesis of [Compound 16]

 [Reaction Scheme 16-4]

                                               [Compound 16]

6.6 g (18 mmol) of the compound represented by [Intermediate 16-a] obtained from 6.5 g (15 mmol) of the intermediate [16-c] obtained in the above reaction scheme [ 0.3 g (1 mmol) of tris (dibenzylidineacetone) dipalladium (0), 0.4 g (1 mmol) of tri-tertiary-butylphosphonium tetrafluoroborate and 0.4 g And 30 mL of ortho-xylene were added, and the mixture was refluxed and stirred for about 5 hours. The reaction solution was concentrated under reduced pressure, and methanol was added to the resulting crystals. The reaction mixture was separated by column chromatography and recrystallized from toluene and methanol to obtain 2.7 g of [Compound 16]. (Yield: 25%)

MS (MALDI-TOF): m / z 721 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.6, 114.1, 116.8, 118.4, 125.4, 145.4, 150, 155.8, 161 [52C]

Synthesis Example 17. Synthesis of [Compound 17]

Synthesis Example 17-1. Synthesis of [intermediate 17-a]

[Reaction Scheme 17-1]

                                                  [Intermediate 17-a]

14.3 g (589 mmol) of magnesium, 3 drops of iodine and 60 mL of tetrahydrofuran were added to a round bottom flask A under nitrogen flow at room temperature, and the mixture was stirred for about 10 minutes. After 125.9 g (540 mmol) of 4-bromobiphenyl and 240 mL of tetrahydrofuran were added dropwise to a flask containing water, the mixture was refluxed and stirred for about 2 hours. After 2 hours, the temperature was brought to room temperature. 30.0 g (246 mmol) of [Intermediate 8-a] synthesized in the above Reaction Scheme 8-1 and 150 mL of tetrahydrofuran were added to another round bottom flask B under nitrogen flow at room temperature and stirred. At the room temperature, the reaction solution prepared in the flask A was slowly added dropwise to the flask B filled with water. Thereafter, the mixture was stirred under reflux for about 1 hour. The temperature was adjusted to 0 占 폚, 34.8 g (368 mmol) of methyl chloroformate was added dropwise, and the mixture was refluxed with stirring for about 1 hour. The temperature was brought to 0 ° C, and the ammonium chloride aqueous solution was added until it became slightly acidic. The resulting solid was filtered and washed with water and heptane. 51 g of [intermediate 17-a] was obtained. (Yield 69%)

Synthesis Example 17-2) Synthesis of [Intermediate 17-b]

 [Reaction Scheme 17-2]

                                        [Intermediate 17-b]

Was obtained in the same manner as in Synthesis Example 1-3, except that [Intermediate 17-a] synthesized in [Reaction Scheme 17-1] was used instead of [Intermediate 1-b] used in [Reaction Scheme 1-3] 17.8 g of Intermediate 17-b]. (Yield: 33%)

Synthesis Example 17-3) Synthesis of [Intermediate 17-c]

 [Reaction Scheme 17-3]

                                                 [Intermediate 17-c]

Using intermediate 3-bromo-9H-carbazole and [Intermediate 17-b] synthesized in the above Reaction Scheme 17-2, 20.9 g of Intermediate 17-c was obtained in the same manner as in Synthesis Example 1-4 . (Yield: 71%)

Synthesis Example 17-4) Synthesis of [Compound 17]

[Reaction Scheme 17-4]

                                                [Compound 17]

The same procedure as in Synthesis Example 15-2 was repeated except that [Intermediate 17-c] synthesized in [Reaction Formula 17-3] was used instead of [Intermediate 15-a] used in the above Reaction Scheme 15-2 [Compound 17] was obtained in an amount of 5.6 g. (Yield: 27%)

MS (MALDI-TOF): m / z 693 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129C,

Synthesis Example 18. Synthesis of Compound 18

[Reaction Scheme 18-1]

[중간체 18-a]

[Intermediate 18-a]

[Reaction Scheme 18-2]

                                                 [Intermediate 18-b]

[Reaction Scheme 18-3]

                                                 [Compound 18]

(2-fluoro [1,1'-biphenyl] -4-) magnesium bromide (0.5M in ethanol) instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 1-2] [Intermediate 18-a] was obtained in the same manner as in Synthesis Examples 1-2 to 1-3 except that the compound of Synthesis Example 1-2 was used in Synthesis Example 1-3, [Intermediate 18-b] prepared by using [Intermediate 18-a] instead of [Intermediate 17-b] used in Intermediate 17- ] Was synthesized. (Yield: 25%)

MS (MALDI-TOF): m / z 711 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 144.9, 150.8, 129.3, 144.5, 50C]

Synthesis Example 19. Synthesis of Compound 19

(4-benzylphenyl) magnesium bromide instead of (2-fluoro [1,1'-biphenyl] -4-) magnesium bromide (0.5M in THF) used in [Synthesis Example 18-1] 6.4 g of [Compound 19] was synthesized in the same manner as in [Reaction Scheme 18-1] to [Reaction Scheme 18-3] in Synthesis Example 18 except that bromide (0.5 M in 2-methyltetrahydrofuran) was used . (Yield: 30%)

MS (MALDI-TOF): m / z 707 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129C,

Synthesis Example 20: Synthesis of Compound 20

Synthesis Example 20-1) Synthesis of [Intermediate 20-a]

 [Reaction formula 20-1]

                                                   [Intermediate 20-a]

Except that pentaduterobromobenzene was used instead of 4-bromobiphenyl used in [Reaction Scheme 17-1] in Synthesis Example 17-1), and dimethyl carbonate was used instead of methyl chloroformate, Synthesis Example 17-1 , 50 g of [intermediate 20-a] was obtained. (Yield: 73%)

Synthesis Example 20-2) Synthesis of [Compound 20]

Synthesis was carried out using the intermediate [20-a] synthesized in Synthesis Example 20-1 instead of the [Intermediate 17-a] used in the above Reaction Scheme 17-2 in Synthesis Example 17-3) 5.8 g (yield 35%) of [Compound 20] was obtained in the same manner as in Example 17-2) and Synthesis Example 17-4).

MS (MALDI-TOF): m / z 622 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

134, 134, 134, 136, 144, 144, 150, 155, 161, [44C], 166, 169,

Synthesis Example 21. Synthesis of [Compound 21]

Synthesis Example 21-1) Synthesis of [Intermediate 21-a]

                                                  [Intermediate 21-a]

After stirring 20.0 g (138.8 mmol) of 2-naphthol, 28.8 g (277.4 mmol) of sodium bisulfite and 160 mL of distilled water and 31.2 mL (166.4 mmol) of 4-bromophenylhydrazine at 120 ° C for 12 hours, distilled water The resulting solid was filtered under reduced pressure. The solid was added to the aqueous hydrochloric acid solution, and the mixture was stirred at 100 ° C for about 1 hour, extracted with dichloromethane, and washed with distilled water and aqueous sodium hydroxide solution. 9.2 g of [intermediate 21-a] was obtained by column chromatography. (Yield: 22.4%)

Synthesis Example 21-2) Synthesis of [Compound 21]

Was obtained in the same manner as in Synthesis Example 14, except that [Intermediate 21-a] prepared in Synthesis Example 21-1 was used instead of 3-bromo-9H-carbazole used in the above [Reaction Scheme 14-3] 4.5 g of [Compound 21] was obtained. (Yield: 33%)

MS (MALDI-TOF): m / z 668 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 143.3, 143.3, 144.3, 143.3, 143.7, 144.3, 149.8, 150, 155.8, 161, 169.1, 161.1, 161.1, 161.1, 161.1, 161.6, 47C]

Synthesis Example 22. Synthesis of [Compound 22]

Synthesis Example 22-1) Synthesis of intermediate [22-a]

 [Reaction formula 22-1]

                               [Intermediate 22-a] [Intermediate 22-b]

[Intermediate 12-a] was obtained by using 2-iodo-1-phenanthrene in place of 3-iodopyridine used in the above Reaction Scheme 13-2 to obtain [Intermediate 13 -b] instead of the compound [Intermediate 22-b].

[Reaction formula 22-2]

[화합물 22]

[Compound 22]

[Compound 22] was synthesized in the same manner as in [Intermediate 22-b] instead of [Intermediate 13-c] used in the above Reaction Scheme 13-4. (9.4 g, yield 37%).

MS (MALDI-TOF): m / z 793 [M] ^< ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.4, 119.8, 119.4, 119.8, 120.1, 121.4, 122.4, 123.2, 123.9, 125.5, 126.4, 126.6, 126.8, 127, 127.5, 127.6, 127.9, 128, 128.3, 128.7, 129, 129.2, 131.4, 138.8, 133.3, 133.3, 134, 134.8, 135.5, 138.3, 143.3, 143.7, 145.4, 150, 155.8, 161 [

Examples 1 to 22

Manufacture of organic light-emitting diodes

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the base pressure was adjusted to ¹ × 10 ^-6 torr. Then, an organic material was added to the ITO using DNTPD (700 Å), α-NPB (300 Å), [Compound 1] - the use as a host (90 wt%) and, to a dopant (piq) ₂ Ir (acac) deposition (300Å) provides a (10 wt%) _{and, Alq 3 (350Å), LiF} (5Å), Al ( 1,000 angstroms) in this order and measured at 0.4 mA.

The structures of DNTPD (700 Å), α-NPB, (piq) ₂ Ir (acac), Alq ₃ and [Compounds 1] to [Compound 22] are as follows.

[DNTPD] [[alpha] -NPB]

_{[(piq) 2 Ir (acac} )] [Alq 3]

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15]

[Compound 16] [Compound 17] [Compound 18]

[Compound 19] [Compound 20] [Compound 21]

[Compound 22]

Example 23

The compound used in the light emitting layer in the device structures of Examples 1 to 22 was selected as [Compound 1] and was made in the same manner except that [PTOEP] was used instead of [(piq) ₂ Ir (acac) ] Is as follows.

     [PTOEP]

Comparative Example 1

The organic light emitting device for the comparative example is the same as the host of the light emitting layer in the device structures of Examples 1 to 22 except that CBP which is widely used as a general phosphorescent host material instead of the organic light emitting compound prepared by the present invention is used The structure of the CBP is as follows.

          [CBP]

Comparative Examples 2 to 9

The organic light emitting devices for Comparative Examples 2 to 9 were fabricated in the same manner except that the following compounds [23] to [30] were used as a host instead of the compound prepared by the invention in the device structure of the above example, It is as follows.

[Compound 23] [Compound 24] [Compound 25]

 [Compound 26] [Compound 27] [Compound 28]

[Compound 29] [Compound 30]

Comparative Example 10

The organic light emitting device for Comparative Example 10 was fabricated in the same manner except that [Compound 23] was used in place of [Compound 1] in the device structure of Example 23. [

The voltage, the current density, the luminance, the color coordinate, and the lifetime of the organic light emitting device manufactured according to Examples 1 to 23 and Comparative Examples 1 to 10 were measured, and the results are shown in Table 1 below. T90 means the time required for the luminance to decrease from the initial luminance (5000 nits) to 90%.

2 shows results of life evaluation (T90 value) of Example 5, Comparative Example 2, and Comparative Example 6.

As can be seen from Table 1 and FIG. 2, the organic light emitting compound in which deuterium is substituted in the quinazoline structure according to the present invention has a much longer lifetime than that in the case where deuterium is not substituted, It is highly likely.

Claims (14)

An organic light-emitting compound represented by the following formula (A).
(A)

In the above formula (A)
The substituent Y is

ego,
R ₁ to R ₁₇ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a carbon having a substituted or unsubstituted heteroatom, O, N or S A heteroaryl group having 2 to 50 carbon atoms, a cyano group, a nitro group, and a halogen group, and may be connected with adjacent substituents to form a monocyclic or polycyclic ring of alicyclic or aromatic, , The carbon atom of the single aromatic ring or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O;
R ₁₈ is a substituent as defined above to R ₁ to R ₁₇ or Y;
Wherein x in the substituent Y is an integer of 1 to 4;
Wherein L ₁ and L ₂ are a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;
M and n are each independently an integer of 1 to 3, and when m and n are 2 or more, each L ₁ may be the same or different and each L ₂ may be the same or different from each other ;
The substituent of one of R ₅ to R ₈ and one of R ₁₀ to R ₁₃ is a single bond bonded to the linking group L 2, respectively;
The 'substituted' in the above 'substituted or unsubstituted' means a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, , An alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms , An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, Group, and an aryloxy group having 1 to 24 carbon atoms. The method according to claim 1,
Wherein the linking groups L ₁ and L ₂ are the same or different and each independently a single bond or any one selected from the following structural formulas 1 to 8.
[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural formula 5] [Structural formula 6] [Structural formula 7] [Structural formula 8]

In the substituents L ₁ and L ₂ , the carbon of the aromatic ring may be bonded to hydrogen or deuterium. The method according to claim 1,
In the above-mentioned formula (A), the substituents R ₁ to R ₁₈ are the same or different, and independently of one another, hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 heteroaryl group; And m and n are 1 or 2. 2. The organic electroluminescent compound according to claim 1, The method according to claim 1,
Wherein the substituents R ₁ to R ₁₇ are not connected to adjacent substituents to form a ring. The method according to claim 1,
Wherein the organic luminescent compound is represented by any one of formulas (1) to (24).

[Chemical Formula 1] < EMI ID =

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

[Chemical Formula 23]
The substituents R ₁ to R ₁₈ bonded to the polycyclic rings in the above formulas (1) to (24) are the same as those of R ₁ to R ₁₇ defined in the above item (1), and each of the substituents R _a and R _b Are the same as R ₁ to R ₁₇ defined in claim 1, and each p is independently an integer of 1 to 6, The method according to claim 4 or 5,
And x in the substituent Y is 3 or 4. The organic electroluminescent compound The method according to claim 4 or 5,
The linking groups L ₁ and L ₂ are the same or different and independently of each other,

or

, And m and n are each 1. The method according to claim 4 or 5,
R ₉ in said substituent Y is selected from the group consisting of deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 heteroaryl group; , ≪ / RTI >
Wherein the linking groups L ₁ and L ₂ are each a single bond. A first electrode;
A second electrode facing the first electrode; And
And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one organic electroluminescent compound selected from the group consisting of the organic electroluminescent compounds according to any one of claims 1 to 5. 10. The method of claim 9,
Wherein the organic layer comprises at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, and an electron injecting layer. 11. The method of claim 10,
An organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
Wherein the light emitting layer comprises a host and a dopant, and the organic light emitting compound is used as a host. 12. The method of claim 11,
Wherein the organic layer further comprises a hole blocking layer or an electron blocking layer. 11. The method of claim 10,
Wherein at least one layer selected from the respective layers is formed by a deposition process or a solution process. 10. The method of claim 9,
The organic light emitting device includes a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a single-color or white-colored flexible lighting device, characterized in that the organic light-emitting device

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